{"目录":[{"abstractInfo":"","abstractInfoCn":"","abstractInfoEn":"","articleNo":"20200300","authorCnList":[],"authorEnList":[],"authorList":[],"authors":"","authorsCn":"","authorsEn":"","categoryName":"目录","categoryNameCn":"目录","categoryNameEn":"Contents","citation":". 第41卷第3期目次. 催化学报, 2020, 41(3): 0-0.","citationCn":". 第41卷第3期目次. 催化学报, 2020, 41(3): 0-0.","citationEn":". Table of Contents for VOL.41 No.3. Chinese Journal of Catalysis, 2020, 41(3): 0-0.","doi":"","figContent":"","figList":[],"firstFig":"","fpage":"0","highCitedState":"","htmlCount":12,"htmlFile":"","id":"3b93a969-eab7-4ec5-9696-d22c6a2ffbcd","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"","keywordCn":"","keywordCnList":[],"keywordEn":"","keywordEnList":[],"keywordList":[],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"0","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":6,"pdfSize":3378.87,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"第41卷第3期目次","titleCn":"第41卷第3期目次","titleEn":"Table of Contents for VOL.41 No.3","viewCount":1008,"volume":"41","year":2020}],"综述":[{"abstractInfo":"褐煤是一个具有复杂结构的低等级煤炭，具有高水分、低发热值和低灰量.此外，褐煤是含有多种杂质的多孔材料，低分子量的有机化合物之间通过氢键结合.各种形式的褐煤含有水分灰硫、硫酸盐硫、黄铁矿硫和挥发物等杂质，现存在多种预处理方法，如10%盐酸预处理，HCl-HF预处理，氧化预处理、溶剂肿胀、溶剂萃取、微波处理、硝酸氧化、微生物脱硫等.<br/>褐煤直接液化可以通过加氢裂化，氧化裂解和烷醇分解反应从低级褐煤中产生各种产物.在催化加氢裂化中，铁基催化剂表现出最小活化且非常高效，而四氢化萘作为适当氢供体溶剂.此外，神华II技术采用悬浮床反应器和铁基催化剂，具有较高的褐煤液化能力.此外，在通过降解、水解、脱硫、脱氮、脱汞和氢化直接液化褐煤的过程中检测到各种有用的产物.液化产物可以分成不同的组分类别，例如芳环产物（前沥青质，沥青质和油）、氧化产物、环状产物和具有烃的烷醇分解产物.液化过程中涉及主要机制包括氧化，自由基形成，碳阳离子形成和烷醇分解.在氢和催化剂存在下褐煤的裂解通常遵循自由基机制褐煤液化的主要产物是单环产物，包括苯酚、甲苯、对伞花烃等环状产物.此外，氧化机理通常产生更多的氧化产物如羧酸等.直接煤液化工艺如IGOR工艺在固定床反应器中运行在290~330℃，容量为200t/d，而神华的DCL工艺在悬浮床反应器中使用5%~7%氢气转化92%煤.工业生产过程中使用的循环溶剂是200多种化合物的混合物，包括蜡，环烷烃，茚类，芘类和芳香族化合物等.然而，由于环数减少，一些芳香族化合物（联苯）在455℃的加氢处理过程中发生开环反应.为了解决这个问题，可使用在萘、菲、蒽作为氢供体溶剂中含有环烷环的芳族化合物来促进液化.<br/>本综述涵盖了各种褐煤和有效铁基催化剂及各种液化产物，尤其涵盖有希望的催化剂，并详细阐明所形成的化合物与裂解反应之间的相关性，且展示典型机理方案，但褐煤和生物质的共液化机制尚未完全阐明，因此需要进一步研究.本文有助于人们开发出更有效的褐煤（低级煤）液化过程催化体系.","abstractInfoCn":"褐煤是一个具有复杂结构的低等级煤炭，具有高水分、低发热值和低灰量.此外，褐煤是含有多种杂质的多孔材料，低分子量的有机化合物之间通过氢键结合.各种形式的褐煤含有水分灰硫、硫酸盐硫、黄铁矿硫和挥发物等杂质，现存在多种预处理方法，如10%盐酸预处理，HCl-HF预处理，氧化预处理、溶剂肿胀、溶剂萃取、微波处理、硝酸氧化、微生物脱硫等.<br/>褐煤直接液化可以通过加氢裂化，氧化裂解和烷醇分解反应从低级褐煤中产生各种产物.在催化加氢裂化中，铁基催化剂表现出最小活化且非常高效，而四氢化萘作为适当氢供体溶剂.此外，神华II技术采用悬浮床反应器和铁基催化剂，具有较高的褐煤液化能力.此外，在通过降解、水解、脱硫、脱氮、脱汞和氢化直接液化褐煤的过程中检测到各种有用的产物.液化产物可以分成不同的组分类别，例如芳环产物（前沥青质，沥青质和油）、氧化产物、环状产物和具有烃的烷醇分解产物.液化过程中涉及主要机制包括氧化，自由基形成，碳阳离子形成和烷醇分解.在氢和催化剂存在下褐煤的裂解通常遵循自由基机制褐煤液化的主要产物是单环产物，包括苯酚、甲苯、对伞花烃等环状产物.此外，氧化机理通常产生更多的氧化产物如羧酸等.直接煤液化工艺如IGOR工艺在固定床反应器中运行在290~330℃，容量为200t/d，而神华的DCL工艺在悬浮床反应器中使用5%~7%氢气转化92%煤.工业生产过程中使用的循环溶剂是200多种化合物的混合物，包括蜡，环烷烃，茚类，芘类和芳香族化合物等.然而，由于环数减少，一些芳香族化合物（联苯）在455℃的加氢处理过程中发生开环反应.为了解决这个问题，可使用在萘、菲、蒽作为氢供体溶剂中含有环烷环的芳族化合物来促进液化.<br/>本综述涵盖了各种褐煤和有效铁基催化剂及各种液化产物，尤其涵盖有希望的催化剂，并详细阐明所形成的化合物与裂解反应之间的相关性，且展示典型机理方案，但褐煤和生物质的共液化机制尚未完全阐明，因此需要进一步研究.本文有助于人们开发出更有效的褐煤（低级煤）液化过程催化体系.","abstractInfoEn":"With the pressure owing to fossil oil shortages, direct liquefaction is attracting significant attention as a highly efficient and low-cost technique for lignite-to-fuel conversion. In this review, the diverse catalytic systems and mechanisms involved in lignite liquefaction are reviewed. The top five global technologies include IGOR (Germany), HTI (the USA), FFI (Russia), NEDOL (Japan), and Shenhua (China), which have already been applied in industrial scales. Among the five technologies, Shenhua (China) outputs as high as 3000 t/d using a suspended bed reactor, iron-based catalyst, and rehydrogenated recycled solvents (paraffin, aromatics, etc.). The conversion of lignite is quite difficult due to the presence of ionic bond and non-covalent interactions, such as hydrogen bonding; thus, it is well recognized that the catalytic liquefaction under relatively mild conditions is more feasible than non-catalytic liquefaction. Iron-based catalysts can efficiently facilitate the lignite liquefaction and promote the lignite cracking aided by a hydrogen-donor solvent; thus, they have attracted interest from researchers globally. The different liquefaction mechanisms of lignite including free radical, oxidation, alkanolysis, and hydrogenation lead to the corresponding products:preasphaltene and asphaltene, mixed carboxylic acids, mixed esters and ethers, and cyclic compounds, respectively. Therefore, the catalytic system of the lignite liquefaction process would be accordingly optimized and modified to afford different products.","articleNo":"20200301","authorCnList":["林凯","  赵晨"],"authorEnList":["Arif Ali","  Chen Zhao"],"authorList":["林凯","  赵晨"],"authors":"林凯,  赵晨","authorsCn":"林凯,  赵晨","authorsEn":"Arif Ali,  Chen Zhao","categoryName":"综述","categoryNameCn":"综述","categoryNameEn":"Reviews","citation":"林凯,  赵晨. 褐煤直接液化技术研究进展. 催化学报, 2020, 41(3): 375-389. doi: S1872-2067(19)63492-3.","citationCn":"林凯,  赵晨. 褐煤直接液化技术研究进展. 催化学报, 2020, 41(3): 375-389. doi: S1872-2067(19)63492-3.","citationEn":"林凯,  赵晨. Direct liquefaction techniques on lignite coal: A review. Chinese Journal of Catalysis, 2020, 41(3): 375-389. doi: S1872-2067(19)63492-3.","doi":"S1872-2067(19)63492-3","figContent":"","figList":[],"firstFig":"","fpage":"375","highCitedState":"","htmlCount":130,"htmlFile":"","id":"c7802053-91d5-42d7-9386-a3e05e366e56","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"直接液化, 催化体系, 液化机理, 褐煤, 铁基催化剂","keywordCn":"直接液化, 催化体系, 液化机理, 褐煤, 铁基催化剂","keywordCnList":["直接液化"," 催化体系"," 液化机理"," 褐煤"," 铁基催化剂"],"keywordEn":"Direct liquefaction, Catalytic system, Mechanism of liquefaction, Lignite coal, Fe-based catalyst","keywordEnList":["Direct liquefaction"," Catalytic system"," Mechanism of liquefaction"," Lignite coal"," Fe-based catalyst"],"keywordList":["直接液化"," 催化体系"," 液化机理"," 褐煤"," 铁基催化剂"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"389","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":13,"pdfSize":934.24,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"褐煤直接液化技术研究进展","titleCn":"褐煤直接液化技术研究进展","titleEn":"Direct liquefaction techniques on lignite coal: A review","viewCount":1184,"volume":"41","year":2020},{"abstractInfo":"金属-空气二次电池在可再生电能的存储和转换方面具有广阔的应用前景.在金属-空气二次电池的空气侧，放电时发生氧还原反应（ORR），充电时发生氧析出反应（OER）.然而，ORR和OER反应的动力学过程缓慢，因此限制了金属-空气二次电池的实际应用.因此，发展高性能ORR和OER电催化剂对金属-空气二次电池的发展尤为重要.目前，大多数的研究集中在ORR或OER的单功能电催化剂上，而关于双功能电催化剂的研究和综述相对较少.两个反应均具有较高的过电位和较缓慢的动力学过程，而且充电过程的高电压会导致ORR催化剂失活，反之亦然.因此，开发针对这两个反应均具有高活性和高稳定性的双功能电催化剂极具挑战性.近年来，研究者对具有低成本和高性能双功能电催化剂进行了探索.这些双功能电催化剂包括碳基材料，过渡金属材料和复合材料.双功能电催化剂可以通过提高本征活性和表观活性两种策略来提高其整体的活性.其中，本征活性与晶体结构和电子结构密切相关，即可以通过调节晶体结构和电子结构来提高其本征活性.例如，可以改变金属-氧键的强度、氧空位浓度等来调变电催化活性.在碳基材料中掺杂杂原子可以改变碳的电荷密度分布，从而实现对电催化活性的提高.此外，其表观活性还可以通过改变形貌并利用协同作用来改善.构建特殊微纳结构是提高电催化活性的最常用策略之一.在这种情况下，电催化剂具有较高的比表面积，大量的活性位点和良好的电子传导性.同时，复合电催化剂组分之间在加速电催化过程中的协同作用不容忽视.本文将聚焦双功能电催化剂的微纳结构设计，并简要讨论了纳米结构的精细调控和对反应机理的认识.<br/>我们认为，未来的工作应继续加强ORR和OER的新型双功能电催化剂的开发，发展更多的合成方法对电催化剂的微纳结构进行调变，并对反应机理进行更深入的研究.首先，通过对结构的精细调变提高电催化剂的本征活性和表观活性.此外，通过多种原位表征方法揭示反应机理，这有助于电催化剂的设计和催化活性的进一步提升.基于此，开发出性能优异的双功能电催化剂以加快用于存储和转换可再生能源的可充电金属-空气二次电池的商业化进程.","abstractInfoCn":"金属-空气二次电池在可再生电能的存储和转换方面具有广阔的应用前景.在金属-空气二次电池的空气侧，放电时发生氧还原反应（ORR），充电时发生氧析出反应（OER）.然而，ORR和OER反应的动力学过程缓慢，因此限制了金属-空气二次电池的实际应用.因此，发展高性能ORR和OER电催化剂对金属-空气二次电池的发展尤为重要.目前，大多数的研究集中在ORR或OER的单功能电催化剂上，而关于双功能电催化剂的研究和综述相对较少.两个反应均具有较高的过电位和较缓慢的动力学过程，而且充电过程的高电压会导致ORR催化剂失活，反之亦然.因此，开发针对这两个反应均具有高活性和高稳定性的双功能电催化剂极具挑战性.近年来，研究者对具有低成本和高性能双功能电催化剂进行了探索.这些双功能电催化剂包括碳基材料，过渡金属材料和复合材料.双功能电催化剂可以通过提高本征活性和表观活性两种策略来提高其整体的活性.其中，本征活性与晶体结构和电子结构密切相关，即可以通过调节晶体结构和电子结构来提高其本征活性.例如，可以改变金属-氧键的强度、氧空位浓度等来调变电催化活性.在碳基材料中掺杂杂原子可以改变碳的电荷密度分布，从而实现对电催化活性的提高.此外，其表观活性还可以通过改变形貌并利用协同作用来改善.构建特殊微纳结构是提高电催化活性的最常用策略之一.在这种情况下，电催化剂具有较高的比表面积，大量的活性位点和良好的电子传导性.同时，复合电催化剂组分之间在加速电催化过程中的协同作用不容忽视.本文将聚焦双功能电催化剂的微纳结构设计，并简要讨论了纳米结构的精细调控和对反应机理的认识.<br/>我们认为，未来的工作应继续加强ORR和OER的新型双功能电催化剂的开发，发展更多的合成方法对电催化剂的微纳结构进行调变，并对反应机理进行更深入的研究.首先，通过对结构的精细调变提高电催化剂的本征活性和表观活性.此外，通过多种原位表征方法揭示反应机理，这有助于电催化剂的设计和催化活性的进一步提升.基于此，开发出性能优异的双功能电催化剂以加快用于存储和转换可再生能源的可充电金属-空气二次电池的商业化进程.","abstractInfoEn":"Water-based rechargeable metal-air batteries play an important role in the storage and conversion of renewable electric energy. However, the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have limited the practical application of rechargeable metal-air batteries. Most of reviews were focused on single functional electrocatalysts while few on bifunctional electrocatalysts. It is indispensable but challenging to design a bifunctional electrocatalyst that is active and stable to the two reactions. Recently, attempts to develop high active bifunctional electrocatalysts for both ORR and OER increase rapidly. Much work is focused on the micro-nano design of advanced structures to improve the performance of bifunctional electrocatalyst. Transition-metal materials, carbon materials and composite materials, and the methods developed to prepare micro-nano structures, such as electrochemical methods, chemical vapor deposition, hydrothermal methods and template methods are reported in literatures. Additionally, many strategies, such as adjustments of electronic structures, oxygen defects, metal-oxygen bonds, interfacial strain, nano composites, heteroatom doping etc., have been used extensively to design bifunctional electrocatalysts. To well understand the achievements in the recent literatures, this review focuses on the micro-nano structural design of materials, and the related methods and strategies are classed into two groups for the improvement of intrinsic and apparent activities. The fine adjustment of nano structures and an in-depth understanding of the reaction mechanism are also discussed briefly.","articleNo":"20200302","authorCnList":["石芳","  朱雪峰","  杨维慎"],"authorEnList":["Fang Shi","  Xuefeng Zhu","  Weishen Yang"],"authorList":["石芳","  朱雪峰","  杨维慎"],"authors":"石芳,  朱雪峰,  杨维慎","authorsCn":"石芳,  朱雪峰,  杨维慎","authorsEn":"Fang Shi,  Xuefeng Zhu,  Weishen Yang","categoryName":"综述","categoryNameCn":"综述","categoryNameEn":"Reviews","citation":"石芳,  朱雪峰,  杨维慎. 金属-空气电池中双功能电催化剂微纳结构设计. 催化学报, 2020, 41(3): 390-403. doi: S1872-2067(19)63514-X.","citationCn":"石芳,  朱雪峰,  杨维慎. 金属-空气电池中双功能电催化剂微纳结构设计. 催化学报, 2020, 41(3): 390-403. doi: S1872-2067(19)63514-X.","citationEn":"石芳,  朱雪峰,  杨维慎. Micro-nanostructural designs of bifunctional electrocatalysts for metal-air batteries. Chinese Journal of Catalysis, 2020, 41(3): 390-403. doi: S1872-2067(19)63514-X.","doi":"S1872-2067(19)63514-X","figContent":"","figList":[],"firstFig":"","fpage":"390","highCitedState":"","htmlCount":143,"htmlFile":"","id":"97b2a20d-532d-422a-8fc9-2f4d7553bec3","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"氧还原反应, 氧析出反应, 可逆金属-空气电池, 双功能电催化剂, 微纳结构","keywordCn":"氧还原反应, 氧析出反应, 可逆金属-空气电池, 双功能电催化剂, 微纳结构","keywordCnList":["氧还原反应"," 氧析出反应"," 可逆金属-空气电池"," 双功能电催化剂"," 微纳结构"],"keywordEn":"Oxygen reduction reaction, Oxygen evolution reaction, Rechargeable metal-air batteries, Bifunctional electrocatalysts, Micro-nano structure","keywordEnList":["Oxygen reduction reaction"," Oxygen evolution reaction"," Rechargeable metal-air batteries"," Bifunctional electrocatalysts"," Micro-nano structure"],"keywordList":["氧还原反应"," 氧析出反应"," 可逆金属-空气电池"," 双功能电催化剂"," 微纳结构"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"403","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":21,"pdfSize":3487.98,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"金属-空气电池中双功能电催化剂微纳结构设计","titleCn":"金属-空气电池中双功能电催化剂微纳结构设计","titleEn":"Micro-nanostructural designs of bifunctional electrocatalysts for metal-air batteries","viewCount":1263,"volume":"41","year":2020}],"论文":[{"abstractInfo":"糠醇是一种重要的高附加值化学品，目前工业上由含半纤维素或木聚糖的生物质原料经过酸脱水先制备糠醛，糠醛再进一步加氢制备糠醇.在实际生产中，这两步反应分别在不同的设备中进行，增加了分离纯化和运输成本目前也很少有研究偶联这两步反应.本工作中，我们制备了一种多功能介孔Cu/SBA-15-SO<sub>3<\/sub>H催化剂用于一锅法一步转化木糖到糠醛，并且通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、傅里叶变换红外光谱（FT-IR）、热重分析（TGA）、电感耦合等离子体发射光谱（ICP-OES）、X射线荧光（XRF）、NH<sub>3<\/sub>-程序升温脱附（NH<sub>3<\/sub>-TPD）和N<sub>2<\/sub>物理吸附等表征检测了负载的酸和金属位点的可用性以及催化剂的物理化学性质，优化了反应温度、氢气压力、反应时间和溶剂体系等反应条件，研究了酸和金属位点的比例以及介孔尺寸对合成糠醇的影响.<br/>XRD表征和TEM及HRTEM图像均表明，在负载了磺酸和Cu之后，均会一定程度上破坏SBA-15的形貌，但是依然可以保持原本的有序介孔结构.XPS表明还原后的Cu主要以+1价的形式存在，也有少量的0价和+2价.红外光谱表明磺酸基团和SBA-15载体以共价键形式紧密结合.氮气吸脱附和相关的BET和BJH计算表明，我们的原位制备方法相比于传统浸渍法，磺酸位点的含量提高了7倍以上.<br/>通过对反应条件的优化，该体系在140℃和4MPaH<sub>2<\/sub>下可以实现62.6%的糠醇收率.过高的温度会引起产物过度加氢生成2-甲基呋喃，而过高的压力会导致原料过度加氢生成木糖醇.合适的溶剂也是反应的关键因素，使用1：3的水/丁醇双相体系，一方面可以有效促进糖的溶解，另一方面可以有效萃取产物，保证了反应的碳平衡.<br/>在对催化剂的筛选中发现，单独的SBA-15几乎无催化活性，Cu/SBA-15主要催化木糖加氢生成木糖醇，SBA-15-SO<sub>3<\/sub>H主要催化木糖脱水生成糠醛，而物理混合的Cu/SBA-15和SBA-15-SO<sub>3<\/sub>H的效率远不如双功能Cu/SBA-15-SO<sub>3<\/sub>H催化剂.通过调节磺酸含量和探究产物时间曲线发现，提高酸性位点可以促进木糖转化，但是过多的酸性位点会导致结焦，降低糠醇收率.共同存在的磺酸酸性位点和铜金属位点保持平衡，协同催化串联反应进行.通过调节SBA-15的孔道结构发现，4nm的孔道最适合反应进行，孔道过大会降低反应的整体碳收率和糠醇收率.<br/>本催化体系实现了从木糖一锅多步法制糠醇，并对催化剂的构效关系进行了研究，对反应条件进行了系统的优化，有希望实际应用到糠醇生产中.","abstractInfoCn":"糠醇是一种重要的高附加值化学品，目前工业上由含半纤维素或木聚糖的生物质原料经过酸脱水先制备糠醛，糠醛再进一步加氢制备糠醇.在实际生产中，这两步反应分别在不同的设备中进行，增加了分离纯化和运输成本目前也很少有研究偶联这两步反应.本工作中，我们制备了一种多功能介孔Cu/SBA-15-SO<sub>3<\/sub>H催化剂用于一锅法一步转化木糖到糠醛，并且通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、傅里叶变换红外光谱（FT-IR）、热重分析（TGA）、电感耦合等离子体发射光谱（ICP-OES）、X射线荧光（XRF）、NH<sub>3<\/sub>-程序升温脱附（NH<sub>3<\/sub>-TPD）和N<sub>2<\/sub>物理吸附等表征检测了负载的酸和金属位点的可用性以及催化剂的物理化学性质，优化了反应温度、氢气压力、反应时间和溶剂体系等反应条件，研究了酸和金属位点的比例以及介孔尺寸对合成糠醇的影响.<br/>XRD表征和TEM及HRTEM图像均表明，在负载了磺酸和Cu之后，均会一定程度上破坏SBA-15的形貌，但是依然可以保持原本的有序介孔结构.XPS表明还原后的Cu主要以+1价的形式存在，也有少量的0价和+2价.红外光谱表明磺酸基团和SBA-15载体以共价键形式紧密结合.氮气吸脱附和相关的BET和BJH计算表明，我们的原位制备方法相比于传统浸渍法，磺酸位点的含量提高了7倍以上.<br/>通过对反应条件的优化，该体系在140℃和4 MPa H<sub>2<\/sub>下可以实现62.6%的糠醇收率.过高的温度会引起产物过度加氢生成2-甲基呋喃，而过高的压力会导致原料过度加氢生成木糖醇.合适的溶剂也是反应的关键因素，使用1：3的水/丁醇双相体系，一方面可以有效促进糖的溶解，另一方面可以有效萃取产物，保证了反应的碳平衡.<br/>在对催化剂的筛选中发现，单独的SBA-15几乎无催化活性，Cu/SBA-15主要催化木糖加氢生成木糖醇，SBA-15-SO<sub>3<\/sub>H主要催化木糖脱水生成糠醛，而物理混合的Cu/SBA-15和SBA-15-SO<sub>3<\/sub>H的效率远不如双功能Cu/SBA-15-SO<sub>3<\/sub>H催化剂.通过调节磺酸含量和探究产物时间曲线发现，提高酸性位点可以促进木糖转化，但是过多的酸性位点会导致结焦，降低糠醇收率.共同存在的磺酸酸性位点和铜金属位点保持平衡，协同催化串联反应进行.通过调节SBA-15的孔道结构发现，4nm的孔道最适合反应进行，孔道过大会降低反应的整体碳收率和糠醇收率.<br/>本催化体系实现了从木糖一锅多步法制糠醇，并对催化剂的构效关系进行了研究，对反应条件进行了系统的优化，有希望实际应用到糠醇生产中.","abstractInfoEn":"The conversion of hemicellulose-derived xylose to furfuryl alcohol is a practical procedure for producing value-added chemicals from biomass. In this study, a bifunctional Cu/SBA-15-SO<sub>3<\/sub>H catalyst was employed for the one-pot catalytic conversion of xylose to furfuryl alcohol with a yield of up to 62.6% at the optimized conditions of 140℃, 4 MPa, and for 6 h in a biphasic water/<i>n<\/i>-butanol solvent. A high reaction temperature resulted in further hydrogenation to 2-methyl furan, while a high hydrogen pressure led to a side hydrogenation reaction to xylitol. The biphasic solvent allowed xylose solvation as well as furfuryl product extraction. The acidic -SO<sub>3<\/sub>H sites and Cu sites co-existed, maintained a balance, and cooperatively catalyzed the cascade conversion. Excessive acidic sites and large pores could promote the xylose conversion, although a low furfuryl alcohol yield was obtained. This catalytic system could be potentially applied to the one-pot synthesis of furfuryl alcohol from hemicellulose-derived xylose.","articleNo":"20200303","authorCnList":["邓天宇","  许光月","  傅尧"],"authorEnList":["Tianyu Deng","  Guangyue Xu","  Yao Fu"],"authorList":["邓天宇","  许光月","  傅尧"],"authors":"邓天宇,  许光月,  傅尧","authorsCn":"邓天宇,  许光月,  傅尧","authorsEn":"Tianyu Deng,  Guangyue Xu,  Yao Fu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"邓天宇,  许光月,  傅尧. Cu/SBA-15-SO<sub>3<\/sub>H催化木糖一锅转化制备糠醇. 催化学报, 2020, 41(3): 404-414. doi: S1872-2067(19)63505-9.","citationCn":"邓天宇,  许光月,  傅尧. Cu/SBA-15-SO<sub>3<\/sub>H催化木糖一锅转化制备糠醇. 催化学报, 2020, 41(3): 404-414. doi: S1872-2067(19)63505-9.","citationEn":"邓天宇,  许光月,  傅尧. One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO<sub>3<\/sub>H catalyst. Chinese Journal of Catalysis, 2020, 41(3): 404-414. doi: S1872-2067(19)63505-9.","doi":"S1872-2067(19)63505-9","figContent":"","figList":[],"firstFig":"","fpage":"404","highCitedState":"","htmlCount":76,"htmlFile":"","id":"e4586467-57fd-4c7d-9852-f1678319b11b","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"生物质, 糠醇, 多相催化, 一锅法合成, 木糖","keywordCn":"生物质, 糠醇, 多相催化, 一锅法合成, 木糖","keywordCnList":["生物质"," 糠醇"," 多相催化"," 一锅法合成"," 木糖"],"keywordEn":"Biomass, Furfuryl alcohol, Heterogeneous catalysis, One-pot synthesis, Xylose","keywordEnList":["Biomass"," Furfuryl alcohol"," Heterogeneous catalysis"," One-pot synthesis"," Xylose"],"keywordList":["生物质"," 糠醇"," 多相催化"," 一锅法合成"," 木糖"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"414","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":7,"pdfSize":1369.96,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"Cu/SBA-15-SO<sub>3<\/sub>H催化木糖一锅转化制备糠醇","titleCn":"Cu/SBA-15-SO<sub>3<\/sub>H催化木糖一锅转化制备糠醇","titleEn":"One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO<sub>3<\/sub>H catalyst","viewCount":1051,"volume":"41","year":2020},{"abstractInfo":"作为便携式电子设备的动力源，直接甲酸燃料电池（DFAFC）具有燃料跨界范围小、电动势大、甲酸无毒、低温下功率密度大等优点，因而引起了人们的极大兴趣.DFAFC商业化的主要挑战之一是阳极电催化剂材料的高成本和低CO耐受性.阳极通常需要高负载的贵金属电催化剂（Pt或Pd）氧化甲酸（HCOOH）以获得所需的电能.完全电氧化甲酸在Pt和Pd表面上会产生强吸附的CO，从而降低了Pt或Pd催化剂的活性.Pt和Pd储量少且价格昂贵，减少Pt和Pd含量且保持催化性能的燃料电池催化剂一直是研究者的奋斗目标.<br/>本文用周期性密度泛函理论（DFT）系统地研究了WC负载的单分子层Pd（Pd/WC（0001））催化剂对甲酸的分解机理，这可为所需的反应路径设计、筛选催化剂提供指导.<br/>Trans-HCOOH通过C-H，O-H，C-O键的活化发生分解.关于吸附，确定了可能反应中间体的最稳定吸附构型.trans-HCOOH，HCOO，mHCOO，cis-COOH，trans-COOH，CO，H<sub>2<\/sub>O，OH和H的吸附过程是化学吸附，而cis-HCOOH和CO<sub>2<\/sub>与Pd/WC（0001）表面的相互作用较弱，是物理吸附.此外，提出了trans-HCOOH分解的不同途径来探索分解机理.trans-HCOOH中O-H，C-H和C-O键的活化能垒分别为0.61，0.77和1.05eV，O-H键断裂的能垒最小，则trans-HCOOH优先通过O-H键断裂生成HCOO.双齿HCOO是HCOOH分解的主要中间体，它可以转变为单齿HCOO，这条路线生成CO<sub>2<\/sub>的能垒比双齿HCOO的低0.04eV.CO<sub>2<\/sub>是HCOO主要解离产物，这一步是总反应的决速步骤.对于cis-COOH和trans-COOH，CO是其主要解离产物.此外，trans-HCOOH也能直接生成CO，但克服的能垒较大.在Pd/WC（0001）表面上分解trans-HCOOH的最有利途径是HCOOH→HCOO→CO<sub>2<\/sub>，其中HCOO脱氢形成CO<sub>2<\/sub>的步骤是速率决定步骤.<br/>本文提供了HCOOH在Pd/WC（0001）表面上分解的活性中间体、能垒和机理的推测，CO形成主要是通过cis-COOH、trans-COOH及HCO的分解，CO<sub>2<\/sub>的形成主要是通过HCOO的分解，CO<sub>2<\/sub>占主导.该结论与Pd（111）面上甲酸分解结果一致，说明WC作为Pd载体没有改变Pd对甲酸的催化性能，但降低了Pd的使用量.<br/>综上，本文阐明了WC负载单分子层Pd催化剂上甲酸催化分解机理，得出甲酸分解的最佳反应路径，为直接甲酸燃料电池设计低贵金属含量、高活性的负载型Pd催化剂提供了理论指导；可用于预测不同载体负载Pd催化剂的性能，大大减少实验成本，以验证提出的实验假设.","abstractInfoCn":"作为便携式电子设备的动力源，直接甲酸燃料电池（DFAFC）具有燃料跨界范围小、电动势大、甲酸无毒、低温下功率密度大等优点，因而引起了人们的极大兴趣.DFAFC商业化的主要挑战之一是阳极电催化剂材料的高成本和低CO耐受性.阳极通常需要高负载的贵金属电催化剂（Pt或Pd）氧化甲酸（HCOOH）以获得所需的电能.完全电氧化甲酸在Pt和Pd表面上会产生强吸附的CO，从而降低了Pt或Pd催化剂的活性.Pt和Pd储量少且价格昂贵，减少Pt和Pd含量且保持催化性能的燃料电池催化剂一直是研究者的奋斗目标.<br/>本文用周期性密度泛函理论（DFT）系统地研究了WC负载的单分子层Pd（Pd/WC（0001））催化剂对甲酸的分解机理，这可为所需的反应路径设计、筛选催化剂提供指导.<br/>Trans-HCOOH通过C-H，O-H，C-O键的活化发生分解.关于吸附，确定了可能反应中间体的最稳定吸附构型.trans-HCOOH，HCOO，mHCOO，cis-COOH，trans-COOH，CO，H<sub>2<\/sub>O，OH和H的吸附过程是化学吸附，而cis-HCOOH和CO<sub>2<\/sub>与Pd/WC（0001）表面的相互作用较弱，是物理吸附.此外，提出了trans-HCOOH分解的不同途径来探索分解机理.trans-HCOOH中O-H，C-H和C-O键的活化能垒分别为0.61，0.77和1.05eV，O-H键断裂的能垒最小，则trans-HCOOH优先通过O-H键断裂生成HCOO.双齿HCOO是HCOOH分解的主要中间体，它可以转变为单齿HCOO，这条路线生成CO<sub>2<\/sub>的能垒比双齿HCOO的低0.04eV.CO<sub>2<\/sub>是HCOO主要解离产物，这一步是总反应的决速步骤.对于cis-COOH和trans-COOH，CO是其主要解离产物.此外，trans-HCOOH也能直接生成CO，但克服的能垒较大.在Pd/WC（0001）表面上分解trans-HCOOH的最有利途径是HCOOH→HCOO→CO<sub>2<\/sub>，其中HCOO脱氢形成CO<sub>2<\/sub>的步骤是速率决定步骤.<br/>本文提供了HCOOH在Pd/WC（0001）表面上分解的活性中间体、能垒和机理的推测，CO形成主要是通过cis-COOH、trans-COOH及HCO的分解，CO<sub>2<\/sub>的形成主要是通过HCOO的分解，CO<sub>2<\/sub>占主导.该结论与Pd（111）面上甲酸分解结果一致，说明WC作为Pd载体没有改变Pd对甲酸的催化性能，但降低了Pd的使用量.<br/>综上，本文阐明了WC负载单分子层Pd催化剂上甲酸催化分解机理，得出甲酸分解的最佳反应路径，为直接甲酸燃料电池设计低贵金属含量、高活性的负载型Pd催化剂提供了理论指导；可用于预测不同载体负载Pd催化剂的性能，大大减少实验成本，以验证提出的实验假设.","abstractInfoEn":"In pursuit of low-cost direct formic acid fuel cells, tungsten carbide (WC) supported Pd catalyst is considered as an ideal candidate for efficient decomposition of formic acid due to low Pd utilization and excellent performance. Herein, different adsorption configurations and active sites of the intermediates, involved in the HCOOH decomposition, on WC(0001)-supported Pd monolayer (Pd/WC(0001)) surface investigated by using density functional theory. The results reveal that trans-HCOOH, HCOO, cis-COOH, trans-COOH, HCO, CO, H<sub>2<\/sub>O, OH and H exhibit chemisorption on Pd/WC(0001) surface, whereas cis-HCOOH and CO<sub>2<\/sub> exhibit weak interactions with Pd/WC(0001) surface. In addition, the minimum energy pathways of HCOOH decomposition are analyzed to generate CO and CO<sub>2<\/sub> due to the fracture of C-H, H-O and C-O bonds. The adsorbed HCOOH, HCOO, mHCOO, cis-COOH and trans-COOH configurations exhibit dissociation rather than desorption. CO formation occurs through the decomposition of cis-COOH, trans-COOH and HCO, whereas the CO<sub>2<\/sub> formation happens due to the decomposition of HCOO. It is found that the most favorable pathway for HCOOH decomposition on Pd/WC(0001) surface is HCOOH→HCOO→CO<sub>2<\/sub>, where the formation of CO<sub>2<\/sub> from HCOO dehydrogenation determines the reaction rate. Overall, CO<sub>2<\/sub> is the most dominant product of HCOOH decomposition on Pd/WC(0001) surface. The presence of WC, as monolayer Pd carrier, does not alter the catalytic behavior of Pd and significantly reduces the Pd utilization.","articleNo":"20200304","authorCnList":["张金花","  佘远斌"],"authorEnList":["Jinhua Zhang","  Yuanbin She"],"authorList":["张金花","  佘远斌"],"authors":"张金花,  佘远斌","authorsCn":"张金花,  佘远斌","authorsEn":"Jinhua Zhang,  Yuanbin She","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"张金花,  佘远斌. DFT法研究HCOOH在Pd/WC(0001)上的分解机理. 催化学报, 2020, 41(3): 415-425. doi: S1872-2067(19)63463-7.","citationCn":"张金花,  佘远斌. DFT法研究HCOOH在Pd/WC(0001)上的分解机理. 催化学报, 2020, 41(3): 415-425. doi: S1872-2067(19)63463-7.","citationEn":"张金花,  佘远斌. Unveiling the decomposition mechanism of formic acid on Pd/WC(0001) surface by using density function theory. Chinese Journal of Catalysis, 2020, 41(3): 415-425. doi: S1872-2067(19)63463-7.","doi":"S1872-2067(19)63463-7","figContent":"","figList":[],"firstFig":"","fpage":"415","highCitedState":"","htmlCount":238,"htmlFile":"","id":"0d6ccfd9-fd24-4957-b32b-51797cf92aff","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"密度泛函理论, 甲酸, 直接甲酸燃料电池, WC(0001)负载单分子层Pd, 分解机理","keywordCn":"密度泛函理论, 甲酸, 直接甲酸燃料电池, WC(0001)负载单分子层Pd, 分解机理","keywordCnList":["密度泛函理论"," 甲酸"," 直接甲酸燃料电池"," WC(0001)负载单分子层Pd"," 分解机理"],"keywordEn":"Density functional theory, Formic acid, Direct formic acid fuel cells, WC(0001)-supported Pd monolayer, Decomposition mechanism","keywordEnList":["Density functional theory"," Formic acid"," Direct formic acid fuel cells"," WC(0001)-supported Pd monolayer"," Decomposition mechanism"],"keywordList":["密度泛函理论"," 甲酸"," 直接甲酸燃料电池"," WC(0001)负载单分子层Pd"," 分解机理"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"425","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":20,"pdfSize":1986.98,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"DFT法研究HCOOH在Pd/WC(0001)上的分解机理","titleCn":"DFT法研究HCOOH在Pd/WC(0001)上的分解机理","titleEn":"Unveiling the decomposition mechanism of formic acid on Pd/WC(0001) surface by using density function theory","viewCount":1490,"volume":"41","year":2020},{"abstractInfo":"半导体光催化技术是目前最有前景的绿色化学技术，可通过利用太阳光降解污染物或制氢.作为有潜力的半导体催化剂，钼酸铋具有合适的带隙（2.58eV）.但是，由于低的量子产量，钼酸铋的光催化性能并不理想.为了提高钼酸铋的光催化性能，研究者多考虑采取构造异质结的方式.石墨相氮化碳（g-C<sub>3<\/sub>N<sub>4<\/sub>）能带位置合适，与多种光催化半导体能带匹配，是构造异质结的常用选择.因此，本文选用g-C<sub>3<\/sub>N<sub>4<\/sub>与钼酸铋复合，构造异质结结构.为了进一步提高光催化性能，多采用负载贵金属（Pt，Au和Pd）作为助催化剂，利用贵金属特有的等离子共振效应，增加光吸收，促进载流子分离，但贵金属价格昂贵.Bi金属单质价格便宜，具备等效的等离子共振效应，是理想的贵金属替代物.钼酸铋可以采取原位还原的方式还原出Bi单质，构造更紧密的界面结构，更有利于载流子传输.Bi的等离子共振效应可以有效提高材料的光吸收能力和光生载流子分离率.<br/>本文采用溶剂热和原位还原方法成功合成了一种新型三元异质结结构g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi（CN/BMO/Bi）空心微球.结果显示，三元异质结结构的最佳配比为0.4CN/BMO/9Bi，该样品表现出最好的光催化降解罗丹明B效率，是纯钼酸铋的9倍.通过计算DRS和XPS的价带数据，0.4CN/BMO/9Bi是一种Z字型异质结.牺牲试剂实验也提供了Z字型异质结的有力证据，测试显示超氧自由基&#183;O<sup>2-<\/sup>（在-0.33eV）是光催化降解的主要基团.但是，钼酸铋的导带位置低于-0.33eV，g-C<sub>3<\/sub>N<sub>4<\/sub>的导带高于-0.33eV，因此g-C<sub>3<\/sub>N<sub>4<\/sub>的导带是唯一的反应位点，从而证明了光生载流子的转移是通过Z字型异质结结构实现的.TEM图显示金属Bi分散在钼酸铋表面.DRS和PL图分析表明金属Bi增加了材料的光吸收能力，同时扮演了中间介质的角色，促进钼酸铋导带的电子和g-C<sub>3<\/sub>N<sub>4<\/sub>价带的空穴快速复合.因此，g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi的优异光催化性能主要归功于Z字型异质结和Bi金属的等离子共振吸收效应，提高了材料的光吸收能力和光生载流子分离率.","abstractInfoCn":"半导体光催化技术是目前最有前景的绿色化学技术，可通过利用太阳光降解污染物或制氢.作为有潜力的半导体催化剂，钼酸铋具有合适的带隙（2.58eV）.但是，由于低的量子产量，钼酸铋的光催化性能并不理想.为了提高钼酸铋的光催化性能，研究者多考虑采取构造异质结的方式.石墨相氮化碳（g-C<sub>3<\/sub>N<sub>4<\/sub>）能带位置合适，与多种光催化半导体能带匹配，是构造异质结的常用选择.因此，本文选用g-C<sub>3<\/sub>N<sub>4<\/sub>与钼酸铋复合，构造异质结结构.为了进一步提高光催化性能，多采用负载贵金属（Pt，Au和Pd）作为助催化剂，利用贵金属特有的等离子共振效应，增加光吸收，促进载流子分离，但贵金属价格昂贵.Bi金属单质价格便宜，具备等效的等离子共振效应，是理想的贵金属替代物.钼酸铋可以采取原位还原的方式还原出Bi单质，构造更紧密的界面结构，更有利于载流子传输.Bi的等离子共振效应可以有效提高材料的光吸收能力和光生载流子分离率.<br/>本文采用溶剂热和原位还原方法成功合成了一种新型三元异质结结构g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi（CN/BMO/Bi）空心微球.结果显示，三元异质结结构的最佳配比为0.4CN/BMO/9Bi，该样品表现出最好的光催化降解罗丹明B效率，是纯钼酸铋的9倍.通过计算DRS和XPS的价带数据，0.4CN/BMO/9Bi是一种Z字型异质结.牺牲试剂实验也提供了Z字型异质结的有力证据，测试显示超氧自由基&#183;O<sup>2-<\/sup>（在-0.33eV）是光催化降解的主要基团.但是，钼酸铋的导带位置低于-0.33eV，g-C<sub>3<\/sub>N<sub>4<\/sub>的导带高于-0.33eV，因此g-C<sub>3<\/sub>N<sub>4<\/sub>的导带是唯一的反应位点，从而证明了光生载流子的转移是通过Z字型异质结结构实现的.TEM图显示金属Bi分散在钼酸铋表面.DRS和PL图分析表明金属Bi增加了材料的光吸收能力，同时扮演了中间介质的角色，促进钼酸铋导带的电子和g-C<sub>3<\/sub>N<sub>4<\/sub>价带的空穴快速复合.因此，g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi的优异光催化性能主要归功于Z字型异质结和Bi金属的等离子共振吸收效应，提高了材料的光吸收能力和光生载流子分离率.","abstractInfoEn":"The surface plasmonic resonance (SPR) effect of Bi can effectively improve the light absorption abilities and photogenerated charge carrier separation rate. In this study, a novel ternary heterojunction of g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi (CN/BMO/Bi) hollow microsphere was successfully fabricated through solvothermal and <i>in situ<\/i> reduction methods. The results revealed that the optimal ternary 0.4CN/BMO/9Bi photocatalyst exhibited the highest photocatalytic efficiency toward rhodamine B (RhB) degradation with nine times that of pure BMO. The DRS and valence band of the X-ray photoelectron spectroscopy spectrum demonstrate that the band structure of 0.4CN/BMO/9Bi is a z-scheme structure. Quenching experiments also provided solid evidence that the &#183;O<sup>2-<\/sup> (at -0.33 eV) is the main species during dye degradation, and the conduction band of g-C<sub>3<\/sub>N<sub>4<\/sub> is only the reaction site, demonstrating that the transfer of photogenerated charge carriers of g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi is through an indirect z-scheme structure. Thus, the enhanced photocatalytic performance was mainly ascribed to the synergetic effect of heterojunction structures between g-C<sub>3<\/sub>N<sub>4<\/sub> and Bi<sub>2<\/sub>MoO<sub>6<\/sub> and the SPR effect of Bi doping, resulting in better optical absorption ability and a lower combination rate of photogenerated charge carriers. The findings in this work provide insight into the synergism of heterostructures and the SPR absorption ability in wastewater treatment.","articleNo":"20200305","authorCnList":["李宁","  高航","  王鑫","  赵苏君","  吕达","  杨国庆","  高雪云","  樊海宽","  高旸钦","  戈磊"],"authorEnList":["Ning Li","  Hang Gao","  Xin Wang","  Sujun Zhao","  Da Lv","  Guoqing Yang","  Xueyun Gao","  Haikuan Fan","  Yangqin Gao","  Lei Ge"],"authorList":["李宁","  高航","  王鑫","  赵苏君","  吕达","  杨国庆","  高雪云","  樊海宽","  高旸钦","  戈磊"],"authors":"李宁,  高航,  王鑫,  赵苏君,  吕达,  杨国庆,  高雪云,  樊海宽,  高旸钦,  戈磊","authorsCn":"李宁,  高航,  王鑫,  赵苏君,  吕达,  杨国庆,  高雪云,  樊海宽,  高旸钦,  戈磊","authorsEn":"Ning Li,  Hang Gao,  Xin Wang,  Sujun Zhao,  Da Lv,  Guoqing Yang,  Xueyun Gao,  Haikuan Fan,  Yangqin Gao,  Lei Ge","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"李宁,  高航,  王鑫,  赵苏君,  吕达,  杨国庆,  高雪云,  樊海宽,  高旸钦,  戈磊. 新型间接Z字结型g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi空心微球等离子共振增强光吸收和光催化性能. 催化学报, 2020, 41(3): 426-434. doi: S1872-2067(19)63478-9.","citationCn":"李宁,  高航,  王鑫,  赵苏君,  吕达,  杨国庆,  高雪云,  樊海宽,  高旸钦,  戈磊. 新型间接Z字结型g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi空心微球等离子共振增强光吸收和光催化性能. 催化学报, 2020, 41(3): 426-434. doi: S1872-2067(19)63478-9.","citationEn":"李宁,  高航,  王鑫,  赵苏君,  吕达,  杨国庆,  高雪云,  樊海宽,  高旸钦,  戈磊. Novel indirect Z-scheme g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi hollow microsphere heterojunctions with SPR-promoted visible absorption and highly enhanced photocatalytic performance. Chinese Journal of Catalysis, 2020, 41(3): 426-434. doi: S1872-2067(19)63478-9.","doi":"S1872-2067(19)63478-9","figContent":"","figList":[],"firstFig":"","fpage":"426","highCitedState":"","htmlCount":190,"htmlFile":"","id":"d286574c-48fb-47ec-b721-befbab517885","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"钼酸铋, 石墨相氮化碳, 金属铋, Z字型异质结, 等离子共振效应, 罗丹明B, 可见光","keywordCn":"钼酸铋, 石墨相氮化碳, 金属铋, Z字型异质结, 等离子共振效应, 罗丹明B, 可见光","keywordCnList":["钼酸铋"," 石墨相氮化碳"," 金属铋"," Z字型异质结"," 等离子共振效应"," 罗丹明B"," 可见光"],"keywordEn":"g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi, Z-scheme catalyst, Surface plasmonic resonance effect, Rhodamine B, Visible light","keywordEnList":["g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi"," Z-scheme catalyst"," Surface plasmonic resonance effect"," Rhodamine B"," Visible light"],"keywordList":["钼酸铋"," 石墨相氮化碳"," 金属铋"," Z字型异质结"," 等离子共振效应"," 罗丹明B"," 可见光"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"434","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":13,"pdfSize":1661.11,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"新型间接Z字结型g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi空心微球等离子共振增强光吸收和光催化性能","titleCn":"新型间接Z字结型g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi空心微球等离子共振增强光吸收和光催化性能","titleEn":"Novel indirect Z-scheme g-C<sub>3<\/sub>N<sub>4<\/sub>/Bi<sub>2<\/sub>MoO<sub>6<\/sub>/Bi hollow microsphere heterojunctions with SPR-promoted visible absorption and highly enhanced photocatalytic performance","viewCount":1348,"volume":"41","year":2020},{"abstractInfo":"近几十年来，随着全球变暖和能源危机的日益严重，对取之不尽、用之不竭的清洁能源技术的需求越来越迫切.1991年Gratzel首次报道了染料敏化太阳能电池（DSSCs），它以低廉的价格、优异的理论功率转换效率（PCE）、环保、多色透明等优点而引起了研究者的关注.Sb<sub>2<\/sub>S<sub>3<\/sub>因其1.5-2.2eV的间隙宽度被认为是最有前途的对电极材料之一.此外，Sb<sub>2<\/sub>S<sub>3<\/sub>是地球中含量丰富的无毒锑矿物的主要成分，还被广泛应用于太阳能转换材料、催化剂、光导探测器等领域.众所周知，石墨烯具有巨大的比表面积、显著的载流子迁移率和优异的热/化学稳定性，这使得提高电子转移效率和电催化活性成为可能.<br/>首先，采用改进的Hummers方法制备了氧化石墨烯纳米片然后采用水热法通过改变Sb源以及实验pH值，合成了Sb<sub>2<\/sub>S<sub>3<\/sub>和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO样品.对样品进行X射线粉末衍射（XRD）、扫描电子显微镜镜（SEM）、投射电子显微镜（TEM）以及比表面积表征.结果表明，在Sb源不变的情况下，Sb<sub>2<\/sub>S<sub>3<\/sub>样品的形貌随pH值的变化而变化.以三乙酸锑为Sb源，在pH=3时，Sb<sub>2<\/sub>S<sub>3<\/sub>的形貌类似于一个完整的纳米棒结构在pH值为6时，样品为不规则球体当pH值为8时，纳米片结构开始出现但当pH=10时，纳米片结构并不均匀.根据XRD分析，只有当pH值为3时，样品的衍射峰才与标准卡（JCPDS42-1393）的衍射峰一致.当以氯化锑作为锑源，样品的形貌由不规则的杆状（pH=3）转变为纳米球（pH=6），然后出现纳米片结构（pH=8）.不同的是，当pH值为10时，纳米薄片形成均一的花状结构.XRD结果表明，除pH值为3外，样品的衍射峰与标准卡（JCPDS42-1393）的值吻合较好.结果表明，合成条件所需的Sb源和碱性环境是合成具有均匀花状结构的纳米片状Sb<sub>2<\/sub>S<sub>3<\/sub>所必不可少的.测得Sb<sub>2<\/sub>S<sub>3<\/sub>的比表面积约为41.72m<sup>2<\/sup>g<sup>-1<\/sup>，平均孔径为31.08nm，Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO的分别为44.53m<sup>2<\/sup>g<sup>-1<\/sup>和22.65nm.Sb<sub>2<\/sub>S<sub>3<\/sub>和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO复合材料均具有介孔结构，为内部电催化剂提供了广阔的通道，从而提高了对电极的催化能力，促进了电化学反应.<br/>将Sb<sub>2<\/sub>S<sub>3<\/sub>纳米花球和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO纳米薄片作为染料敏化太阳能电池的对电极进行了测试，由于石墨烯的引入，后者比前者具有更好的电催化性能.电化学实验结果表明，与Sb<sub>2<\/sub>S<sub>3<\/sub>，RGO，Pt作为对电极相比，制备的Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO纳米薄片具有更好的催化活性、电荷转移能力和电化学稳定性，Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO的功率转换效率达到8.17%，优于标准Pt对电极（7.75%）.","abstractInfoCn":"近几十年来，随着全球变暖和能源危机的日益严重，对取之不尽、用之不竭的清洁能源技术的需求越来越迫切.1991年Gratzel首次报道了染料敏化太阳能电池（DSSCs），它以低廉的价格、优异的理论功率转换效率（PCE）、环保、多色透明等优点而引起了研究者的关注.Sb<sub>2<\/sub>S<sub>3<\/sub>因其1.5-2.2eV的间隙宽度被认为是最有前途的对电极材料之一.此外，Sb<sub>2<\/sub>S<sub>3<\/sub>是地球中含量丰富的无毒锑矿物的主要成分，还被广泛应用于太阳能转换材料、催化剂、光导探测器等领域.众所周知，石墨烯具有巨大的比表面积、显著的载流子迁移率和优异的热/化学稳定性，这使得提高电子转移效率和电催化活性成为可能.<br/>首先，采用改进的Hummers方法制备了氧化石墨烯纳米片然后采用水热法通过改变Sb源以及实验pH值，合成了Sb<sub>2<\/sub>S<sub>3<\/sub>和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO样品.对样品进行X射线粉末衍射（XRD）、扫描电子显微镜镜（SEM）、投射电子显微镜（TEM）以及比表面积表征.结果表明，在Sb源不变的情况下，Sb<sub>2<\/sub>S<sub>3<\/sub>样品的形貌随pH值的变化而变化.以三乙酸锑为Sb源，在pH=3时，Sb<sub>2<\/sub>S<sub>3<\/sub>的形貌类似于一个完整的纳米棒结构在pH值为6时，样品为不规则球体当pH值为8时，纳米片结构开始出现但当pH=10时，纳米片结构并不均匀.根据XRD分析，只有当pH值为3时，样品的衍射峰才与标准卡（JCPDS 42-1393）的衍射峰一致.当以氯化锑作为锑源，样品的形貌由不规则的杆状（pH=3）转变为纳米球（pH=6），然后出现纳米片结构（pH=8）.不同的是，当pH值为10时，纳米薄片形成均一的花状结构.XRD结果表明，除pH值为3外，样品的衍射峰与标准卡（JCPDS 42-1393）的值吻合较好.结果表明，合成条件所需的Sb源和碱性环境是合成具有均匀花状结构的纳米片状Sb<sub>2<\/sub>S<sub>3<\/sub>所必不可少的.测得Sb<sub>2<\/sub>S<sub>3<\/sub>的比表面积约为41.72m<sup>2<\/sup>g<sup>-1<\/sup>，平均孔径为31.08 nm，Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO的分别为44.53m<sup>2<\/sup>g<sup>-1<\/sup>和22.65nm.Sb<sub>2<\/sub>S<sub>3<\/sub>和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO复合材料均具有介孔结构，为内部电催化剂提供了广阔的通道，从而提高了对电极的催化能力，促进了电化学反应.<br/>将Sb<sub>2<\/sub>S<sub>3<\/sub>纳米花球和Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO纳米薄片作为染料敏化太阳能电池的对电极进行了测试，由于石墨烯的引入，后者比前者具有更好的电催化性能.电化学实验结果表明，与Sb<sub>2<\/sub>S<sub>3<\/sub>，RGO，Pt作为对电极相比，制备的Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO纳米薄片具有更好的催化活性、电荷转移能力和电化学稳定性，Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO的功率转换效率达到8.17%，优于标准Pt对电极（7.75%）.","abstractInfoEn":"In this work, we initially synthesized Sb<sub>2<\/sub>S<sub>3<\/sub> with uniform flower-like structures via a facile hydrothermal method through the modification of the Sb source and pH value. Afterward, Sb<sub>2<\/sub>S<sub>3<\/sub> with a nanosheet structure was successfully synthesized on reduced graphene oxide (Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO). The flower-like Sb<sub>2<\/sub>S<sub>3<\/sub> and the Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO nanosheets were tested as the counter electrode (CE) of dye-sensitized solar cells, and the latter exhibited a higher electrocatalytic property than the former owing to the introduction of graphene. The results from electrochemical tests indicated that the as-prepared Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO nanosheets possess higher catalytic activity, charge-transfer ability, and electrochemical stability than Sb<sub>2<\/sub>S<sub>3<\/sub>, RGO, and Pt CEs. More notably, the power conversion efficiency of Sb<sub>2<\/sub>S<sub>3<\/sub>@RGO reached 8.17%, which was higher than that of the standard Pt CE (7.75%).","articleNo":"20200306","authorCnList":["陈学","  李雪敏","  卫朋坤","  马小勇","  喻其林","  刘璐"],"authorEnList":["Xue Chen","  Xuemin Li","  Pengkun Wei","  Xiaoyong Ma","  Qinlin Yu","  Lu Liu"],"authorList":["陈学","  李雪敏","  卫朋坤","  马小勇","  喻其林","  刘璐"],"authors":"陈学,  李雪敏,  卫朋坤,  马小勇,  喻其林,  刘璐","authorsCn":"陈学,  李雪敏,  卫朋坤,  马小勇,  喻其林,  刘璐","authorsEn":"Xue Chen,  Xuemin Li,  Pengkun Wei,  Xiaoyong Ma,  Qinlin Yu,  Lu Liu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"陈学,  李雪敏,  卫朋坤,  马小勇,  喻其林,  刘璐. 选择性合成不同形貌的Sb<sub>2<\/sub>S<sub>3<\/sub>纳米结构应用于高性能的染料敏化太阳能电池. 催化学报, 2020, 41(3): 435-441. doi: S1872-2067(19)63493-5.","citationCn":"陈学,  李雪敏,  卫朋坤,  马小勇,  喻其林,  刘璐. 选择性合成不同形貌的Sb<sub>2<\/sub>S<sub>3<\/sub>纳米结构应用于高性能的染料敏化太阳能电池. 催化学报, 2020, 41(3): 435-441. doi: S1872-2067(19)63493-5.","citationEn":"陈学,  李雪敏,  卫朋坤,  马小勇,  喻其林,  刘璐. Selective synthesis of Sb<sub>2<\/sub>S<sub>3<\/sub> nanostructures with different morphologies for high performance in dye-sensitized solar cells. Chinese Journal of Catalysis, 2020, 41(3): 435-441. doi: S1872-2067(19)63493-5.","doi":"S1872-2067(19)63493-5","figContent":"","figList":[],"firstFig":"","fpage":"435","highCitedState":"","htmlCount":36,"htmlFile":"","id":"f5d31158-743f-450a-9ffb-691e08b37939","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"Sb<sub>2<\/sub>S<sub>3<\/sub>, 还原性石墨烯, 对电极, 染料敏化电池, 功率转换效率","keywordCn":"Sb<sub>2<\/sub>S<sub>3<\/sub>, 还原性石墨烯, 对电极, 染料敏化电池, 功率转换效率","keywordCnList":["Sb<sub>2<\/sub>S<sub>3<\/sub>"," 还原性石墨烯"," 对电极"," 染料敏化电池"," 功率转换效率"],"keywordEn":"Sb<sub>2<\/sub>S<sub>3<\/sub>, Reduced graphene oxide, Counter electrode, Dye-sensitized cells, Power conversion efficiency","keywordEnList":["Sb<sub>2<\/sub>S<sub>3<\/sub>"," Reduced graphene oxide"," Counter electrode"," Dye-sensitized cells"," Power conversion efficiency"],"keywordList":["Sb<sub>2<\/sub>S<sub>3<\/sub>"," 还原性石墨烯"," 对电极"," 染料敏化电池"," 功率转换效率"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"441","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":5,"pdfSize":1239.4,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"选择性合成不同形貌的Sb<sub>2<\/sub>S<sub>3<\/sub>纳米结构应用于高性能的染料敏化太阳能电池","titleCn":"选择性合成不同形貌的Sb<sub>2<\/sub>S<sub>3<\/sub>纳米结构应用于高性能的染料敏化太阳能电池","titleEn":"Selective synthesis of Sb<sub>2<\/sub>S<sub>3<\/sub> nanostructures with different morphologies for high performance in dye-sensitized solar cells","viewCount":986,"volume":"41","year":2020},{"abstractInfo":"低碳烷烃是一类主要的挥发性有机污染物（VOCs），广泛生成于汽车尾气以及各种工业过程如煤处理、石油精炼以及天然气处理等.随着对环保要求的日益提高，对高效VOCs消除技术的需求愈加迫切.催化完全氧化（催化燃烧）技术具有起燃温度低、能耗低、净化效果好（无二次污染）等优点，因而极具应用潜力.对于低碳烷烃的催化燃烧，贵金属催化剂如Pt和Pd等具有很高的反应活性，但存在价格昂贵并易中毒等缺陷限制了其商业应用.另一方面，过渡金属氧化物由于其价格低廉、抗中毒性能优异及热稳定性好等特点受到广泛关注.Cu，Mn，Co，Fe等氧化物都具有良好的催化活性，其中Co氧化物由于其在丙烷催化燃烧中的高活性受到关注.而在Co氧化物中添加第二金属更能促进其反应性能.因此本文制备了一系列不同Co/Cr比例的复合氧化物用于丙烷催化燃烧，考察了催化剂结构和表面性质对其反应行为的影响，并通过反应动力学和原位光谱技术对反应机理进行了探索.<br/>实验结果表明，随着Co/Cr比例的变化，催化剂的晶相结构、颗粒尺寸、比表面积、表面酸性以及氧化还原性等特性均发生了明显变化，进而影响了其反应行为.当Co/Cr比例为1/2时（1Co2Cr），催化剂为尖晶石结构并具有最大的比表面积.该催化剂上具有最高的反应活性（250℃时反应速率为1.38μmolg<sup>-1<\/sup>s<sup>-1<\/sup>），可归因于其最高的表面酸性和低温氧化还原性能的协同作用.反应动力学结果表明，1Co2Cr催化剂上丙烷和氧气的反应级数分别为0.58&#177;0.03和0.34&#177;0.05，低于2Co1Cr（分别为0.77&#177;0.02和0.98&#177;0.16）和1Co5Cr（分别为0.66&#177;0.05和1.30&#177;0.11），表明1122Cr催化剂相比后二者具有更高的丙烷和氧气表面覆盖度，得益于其更高的表面酸性和更好的低温氧化还原性能.此外，原位红外光谱表明，在反应过程中，1Co2Cr催化剂上的主要表面物种为多齿碳酸盐，该物种在低温时（<250℃）在表面积聚，但在高温时被分解.","abstractInfoCn":"低碳烷烃是一类主要的挥发性有机污染物（VOCs），广泛生成于汽车尾气以及各种工业过程如煤处理、石油精炼以及天然气处理等.随着对环保要求的日益提高，对高效VOCs消除技术的需求愈加迫切.催化完全氧化（催化燃烧）技术具有起燃温度低、能耗低、净化效果好（无二次污染）等优点，因而极具应用潜力.对于低碳烷烃的催化燃烧，贵金属催化剂如Pt和Pd等具有很高的反应活性，但存在价格昂贵并易中毒等缺陷限制了其商业应用.另一方面，过渡金属氧化物由于其价格低廉、抗中毒性能优异及热稳定性好等特点受到广泛关注.Cu，Mn，Co，Fe等氧化物都具有良好的催化活性，其中Co氧化物由于其在丙烷催化燃烧中的高活性受到关注.而在Co氧化物中添加第二金属更能促进其反应性能.因此本文制备了一系列不同Co/Cr比例的复合氧化物用于丙烷催化燃烧，考察了催化剂结构和表面性质对其反应行为的影响，并通过反应动力学和原位光谱技术对反应机理进行了探索.<br/>实验结果表明，随着Co/Cr比例的变化，催化剂的晶相结构、颗粒尺寸、比表面积、表面酸性以及氧化还原性等特性均发生了明显变化，进而影响了其反应行为.当Co/Cr比例为1/2时（1Co2Cr），催化剂为尖晶石结构并具有最大的比表面积.该催化剂上具有最高的反应活性（250℃时反应速率为1.38μmol g<sup>-1<\/sup> s<sup>-1<\/sup>），可归因于其最高的表面酸性和低温氧化还原性能的协同作用.反应动力学结果表明，1Co2Cr催化剂上丙烷和氧气的反应级数分别为0.58 &#177;0.03和0.34 &#177;0.05，低于2Co1Cr（分别为0.77 &#177;0.02和0.98 &#177;0.16）和1Co5Cr（分别为0.66 &#177;0.05和1.30 &#177;0.11），表明1122Cr催化剂相比后二者具有更高的丙烷和氧气表面覆盖度，得益于其更高的表面酸性和更好的低温氧化还原性能.此外，原位红外光谱表明，在反应过程中，1Co2Cr催化剂上的主要表面物种为多齿碳酸盐，该物种在低温时（< 250℃）在表面积聚，但在高温时被分解.","abstractInfoEn":"A series of Co-Cr-O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane. The reaction behaviors are closely related to the structural features of the mixed oxides. The catalyst with a Co/Cr molar ratio of 1:2 (1Co2Cr) and a spinel structure has the best activity (with a reaction rate of 1.38 μmol g<sup>-1<\/sup> s<sup>-1<\/sup> at 250℃), which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility, as evidenced by the temperature-programmed desorption of ammonia, reduction of hydrogen, and surface reaction of propane. Kinetic study shows that the reaction orders of propane and oxygen on the 1Co2Cr catalyst (0.58 &#177; 0.03 and 0.34 &#177;0.05, respectively) are lower than those on the 2Co1Cr catalyst (0.77 &#177;0.02 and 0.98 &#177;0.16, respectively) and 1Co5Cr (0.66 &#177;0.05 and 1.30 &#177;0.11, respectively), indicating that the coverages of propane and oxygen on 1Co2Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility. In addition, in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1Co2Cr during the reaction are polydentate carbonate species, which accumulate on the surface at low temperatures (< 250℃) but decompose at relatively high temperatures.","articleNo":"20200307","authorCnList":["廖文敏","  赵培培","  岑丙横","  贾爱平","  鲁继青","  罗孟飞"],"authorEnList":["Wen-Min Liao","  Pei-Pei Zhao","  Bing-Heng Cen","  Ai-Ping Jia","  Ji-Qing Lu","  Meng-Fei Luo"],"authorList":["廖文敏","  赵培培","  岑丙横","  贾爱平","  鲁继青","  罗孟飞"],"authors":"廖文敏,  赵培培,  岑丙横,  贾爱平,  鲁继青,  罗孟飞","authorsCn":"廖文敏,  赵培培,  岑丙横,  贾爱平,  鲁继青,  罗孟飞","authorsEn":"Wen-Min Liao,  Pei-Pei Zhao,  Bing-Heng Cen,  Ai-Ping Jia,  Ji-Qing Lu,  Meng-Fei Luo","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"廖文敏,  赵培培,  岑丙横,  贾爱平,  鲁继青,  罗孟飞. Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究. 催化学报, 2020, 41(3): 442-453. doi: S1872-2067(19)63480-7.","citationCn":"廖文敏,  赵培培,  岑丙横,  贾爱平,  鲁继青,  罗孟飞. Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究. 催化学报, 2020, 41(3): 442-453. doi: S1872-2067(19)63480-7.","citationEn":"廖文敏,  赵培培,  岑丙横,  贾爱平,  鲁继青,  罗孟飞. Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation. Chinese Journal of Catalysis, 2020, 41(3): 442-453. doi: S1872-2067(19)63480-7.","doi":"S1872-2067(19)63480-7","figContent":"","figList":[],"firstFig":"","fpage":"442","highCitedState":"","htmlCount":120,"htmlFile":"","id":"6dfb5e43-33eb-403d-8fc6-c69339c37c86","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"丙烷催化燃烧, Co-Cr复合氧化物, 氧化还原性能, 表面酸性, 反应动力学","keywordCn":"丙烷催化燃烧, Co-Cr复合氧化物, 氧化还原性能, 表面酸性, 反应动力学","keywordCnList":["丙烷催化燃烧"," Co-Cr复合氧化物"," 氧化还原性能"," 表面酸性"," 反应动力学"],"keywordEn":"Propane combustion, Co-Cr mixed oxides, Reducibility, Surface acidity, Kinetics","keywordEnList":["Propane combustion"," Co-Cr mixed oxides"," Reducibility"," Surface acidity"," Kinetics"],"keywordList":["丙烷催化燃烧"," Co-Cr复合氧化物"," 氧化还原性能"," 表面酸性"," 反应动力学"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"453","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":5,"pdfSize":1112.97,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究","titleCn":"Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究","titleEn":"Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation","viewCount":1293,"volume":"41","year":2020},{"abstractInfo":"光催化分解水制氢和还原CO<sub>2<\/sub>是太阳能利用领域的研究热点，对清洁能源的转化具有重要意义.石墨相氮化碳（CN）作为一种非金属半导体，是一种非常有开发潜力的光催化材料.然而限于其聚合物本质，光催化效率仍有待进一步提高.原位非金属掺杂可以利用元素电子结构调控电荷分布，优化光生电荷传输性能.同时，半导体复合，尤其是2D层状复合结构的构筑，可充分发挥2D半导体的优势，合适的能带交错有利于光生电荷的传输，可在一定程度上加速催化反应的进行.<br/>本文首先以草酸为氧掺杂源，采用二步煅烧法合成氧掺杂氮化碳纳米片催化剂（CNO）.在二次煅烧和氧掺杂共同作用下，增大了CN层间距和多孔性，颗粒尺寸减小，同时增强了对光的吸光性，拓展了可见光吸收范围.接下来采用一步水热合成法得到ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO（ZC）复合材料，在可见光照射下通过分解水制氢和CO<sub>2<\/sub>还原反应对复合材料进行光催化还原性能评价.采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱（XPS）、荧光光谱（PL）、光电化学测试等方法对ZC进行详细的结构表征和分析.XRD和XPS结果表明，经过一步直接水热可得到层状ZC复合材料，高倍TEM进一步证实二者形成均一的2D异质复合材料.N<sub>2<\/sub>-吸附-脱附曲线表明，复合材料具有较大的比表面积和均一的孔结构分布，主要得益于O掺杂CNO纳米片的多孔性结构.光电性质测试结果表明，相比于CNO，复合材料具有降低的荧光发射强度和延长的荧光寿命，表明复合产物显著抑制了光生电荷的复合.电化学测试进一步表明，复合异质结的构筑有利于光生载流子的产生，同时降低了界面电荷转移电阻，提高了电荷迁移速率.因此，多孔2D异质结构的构筑对促进CN基半导体光催化还原具有重要作用.<br/>在可见光照射下（<i>λ<\/i>>400nm），复合材料表现出优异的光催化还原性能，且随着CNO含量的增加催化活性不断提高，其中ZC40%（CNO质量比40%）具有最佳的催化活性，其产氢速率达188.4μmol/h，约是ZnIn<sub>2<\/sub>S<sub>4<\/sub>和CNO的2.1倍.同时，光催化还原CO<sub>2<\/sub>测试表明，复合材料具有显著提高的CO和CH<sub>4<\/sub>产率，其中CO为主要反应产物.ZC40%的CO产生速率为12.69μmol/h，分别是ZnIn<sub>2<\/sub>S<sub>4<\/sub>和CNO的2.2倍和14.0倍.对催化剂进行连续光反应，结果表明，复合催化剂具有优异的结构稳定性和活性稳定性，能够持续发生光还原反应制取H<sub>2<\/sub>和CO.","abstractInfoCn":"光催化分解水制氢和还原CO<sub>2<\/sub>是太阳能利用领域的研究热点，对清洁能源的转化具有重要意义.石墨相氮化碳（CN）作为一种非金属半导体，是一种非常有开发潜力的光催化材料.然而限于其聚合物本质，光催化效率仍有待进一步提高.原位非金属掺杂可以利用元素电子结构调控电荷分布，优化光生电荷传输性能.同时，半导体复合，尤其是2D层状复合结构的构筑，可充分发挥2D半导体的优势，合适的能带交错有利于光生电荷的传输，可在一定程度上加速催化反应的进行.<br/>本文首先以草酸为氧掺杂源，采用二步煅烧法合成氧掺杂氮化碳纳米片催化剂（CNO）.在二次煅烧和氧掺杂共同作用下，增大了CN层间距和多孔性，颗粒尺寸减小，同时增强了对光的吸光性，拓展了可见光吸收范围.接下来采用一步水热合成法得到ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO（ZC）复合材料，在可见光照射下通过分解水制氢和CO<sub>2<\/sub>还原反应对复合材料进行光催化还原性能评价.采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱（XPS）、荧光光谱（PL）、光电化学测试等方法对ZC进行详细的结构表征和分析.XRD和XPS结果表明，经过一步直接水热可得到层状ZC复合材料，高倍TEM进一步证实二者形成均一的2D异质复合材料.N<sub>2<\/sub>-吸附-脱附曲线表明，复合材料具有较大的比表面积和均一的孔结构分布，主要得益于O掺杂CNO纳米片的多孔性结构.光电性质测试结果表明，相比于CNO，复合材料具有降低的荧光发射强度和延长的荧光寿命，表明复合产物显著抑制了光生电荷的复合.电化学测试进一步表明，复合异质结的构筑有利于光生载流子的产生，同时降低了界面电荷转移电阻，提高了电荷迁移速率.因此，多孔2D异质结构的构筑对促进CN基半导体光催化还原具有重要作用.<br/>在可见光照射下（<i>λ<\/i> > 400nm），复合材料表现出优异的光催化还原性能，且随着CNO含量的增加催化活性不断提高，其中ZC 40%（CNO质量比40%）具有最佳的催化活性，其产氢速率达188.4μmol/h，约是ZnIn<sub>2<\/sub>S<sub>4<\/sub>和CNO的2.1倍.同时，光催化还原CO<sub>2<\/sub>测试表明，复合材料具有显著提高的CO和CH<sub>4<\/sub>产率，其中CO为主要反应产物.ZC 40%的CO产生速率为12.69μmol/h，分别是ZnIn<sub>2<\/sub>S<sub>4<\/sub>和CNO的2.2倍和14.0倍.对催化剂进行连续光反应，结果表明，复合催化剂具有优异的结构稳定性和活性稳定性，能够持续发生光还原反应制取H<sub>2<\/sub>和CO.","abstractInfoEn":"Photocatalytic H<sub>2<\/sub> production and CO<sub>2<\/sub> reduction have attracted considerable attention for clean energy development. In this work, we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride (CNO) nanosheets into ZnIn<sub>2<\/sub>S<sub>4<\/sub> (ZIS) microflowers by a one-step hydrothermal method. A well-fitted 2D hierarchical hybrid heterostructure was fabricated. Under visible light irradiation, the ZIS@CNO composite with 40 wt% CNO (ZC 40%) showed the highest hydrogen evolution rate from water (188.4 μmol&#183;h<sup>-1<\/sup>), which was approximately 2.1 times higher than those of CNO and ZIS (88.6 and 90.2 μmol&#183;h<sup>-1<\/sup>, respectively). Furthermore, the selective CO production rates of ZC 40% (12.69 μmol&#183;h<sup>-1<\/sup>) were 2.2 and 14.0 times higher than those of ZIS (5.85 μmol&#183;h<sup>-1<\/sup>) and CNO (0.91 μmol&#183;h<sup>-1<\/sup>), respectively, and the CH<sub>4<\/sub> production rate of ZC 40% was 1.18 μmol&#183;h<sup>-1<\/sup>. This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS, thereby efficiently avoiding recombination of electron-hole pairs.","articleNo":"20200308","authorCnList":["祝凯","  欧阳杰","  曾黔","  孟苏刚","  滕伟","  宋艳华","  唐盛","  崔言娟"],"authorEnList":["Kai Zhu","  Jie Ou-Yang","  Qian Zeng","  Sugang Meng","  Wei Teng","  Yanhua Song","  Sheng Tang","  Yanjuan Cui"],"authorList":["祝凯","  欧阳杰","  曾黔","  孟苏刚","  滕伟","  宋艳华","  唐盛","  崔言娟"],"authors":"祝凯,  欧阳杰,  曾黔,  孟苏刚,  滕伟,  宋艳华,  唐盛,  崔言娟","authorsCn":"祝凯,  欧阳杰,  曾黔,  孟苏刚,  滕伟,  宋艳华,  唐盛,  崔言娟","authorsEn":"Kai Zhu,  Jie Ou-Yang,  Qian Zeng,  Sugang Meng,  Wei Teng,  Yanhua Song,  Sheng Tang,  Yanjuan Cui","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"祝凯,  欧阳杰,  曾黔,  孟苏刚,  滕伟,  宋艳华,  唐盛,  崔言娟. ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO多级纳米片用于光催化分解水制氢和还原CO<sub>2<\/sub>. 催化学报, 2020, 41(3): 454-463. doi: S1872-2067(19)63494-7.","citationCn":"祝凯,  欧阳杰,  曾黔,  孟苏刚,  滕伟,  宋艳华,  唐盛,  崔言娟. ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO多级纳米片用于光催化分解水制氢和还原CO<sub>2<\/sub>. 催化学报, 2020, 41(3): 454-463. doi: S1872-2067(19)63494-7.","citationEn":"祝凯,  欧阳杰,  曾黔,  孟苏刚,  滕伟,  宋艳华,  唐盛,  崔言娟. Fabrication of hierarchical ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO nanosheets for photocatalytic hydrogen production and CO<sub>2<\/sub> photoreduction. Chinese Journal of Catalysis, 2020, 41(3): 454-463. doi: S1872-2067(19)63494-7.","doi":"S1872-2067(19)63494-7","figContent":"","figList":[],"firstFig":"","fpage":"454","highCitedState":"","htmlCount":108,"htmlFile":"","id":"a6268079-a3ed-44ef-8521-11c84652fd72","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"ZnIn<sub>2<\/sub>S<sub>4<\/sub>, 氧掺杂氮化碳, 光催化, 产氢, CO<sub>2<\/sub>还原","keywordCn":"ZnIn<sub>2<\/sub>S<sub>4<\/sub>, 氧掺杂氮化碳, 光催化, 产氢, CO<sub>2<\/sub>还原","keywordCnList":["ZnIn<sub>2<\/sub>S<sub>4<\/sub>"," 氧掺杂氮化碳"," 光催化"," 产氢"," CO<sub>2<\/sub>还原"],"keywordEn":"ZnIn<sub>2<\/sub>S<sub>4<\/sub>, Oxygen doped carbon nitride, Photocatalysis, H<sub>2<\/sub> production, CO<sub>2<\/sub> reduction","keywordEnList":["ZnIn<sub>2<\/sub>S<sub>4<\/sub>"," Oxygen doped carbon nitride"," Photocatalysis"," H<sub>2<\/sub> production"," CO<sub>2<\/sub> reduction"],"keywordList":["ZnIn<sub>2<\/sub>S<sub>4<\/sub>"," 氧掺杂氮化碳"," 光催化"," 产氢"," CO<sub>2<\/sub>还原"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"463","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":9,"pdfSize":1190.5,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO多级纳米片用于光催化分解水制氢和还原CO<sub>2<\/sub>","titleCn":"ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO多级纳米片用于光催化分解水制氢和还原CO<sub>2<\/sub>","titleEn":"Fabrication of hierarchical ZnIn<sub>2<\/sub>S<sub>4<\/sub>@CNO nanosheets for photocatalytic hydrogen production and CO<sub>2<\/sub> photoreduction","viewCount":1496,"volume":"41","year":2020},{"abstractInfo":"光催化作为一种环境友好型、低能耗的技术，在环境净化等领域倍受关注.传统光催化剂，如TiO<sub>2<\/sub>，ZnO，V<sub>2<\/sub>O<sub>5<\/sub>和WO<sub>3<\/sub>等具有较高的光敏性，其价格低廉，自然无毒，常用于光电反应的应用当中.然而，这些催化剂具有较宽的禁带宽度，只能在紫外光下响应.为此，设计一种较窄带隙的高可见光活性的光催化剂具有一定的意义.近年来，氯氧化铋光催化剂受到了越来越多的关注，其在紫外光下具有非常优异的光催化性能.并且，研究者们已成功合成出非化学计量比的氯氧化铋，如Bi<sub>3<\/sub>O<sub>4<\/sub>Cl（2.60eV），Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>（2.10eV），Bi<sub>12<\/sub>O<sub>15<\/sub>Cl<sub>6<\/sub>（2.86eV）和Bi<sub>24<\/sub>O<sub>31<\/sub>Cl<sub>10<\/sub>（2.70eV）等光催化剂.研究表明，较低的Cl/O比可能会减小催化剂的带隙宽度，并提高其光催化性能；其中Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>的Cl/O比最小，是最有潜力的氯氧化铋光催化剂.然而，Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>具有较高的光生电子空穴复合率，会极大的减弱其光催化活性.因此，将Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>与具有高稳定性，结构相似且空穴复合率低的BiOCl相结合，将会极大提高在可见光下Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>的光催化活性.本文采用了超声水热法成功制备了具有高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料，用于去除染料和药物废水.扫描电子显微镜和比表面积分析仪的结果表明，纳米复合材料具有良好的分散性，结构为花瓣形状，其平均厚度为20至50nm，且具有较高的比表面积.紫外-可见漫反射和光致发光光谱分析表明，纳米复合材料具有良好的可见光吸收性能，并且光生电子空穴复合率远低于Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>.其在可见光下降解罗丹明B（/环丙沙星）的动力学常数分别约为Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>，BiOCl和P25的8.14（/4.94），64.66（/11.91）和42.63（/36.07）倍.合适的形态，结构和光电性能是此纳米复合光催化剂具有优异光催化性能的原因.<br/>此外，该催化剂还显示出较宽的pH适用范围和优异的可重复利用性，有利于实际利用.机理研究表明，降解罗丹明B的主要活性物质是光生空穴和超氧自由基.总之，本文开发了一种绿色、稳定、高效的可见光光催化剂，对BiOCl基的光催化剂的研究作出了一定的贡献.","abstractInfoCn":"光催化作为一种环境友好型、低能耗的技术，在环境净化等领域倍受关注.传统光催化剂，如TiO<sub>2<\/sub>，ZnO，V<sub>2<\/sub>O<sub>5<\/sub>和WO<sub>3<\/sub>等具有较高的光敏性，其价格低廉，自然无毒，常用于光电反应的应用当中.然而，这些催化剂具有较宽的禁带宽度，只能在紫外光下响应.为此，设计一种较窄带隙的高可见光活性的光催化剂具有一定的意义.近年来，氯氧化铋光催化剂受到了越来越多的关注，其在紫外光下具有非常优异的光催化性能.并且，研究者们已成功合成出非化学计量比的氯氧化铋，如Bi<sub>3<\/sub>O<sub>4<\/sub>Cl（2.60eV），Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>（2.10eV），Bi<sub>12<\/sub>O<sub>15<\/sub>Cl<sub>6<\/sub>（2.86eV）和Bi<sub>24<\/sub>O<sub>31<\/sub>Cl<sub>10<\/sub>（2.70eV）等光催化剂.研究表明，较低的Cl/O比可能会减小催化剂的带隙宽度，并提高其光催化性能；其中Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>的Cl/O比最小，是最有潜力的氯氧化铋光催化剂.然而，Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>具有较高的光生电子空穴复合率，会极大的减弱其光催化活性.因此，将Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>与具有高稳定性，结构相似且空穴复合率低的BiOCl相结合，将会极大提高在可见光下Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>的光催化活性.本文采用了超声水热法成功制备了具有高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料，用于去除染料和药物废水.扫描电子显微镜和比表面积分析仪的结果表明，纳米复合材料具有良好的分散性，结构为花瓣形状，其平均厚度为20至50nm，且具有较高的比表面积.紫外-可见漫反射和光致发光光谱分析表明，纳米复合材料具有良好的可见光吸收性能，并且光生电子空穴复合率远低于Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>.其在可见光下降解罗丹明B（/环丙沙星）的动力学常数分别约为Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>，BiOCl和P25的8.14（/4.94），64.66（/11.91）和42.63（/36.07）倍.合适的形态，结构和光电性能是此纳米复合光催化剂具有优异光催化性能的原因.<br/>此外，该催化剂还显示出较宽的pH适用范围和优异的可重复利用性，有利于实际利用.机理研究表明，降解罗丹明B的主要活性物质是光生空穴和超氧自由基.总之，本文开发了一种绿色、稳定、高效的可见光光催化剂，对BiOCl基的光催化剂的研究作出了一定的贡献.","abstractInfoEn":"A BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub> nanocomposite with a high visible-light response and a low photoinduced electron-hole pair recombination rate was successfully synthesized using an ultrasonic-hydrothermal method. The texture, structure, optical, and photocatalytic properties of the composite were characterized. The results showed that the composite had a sheet flower-like structure with a large specific surface area. Ultraviolet-visible diffuse reflection spectra and photoluminescence spectra showed that the composite had an excellent visible-light response and a low recombination rate of photoinduced electron hole pairs. The photocatalytic property of the composite was evaluated by the removal efficiency of rhodamine B and ciprofloxacin under visible-light illumination. The composite's reaction rate constant of removing rhodamine B (/ciprofloxacin) was approximately 8.14 (/4.94), 42.63 (/11.91) and 64.66 (/36.07) times that of Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>, P25, and BiOCl, respectively. Furthermore, the composite showed a wide applicable pH range and excellent reusability. Mechanism analysis showed that photogenerated holes played a dominant role and &#183;O<sub>2<\/sub><sup>-<\/sup> also contributed to photocatalytic degradation. In summary, this study presents a high-efficiency photocatalyst for wastewater treatment.","articleNo":"20200309","authorCnList":["龙泽清","  仙光","  张光明","  张涛","  李雪梅"],"authorEnList":["Zeqing Long","  Guang Xian","  Guangming Zhang","  Tao Zhang","  Xuemei Li"],"authorList":["龙泽清","  仙光","  张光明","  张涛","  李雪梅"],"authors":"龙泽清,  仙光,  张光明,  张涛,  李雪梅","authorsCn":"龙泽清,  仙光,  张光明,  张涛,  李雪梅","authorsEn":"Zeqing Long,  Guang Xian,  Guangming Zhang,  Tao Zhang,  Xuemei Li","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"龙泽清,  仙光,  张光明,  张涛,  李雪梅. 超声水热法制备高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料去除染料和药物废水. 催化学报, 2020, 41(3): 464-473. doi: S1872-2067(19)63474-1.","citationCn":"龙泽清,  仙光,  张光明,  张涛,  李雪梅. 超声水热法制备高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料去除染料和药物废水. 催化学报, 2020, 41(3): 464-473. doi: S1872-2067(19)63474-1.","citationEn":"龙泽清,  仙光,  张光明,  张涛,  李雪梅. BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub> nanocomposite with high visible-light photocatalytic activity prepared by an ultrasonic hydrothermal method for removing dye and pharmaceutical. Chinese Journal of Catalysis, 2020, 41(3): 464-473. doi: S1872-2067(19)63474-1.","doi":"S1872-2067(19)63474-1","figContent":"","figList":[],"firstFig":"","fpage":"464","highCitedState":"","htmlCount":77,"htmlFile":"","id":"645f9ff6-099d-41f2-ba44-74bc226ff8c0","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>, 纳米复合材料, 绿色技术, 可见光光催化","keywordCn":"BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>, 纳米复合材料, 绿色技术, 可见光光催化","keywordCnList":["BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>"," 纳米复合材料"," 绿色技术"," 可见光光催化"],"keywordEn":"BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>, Nanocomposite, Green technology, Visible-light photocatalysis","keywordEnList":["BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>"," Nanocomposite"," Green technology"," Visible-light photocatalysis"],"keywordList":["BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>"," 纳米复合材料"," 绿色技术"," 可见光光催化"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"473","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":9,"pdfSize":2056.73,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"超声水热法制备高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料去除染料和药物废水","titleCn":"超声水热法制备高可见光催化活性的BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub>纳米复合材料去除染料和药物废水","titleEn":"BiOCl-Bi<sub>12<\/sub>O<sub>17<\/sub>Cl<sub>2<\/sub> nanocomposite with high visible-light photocatalytic activity prepared by an ultrasonic hydrothermal method for removing dye and pharmaceutical","viewCount":1477,"volume":"41","year":2020},{"abstractInfo":"偶氮类合成色素具有遗传毒性、致癌性和致泻性，而食源性致病菌易引发细菌性感染和食物中毒事件，食品加工过程中产生的色素废水和致病菌废水若未经妥善处理就排入水体，会对水体及环境造成污染，废水中的偶氮类色素和致病菌还会通过食物链对人体健康产生威胁.因此，寻求更为高效、绿色、安全的处理技术和净化材料有效去除食品废水中高污染性和毒害性的偶氮类色素和致病菌显得尤为迫切.<br/>g-C<sub>3<\/sub>N<sub>4<\/sub>是一种具有可见光响应的有机半导体光催化材料，广泛应用于降解污染物、杀灭致病菌、催化有机反应等领域.然而，g-C<sub>3<\/sub>N<sub>4<\/sub>本身存在着比表面积小、光吸收性能差、光氧化能力低以及光生载流子迁移效率低等缺点，限制了其光催化性能.针对上述问题，我们对g-C<sub>3<\/sub>N<sub>4<\/sub>的空间和电子结构进行了设计，将形貌调控、元素掺杂和助催化剂修饰三种改性方法相结合，以获得兼具大比表面积、优异光吸收性能、强氧化能力以及快速光生载流子迁移能力的高活性g-C<sub>3<\/sub>N<sub>4<\/sub>基光催化体系.<br/>本文通过水热法制备了氧掺杂多孔氮化碳（PCNO），通过酸剥离法制备了氧化石墨烯量子点（ox-GQDs），最后通过自组装法将助催化剂ox-GQDs修饰到PCNO上，制备了ox-GQDs/PCNO复合光催化剂.零维的ox-GQDs可以通过氢键、π-π作用和化学键作用，与二维的PCNO实现紧密接触，均匀地分散在PCNO的表面和内部孔道上.由于ox-GQDs独特的上转换特性、电子捕获能力和过氧化物酶活性，ox-GQDs/PCNO复合光催化剂具有比PCNO更佳的光吸收性能、更高的电荷转移效率以及更强的光氧化能力.因此，ox-GQDs/PCNO复合材料在降解偶氮类色素和杀灭致病菌方面均表现出更为优异的可见光催化性能，活性最佳的复合材料ox-GQDs-0.2%/PCNO降解偶氮类色素苋菜红的速率常数约是PCNO的3.1倍，并且该材料能在可见光照射4h内杀灭99.6%的大肠杆菌，远超过PCNO31.9%的抗菌活性.另外，光生空穴、超氧自由基和羟基自由基被证实是ox-GQDs/PCNO体系在光催化反应中产生的活性物种，可以彻底矿化偶氮类色素并有效杀灭致病菌.本研究可以拓展g-C<sub>3<\/sub>N<sub>4<\/sub>基光催化剂在环境净化领域的应用前景，并为阐明ox-GQDs在复合光催化体系中的作用提供新的见解.","abstractInfoCn":"偶氮类合成色素具有遗传毒性、致癌性和致泻性，而食源性致病菌易引发细菌性感染和食物中毒事件，食品加工过程中产生的色素废水和致病菌废水若未经妥善处理就排入水体，会对水体及环境造成污染，废水中的偶氮类色素和致病菌还会通过食物链对人体健康产生威胁.因此，寻求更为高效、绿色、安全的处理技术和净化材料有效去除食品废水中高污染性和毒害性的偶氮类色素和致病菌显得尤为迫切.<br/>g-C<sub>3<\/sub>N<sub>4<\/sub>是一种具有可见光响应的有机半导体光催化材料，广泛应用于降解污染物、杀灭致病菌、催化有机反应等领域.然而，g-C<sub>3<\/sub>N<sub>4<\/sub>本身存在着比表面积小、光吸收性能差、光氧化能力低以及光生载流子迁移效率低等缺点，限制了其光催化性能.针对上述问题，我们对g-C<sub>3<\/sub>N<sub>4<\/sub>的空间和电子结构进行了设计，将形貌调控、元素掺杂和助催化剂修饰三种改性方法相结合，以获得兼具大比表面积、优异光吸收性能、强氧化能力以及快速光生载流子迁移能力的高活性g-C<sub>3<\/sub>N<sub>4<\/sub>基光催化体系.<br/>本文通过水热法制备了氧掺杂多孔氮化碳（PCNO），通过酸剥离法制备了氧化石墨烯量子点（ox-GQDs），最后通过自组装法将助催化剂ox-GQDs修饰到PCNO上，制备了ox-GQDs/PCNO复合光催化剂.零维的ox-GQDs可以通过氢键、π-π作用和化学键作用，与二维的PCNO实现紧密接触，均匀地分散在PCNO的表面和内部孔道上.由于ox-GQDs独特的上转换特性、电子捕获能力和过氧化物酶活性，ox-GQDs/PCNO复合光催化剂具有比PCNO更佳的光吸收性能、更高的电荷转移效率以及更强的光氧化能力.因此，ox-GQDs/PCNO复合材料在降解偶氮类色素和杀灭致病菌方面均表现出更为优异的可见光催化性能，活性最佳的复合材料ox-GQDs-0.2%/PCNO降解偶氮类色素苋菜红的速率常数约是PCNO的3.1倍，并且该材料能在可见光照射4 h内杀灭99.6%的大肠杆菌，远超过PCNO 31.9%的抗菌活性.另外，光生空穴、超氧自由基和羟基自由基被证实是ox-GQDs/PCNO体系在光催化反应中产生的活性物种，可以彻底矿化偶氮类色素并有效杀灭致病菌.本研究可以拓展g-C<sub>3<\/sub>N<sub>4<\/sub>基光催化剂在环境净化领域的应用前景，并为阐明ox-GQDs在复合光催化体系中的作用提供新的见解.","abstractInfoEn":"Oxidized nanoporous g-C<sub>3<\/sub>N<sub>4<\/sub> (PCNO) decorated with graphene oxide quantum dots (ox-GQDs) was successfully prepared by a facile self-assembly method. As co-catalysts, the ultrasmall zero-dimensional (0D) ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO, as well as intimate contact with PCNO through hydrogen bonding, π-π, and chemical bonding interactions. In contrast with PCNO, the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability, higher charge-transfer efficiency, enhanced photooxidation capacity, and increased amounts of reactive species due to the upconversion properties, strong electron capturing ability, and peroxidase-like activity of the ox-GQDs. Therefore, the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced. Remarkably, the composite with a 0.2 wt.% deposited amount of ox-GQDs (ox-GQDs-0.2%/PCNO) exhibited optimum amaranth photodegradation activity, with a corresponding rate about 3.1 times as high as that of PCNO. In addition, ox-GQDs-0.2%/PCNO could inactivate about 99.6% of <i>Escherichia coli<\/i> (<i>E. coli<\/i>) cells after 4 h of visible light irradiation, whereas only~31.9% of <i>E. coli<\/i> cells were killed by PCNO. Furthermore, h<sup>+<\/sup>,&#183;O<sub>2<\/sub><sup>-<\/sup>, and&#183;OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system; these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.","articleNo":"20200310","authorCnList":["徐婧","  黄金","  王周平","  朱永法"],"authorEnList":["Jing Xu","  Jin Huang","  Zhouping Wang","  Yongfa Zhu"],"authorList":["徐婧","  黄金","  王周平","  朱永法"],"authors":"徐婧,  黄金,  王周平,  朱永法","authorsCn":"徐婧,  黄金,  王周平,  朱永法","authorsEn":"Jing Xu,  Jin Huang,  Zhouping Wang,  Yongfa Zhu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"徐婧,  黄金,  王周平,  朱永法. 氧化石墨烯量子点修饰氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>在光催化降解和抗菌中的应用. 催化学报, 2020, 41(3): 474-484. doi: S1872-2067(19)63501-1.","citationCn":"徐婧,  黄金,  王周平,  朱永法. 氧化石墨烯量子点修饰氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>在光催化降解和抗菌中的应用. 催化学报, 2020, 41(3): 474-484. doi: S1872-2067(19)63501-1.","citationEn":"徐婧,  黄金,  王周平,  朱永法. Enhanced visible-light photocatalytic degradation and disinfection performance of oxidized nanoporous g-C<sub>3<\/sub>N<sub>4<\/sub> <i>via<\/i> decoration with graphene oxide quantum dots. Chinese Journal of Catalysis, 2020, 41(3): 474-484. doi: S1872-2067(19)63501-1.","doi":"S1872-2067(19)63501-1","figContent":"","figList":[],"firstFig":"","fpage":"474","highCitedState":"","htmlCount":105,"htmlFile":"","id":"893cc4e3-0b73-4bc9-b5ff-f1cff7f7250a","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"光催化, 氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>, 氧化石墨烯量子点, 降解, 抗菌","keywordCn":"光催化, 氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>, 氧化石墨烯量子点, 降解, 抗菌","keywordCnList":["光催化"," 氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>"," 氧化石墨烯量子点"," 降解"," 抗菌"],"keywordEn":"Photocatalysis, Oxidized nanoporous g-C<sub>3<\/sub>N<sub>4<\/sub>, Graphene oxide quantum dots, Degradation, Disinfection","keywordEnList":["Photocatalysis"," Oxidized nanoporous g-C<sub>3<\/sub>N<sub>4<\/sub>"," Graphene oxide quantum dots"," Degradation"," Disinfection"],"keywordList":["光催化"," 氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>"," 氧化石墨烯量子点"," 降解"," 抗菌"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"484","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":10,"pdfSize":1342.9,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"氧化石墨烯量子点修饰氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>在光催化降解和抗菌中的应用","titleCn":"氧化石墨烯量子点修饰氧掺杂多孔g-C<sub>3<\/sub>N<sub>4<\/sub>在光催化降解和抗菌中的应用","titleEn":"Enhanced visible-light photocatalytic degradation and disinfection performance of oxidized nanoporous g-C<sub>3<\/sub>N<sub>4<\/sub> <i>via<\/i> decoration with graphene oxide quantum dots","viewCount":1157,"volume":"41","year":2020},{"abstractInfo":"共价有机框架（COFs）材料是继金属-有机框架材料之后，在拓扑学基础上发展起来的又一类多孔材料.这类材料是由轻质元素（C，H，O，N，B，Si等）通过可逆共价键连接而成的结晶性有机多孔聚合物，具有比表面积大、骨架密度低、孔道结构规整、可人为设计以及表面易修饰改性等特点，自2005年首次报道以来就引起了人们的广泛关注.经过十多年的发展，COFs材料已经被广泛用于气体吸附/分离、光电、能量存储、非均相催化等研究领域.由于材料的多孔性以及相对稳定的特点，近年来COFs材料作为催化剂或催化剂载体用于多相催化反应已经成为该领域的一个研究热点.但是到目前为止，COFs材料的离子化改性用于异相催化相关研究还相对较少.本文选择二维骨架中含有羟基基团的H<sub>2<\/sub>P-DHPhCOF作为载体，通过两步接枝反应成功地将咪唑型离子液体引入到COF材料的孔道中采用红外光谱、核磁共振、粉末X射线衍射、热失重分析等方法详细地表征了COF材料在后修饰过程中的变化.研究发现，1，4-二溴丁烷与N-甲基咪唑基团的引入占据了部分孔道，导致框架材料的孔径和孔容减小.同时，我们还将该改性后的离子型COF材料在DMSO/盐酸溶液中消解，利用核磁共振波谱计算了离子化程度.实验结果表明，N-甲基咪唑的接枝率约为4.9wt%.在既定的反应条件下，将该离子化的COF材料作为多相催化剂用于CO<sub>2<\/sub>和环氧化合物之间的环加成反应.以环氧氯丙烷作为测试底物，发现该离子型催化剂的催化性能与H<sub>2<\/sub>P-DHPhCOF相比有大副度提高，转化率达到了91%（120℃，24h，CO<sub>2<\/sub>压力位1.0MPa）.在相同的条件下，该催化剂还对其他的环氧化合物具有一定的催化效果，其中环氧丙烷的转化率高达95%，且目标产物碳酸丙烯酯的选择性为100%.然而，对于大分子的环氧化合物，转化率和产率均较低，表明催化剂具有明显的尺寸选择性.此外，我们还以环氧氯丙烷的环加成反应为例考察了催化剂的循环稳定性，经过连续的5次循环，催化剂的催化活性得到了有效保持.我们的研究表明COF材料作为异相催化剂用于多相催化具有潜在的应用前景.而且，由于离子型多孔材料具有可交换的性质，我们可以通过将不同功能的反离子交换到孔道中，从而得到具有不同功能特性的多孔材料.因此，离子化共价有机框架材料是一类集多孔、高比表面积、可人为设计等性质于一体的新型多孔材料，有望应用于更加广泛的研究领域.","abstractInfoCn":"共价有机框架（COFs）材料是继金属-有机框架材料之后，在拓扑学基础上发展起来的又一类多孔材料.这类材料是由轻质元素（C，H，O，N，B，Si等）通过可逆共价键连接而成的结晶性有机多孔聚合物，具有比表面积大、骨架密度低、孔道结构规整、可人为设计以及表面易修饰改性等特点，自2005年首次报道以来就引起了人们的广泛关注.经过十多年的发展，COFs材料已经被广泛用于气体吸附/分离、光电、能量存储、非均相催化等研究领域.由于材料的多孔性以及相对稳定的特点，近年来COFs材料作为催化剂或催化剂载体用于多相催化反应已经成为该领域的一个研究热点.但是到目前为止，COFs材料的离子化改性用于异相催化相关研究还相对较少.本文选择二维骨架中含有羟基基团的H<sub>2<\/sub>P-DHPh COF作为载体，通过两步接枝反应成功地将咪唑型离子液体引入到COF材料的孔道中采用红外光谱、核磁共振、粉末X射线衍射、热失重分析等方法详细地表征了COF材料在后修饰过程中的变化.研究发现，1，4-二溴丁烷与N-甲基咪唑基团的引入占据了部分孔道，导致框架材料的孔径和孔容减小.同时，我们还将该改性后的离子型COF材料在DMSO/盐酸溶液中消解，利用核磁共振波谱计算了离子化程度.实验结果表明，N-甲基咪唑的接枝率约为4.9 wt%.在既定的反应条件下，将该离子化的COF材料作为多相催化剂用于CO<sub>2<\/sub>和环氧化合物之间的环加成反应.以环氧氯丙烷作为测试底物，发现该离子型催化剂的催化性能与H<sub>2<\/sub>P-DHPh COF相比有大副度提高，转化率达到了91%（120℃，24h，CO<sub>2<\/sub>压力位1.0MPa）.在相同的条件下，该催化剂还对其他的环氧化合物具有一定的催化效果，其中环氧丙烷的转化率高达95%，且目标产物碳酸丙烯酯的选择性为100%.然而，对于大分子的环氧化合物，转化率和产率均较低，表明催化剂具有明显的尺寸选择性.此外，我们还以环氧氯丙烷的环加成反应为例考察了催化剂的循环稳定性，经过连续的5次循环，催化剂的催化活性得到了有效保持.我们的研究表明COF材料作为异相催化剂用于多相催化具有潜在的应用前景.而且，由于离子型多孔材料具有可交换的性质，我们可以通过将不同功能的反离子交换到孔道中，从而得到具有不同功能特性的多孔材料.因此，离子化共价有机框架材料是一类集多孔、高比表面积、可人为设计等性质于一体的新型多孔材料，有望应用于更加广泛的研究领域.","abstractInfoEn":"Covalent organic frameworks (COFs), with two dimensional (2D-) or three dimensional (3D-) structures, have accessible open channels or nanopores, with uniform sizes ranging from angstroms to nanometers and have emerged as an excellent and promising platform for designing catalysts or catalyst carriers. Herein, a 2D-COF grafted with a 1-alkyl-3-methylimidazolium-based ionic liquid (AMIMBr@H<sub>2<\/sub>P-DHPh COF) on the channel walls was synthesized and utilized as a highly efficient heterogeneous catalyst for the chemical fixation of CO<sub>2<\/sub> via a reaction with epoxides under solvent-free and co-catalyst-free conditions. The as-synthesized AMIMBr@H<sub>2<\/sub>P-DHPh COF shows excellent catalytic activity in promoting the cycloaddition reactions between epoxide and CO<sub>2<\/sub>; the excellent catalytic activity was maintained for up to five cycles. Advantages like high porosity, functional versatility, easy modification of COFs, and high catalytic activity of ionic liquids, have been realized in a single material.","articleNo":"20200311","authorCnList":["张衍","  胡慧","  居佳","  闫欠欠","  Vasanthakumar Arumugam","  景学超","  蔡华强","  高艳安"],"authorEnList":["Yan Zhang","  Hui Hu","  Jia Ju","  Qianqian Yan","  Vasanthakumar Arumugam","  Xuechao Jing","  Huaqiang Cai","  Yanan Gao"],"authorList":["张衍","  胡慧","  居佳","  闫欠欠","  Vasanthakumar Arumugam","  景学超","  蔡华强","  高艳安"],"authors":"张衍,  胡慧,  居佳,  闫欠欠,  Vasanthakumar Arumugam,  景学超,  蔡华强,  高艳安","authorsCn":"张衍,  胡慧,  居佳,  闫欠欠,  Vasanthakumar Arumugam,  景学超,  蔡华强,  高艳安","authorsEn":"Yan Zhang,  Hui Hu,  Jia Ju,  Qianqian Yan,  Vasanthakumar Arumugam,  Xuechao Jing,  Huaqiang Cai,  Yanan Gao","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"张衍,  胡慧,  居佳,  闫欠欠,  Vasanthakumar Arumugam,  景学超,  蔡华强,  高艳安. 共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究. 催化学报, 2020, 41(3): 485-493. doi: S1872-2067(19)63487-X.","citationCn":"张衍,  胡慧,  居佳,  闫欠欠,  Vasanthakumar Arumugam,  景学超,  蔡华强,  高艳安. 共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究. 催化学报, 2020, 41(3): 485-493. doi: S1872-2067(19)63487-X.","citationEn":"张衍,  胡慧,  居佳,  闫欠欠,  Vasanthakumar Arumugam,  景学超,  蔡华强,  高艳安. Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide. Chinese Journal of Catalysis, 2020, 41(3): 485-493. doi: S1872-2067(19)63487-X.","doi":"S1872-2067(19)63487-X","figContent":"","figList":[],"firstFig":"","fpage":"485","highCitedState":"","htmlCount":84,"htmlFile":"","id":"74af3282-88cc-4865-8e5e-09ab8d468ba0","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"共价有机框架, 离子化, 催化剂, 环加成反应","keywordCn":"共价有机框架, 离子化, 催化剂, 环加成反应","keywordCnList":["共价有机框架"," 离子化"," 催化剂"," 环加成反应"],"keywordEn":"Covalent organic framework, Ionization, CO<sub>2<\/sub>, Cycloaddition","keywordEnList":["Covalent organic framework"," Ionization"," CO<sub>2<\/sub>"," Cycloaddition"],"keywordList":["共价有机框架"," 离子化"," 催化剂"," 环加成反应"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"493","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":9,"pdfSize":1592.73,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究","titleCn":"共价有机框架材料的离子化改性及其催化合成环碳酸酯的性能研究","titleEn":"Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide","viewCount":1057,"volume":"41","year":2020},{"abstractInfo":"甘油是生物柴油生产过程中生成的副产物，随着生物柴油产量的快速增长，甘油的量也迅速增加.据估计，到2020年甘油的产量将比需求量高出6倍.因此，将过剩的甘油转化为其它更有价值的化学品具有重要意义.<br/>在已经发表的文献中，各种碳材料负载的Pt催化剂被广泛应用于液相中甘油的选择性氧化.但是，由于Pt纳米颗粒与碳载体之间相互作用较弱，因此Pt纳米颗粒易团聚和流失，而且Pt的过度氧化和有机羧酸的强吸附也导致Pt催化剂失活.最近的研究表明，采用含氮的碳载体可以增强Pt与载体间的相互作用，这种载体还有可能将电子转移给Pt，从而有效提高Pt的分散度、活性和稳定性.与此同时，引入其它金属如Co，Cu，Bi，Sb等与Pt形成合金也能有效改善催化剂的活性和稳定性.我们在前期工作中曾经发现多壁碳纳米管（MWCNTs）负载的PtSb合金在甘油氧化反应中具有很高的活性和二羟基丙酮选择性，可以抑制C-C裂解，并提高了催化剂的稳定性.但是在MWCNTs上组装PtSb颗粒的过程繁琐且危险，需要对载体进行氧化（浓硝酸）、嫁接硫醇、浸渍金属、高温还原等，同时MWCNTs的价格也较高.<br/>本文采用简单的热解方法将氮和锑同时引入到碳基载体中，并用此载体制备了具有核壳结构的Sb@PtSb<sub>2<\/sub>/NC催化剂.首先将葡萄糖、三聚氰胺和SbCl<sub>3<\/sub>混合后在氮气中于700℃热解得到含Sb和N的多孔碳载体，再通过浸渍还原法将Pt还原并负载到该载体上即得到具有核壳结构的Sb@PtSb<sub>2<\/sub>/NC催化剂.该催化剂对催化甘油氧化具有较高的活性，同时具有较好的稳定性.氮气吸附表征表明，引入N和Sb都能提高载体的比表面积和孔体积，其中Sb的引入使得催化剂表面形成了多孔结构（SEM表征）.XRD、TEM和EDS表征证明了具有核壳结构的Sb@PtSb<sub>2<\/sub>颗粒在载体表面上的生成.Raman光谱表明N和Sb的引入增加了碳缺陷，有可能带来新的活性位点.O<sub>2<\/sub>-TPD表征表明Sb@PtSb<sub>2<\/sub>/NC对氧的吸附量远高于Pt/NC，这可能归因于PtSb<sub>2<\/sub>合金中Pt-Sb金属间的原子间距增大，有利于氧的吸附和表面扩散，从而显著提高了催化剂活性.XPS表征表明了从N到Pt的电子转移，而这种富含电子的Pt具有更高的活性.将制备的催化剂用于考评催化甘油氧化的活性，发现相比于Pt/NC，Sb@PtSb<sub>2<\/sub>/NC催化剂催化甘油氧化具有显著增加的活性，二羟基丙酮选择性也明显提高，在60℃，0.6MPaO<sub>2<\/sub>气氛下，100mg催化剂与5mL0.2g/mL甘油水溶液反应3h得到了65.3%的甘油转化率，以及39.2%的二羟基丙酮选择性和51.8%的甘油酸选择性.这可能归因于载体比表面积的增加、更多的碳缺陷，以及PtSb<sub>2<\/sub>合金的形成.使用五次后的催化剂仍保持较高的催化活性，证实了该催化剂具有较好的稳定性.","abstractInfoCn":"甘油是生物柴油生产过程中生成的副产物，随着生物柴油产量的快速增长，甘油的量也迅速增加.据估计，到2020年甘油的产量将比需求量高出6倍.因此，将过剩的甘油转化为其它更有价值的化学品具有重要意义.<br/>在已经发表的文献中，各种碳材料负载的Pt催化剂被广泛应用于液相中甘油的选择性氧化.但是，由于Pt纳米颗粒与碳载体之间相互作用较弱，因此Pt纳米颗粒易团聚和流失，而且Pt的过度氧化和有机羧酸的强吸附也导致Pt催化剂失活.最近的研究表明，采用含氮的碳载体可以增强Pt与载体间的相互作用，这种载体还有可能将电子转移给Pt，从而有效提高Pt的分散度、活性和稳定性.与此同时，引入其它金属如Co，Cu，Bi，Sb等与Pt形成合金也能有效改善催化剂的活性和稳定性.我们在前期工作中曾经发现多壁碳纳米管（MWCNTs）负载的PtSb合金在甘油氧化反应中具有很高的活性和二羟基丙酮选择性，可以抑制C-C裂解，并提高了催化剂的稳定性.但是在MWCNTs上组装PtSb颗粒的过程繁琐且危险，需要对载体进行氧化（浓硝酸）、嫁接硫醇、浸渍金属、高温还原等，同时MWCNTs的价格也较高.<br/>本文采用简单的热解方法将氮和锑同时引入到碳基载体中，并用此载体制备了具有核壳结构的Sb@PtSb<sub>2<\/sub>/NC催化剂.首先将葡萄糖、三聚氰胺和SbCl<sub>3<\/sub>混合后在氮气中于700℃热解得到含Sb和N的多孔碳载体，再通过浸渍还原法将Pt还原并负载到该载体上即得到具有核壳结构的Sb@PtSb<sub>2<\/sub>/NC催化剂.该催化剂对催化甘油氧化具有较高的活性，同时具有较好的稳定性.氮气吸附表征表明，引入N和Sb都能提高载体的比表面积和孔体积，其中Sb的引入使得催化剂表面形成了多孔结构（SEM表征）.XRD、TEM和EDS表征证明了具有核壳结构的Sb@PtSb<sub>2<\/sub>颗粒在载体表面上的生成.Raman光谱表明N和Sb的引入增加了碳缺陷，有可能带来新的活性位点.O<sub>2<\/sub>-TPD表征表明Sb@PtSb<sub>2<\/sub>/NC对氧的吸附量远高于Pt/NC，这可能归因于PtSb<sub>2<\/sub>合金中Pt-Sb金属间的原子间距增大，有利于氧的吸附和表面扩散，从而显著提高了催化剂活性.XPS表征表明了从N到Pt的电子转移，而这种富含电子的Pt具有更高的活性.将制备的催化剂用于考评催化甘油氧化的活性，发现相比于Pt/NC，Sb@PtSb<sub>2<\/sub>/NC催化剂催化甘油氧化具有显著增加的活性，二羟基丙酮选择性也明显提高，在60℃，0.6MPa O<sub>2<\/sub>气氛下，100mg催化剂与5mL 0.2g/mL甘油水溶液反应3h得到了65.3%的甘油转化率，以及39.2%的二羟基丙酮选择性和51.8%的甘油酸选择性.这可能归因于载体比表面积的增加、更多的碳缺陷，以及PtSb<sub>2<\/sub>合金的形成.使用五次后的催化剂仍保持较高的催化活性，证实了该催化剂具有较好的稳定性.","abstractInfoEn":"Selective oxidation of glycerol with molecular oxygen in base-free aqueous solutions has become a hot topic, as the rapidly increasing production of biodiesel is creating a surplus of glycerol. In this work, an N-doped-carbon-supported core-shell structured Sb@PtSb<sub>2<\/sub> hybrid catalyst was prepared via a facile synthesis route, in which a mixture of glucose, melamine, and SbCl<sub>3<\/sub> (Sb-NC) was pyrolyzed, then impregnated with Pt by immersion in an aqueous solution of H<sub>2<\/sub>PtCl<sub>6<\/sub>, and further treated in hydrogen flow. Characterization of the catalyst products indicated that introducing SbCl<sub>3<\/sub> can increase the surface area of the binary glucose + melamine pyrolyzed support (NC), and Sb@PtSb<sub>2<\/sub> hybrids could be formed on the surface of an Sb-NC support during hydrogen treatment at 700℃. It was found that the Sb@PtSb<sub>2<\/sub>/NC catalyst was more active for the selective oxidation of glycerol in a base-free aqueous solution than Sb-free NC-supported Pt (Pt/NC). Further characterization also indicated that the promising performance of Sb@PtSb<sub>2<\/sub>/NC might be attributed to its enhanced oxygen activation.","articleNo":"20200312","authorCnList":["杨丽华","  何天衢","  赖楚钧","  陈平","  侯昭胤"],"authorEnList":["Lihua Yang","  Tianqu He","  Chujun Lai","  Ping Chen","  Zhaoyin Hou"],"authorList":["杨丽华","  何天衢","  赖楚钧","  陈平","  侯昭胤"],"authors":"杨丽华,  何天衢,  赖楚钧,  陈平,  侯昭胤","authorsCn":"杨丽华,  何天衢,  赖楚钧,  陈平,  侯昭胤","authorsEn":"Lihua Yang,  Tianqu He,  Chujun Lai,  Ping Chen,  Zhaoyin Hou","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"杨丽华,  何天衢,  赖楚钧,  陈平,  侯昭胤. 氮掺杂碳负载Sb@PtSb<sub>2<\/sub>催化剂的制备及其在甘油选择性氧化反应中的应用. 催化学报, 2020, 41(3): 494-502. doi: S1872-2067(19)63476-5.","citationCn":"杨丽华,  何天衢,  赖楚钧,  陈平,  侯昭胤. 氮掺杂碳负载Sb@PtSb<sub>2<\/sub>催化剂的制备及其在甘油选择性氧化反应中的应用. 催化学报, 2020, 41(3): 494-502. doi: S1872-2067(19)63476-5.","citationEn":"杨丽华,  何天衢,  赖楚钧,  陈平,  侯昭胤. Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb<sub>2<\/sub> hybrid. Chinese Journal of Catalysis, 2020, 41(3): 494-502. doi: S1872-2067(19)63476-5.","doi":"S1872-2067(19)63476-5","figContent":"","figList":[],"firstFig":"","fpage":"494","highCitedState":"","htmlCount":169,"htmlFile":"","id":"8870d38b-8bb9-4862-b377-d5933648c13a","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"甘油, 氧化, 无碱溶液, Sb@PtSb<sub>2<\/sub>, 合金","keywordCn":"甘油, 氧化, 无碱溶液, Sb@PtSb<sub>2<\/sub>, 合金","keywordCnList":["甘油"," 氧化"," 无碱溶液"," Sb@PtSb<sub>2<\/sub>"," 合金"],"keywordEn":"Glycerol, Oxidation, Base-free solution, Sb@PtSb<sub>2<\/sub>, Alloy","keywordEnList":["Glycerol"," Oxidation"," Base-free solution"," Sb@PtSb<sub>2<\/sub>"," Alloy"],"keywordList":["甘油"," 氧化"," 无碱溶液"," Sb@PtSb<sub>2<\/sub>"," 合金"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"502","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":10,"pdfSize":1696.08,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"氮掺杂碳负载Sb@PtSb<sub>2<\/sub>催化剂的制备及其在甘油选择性氧化反应中的应用","titleCn":"氮掺杂碳负载Sb@PtSb<sub>2<\/sub>催化剂的制备及其在甘油选择性氧化反应中的应用","titleEn":"Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb<sub>2<\/sub> hybrid","viewCount":1254,"volume":"41","year":2020},{"abstractInfo":"高级氧化工艺（AOPs）是一种处理有机污染物的极具吸引力的技术.大量的前期研究工作集中在通过芬顿反应（Fenton）降解有机污染物.然而，芬顿反应需要在酸性条件下进行，必须在其过程中进行预处理.同时，反应后产生的含铁污泥需要进一步处理以满足排放要求，从而限制了芬顿反应的发展.作为另一种AOPs，光催化技术因反应条件温和、操作简单和选择性好等优点受到广泛关注.研究表明，各种铁基和铜半导体光催化材料形成光-芬顿（Photo-Fenton）系统，可有效解决芬顿反应中高价金属离子/低价金属离子的循环问题.为了充分利用芬顿氧化技术和光催化氧化技术在降解有机污染物方面的各自优势，构建具有宽太阳光谱响应的新型光芬顿催化剂具有重要意义.<br/>由于其独特的层状结构和优越的有机物光催化性能，Bi<sub>2<\/sub>WO<sub>6<\/sub>作为结构最为简单的钙钛矿型层状氧化物，其禁带宽度为2.6-2.8eV，可响应可见光，已成研究最多的光催化材料之一.研究表明，将Bi<sub>2<\/sub>WO<sub>6<\/sub>与合适的助催化剂耦合以构建异质结是提高光生载流子分离效率、拓宽Bi<sub>2<\/sub>WO<sub>6<\/sub>可见光响应范围的一种有效策略.在众多的窄带隙半导体助催化材料中，Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>作为一种p-型窄带隙半导体，可以响应可见光甚至近红外光.近年来，已经广泛报道了Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>可以作为与其他半导体光催化剂进行结合以提高光催化活性的有效助催化剂.<br/>在本文中，新型Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>（CZTS/BWO）异质结构通过简单的二次溶剂热法构建.异质结的成功形成得到了一系列表征方法的证实，比如XPS和HR-TEM.光催化活性结果表明，制备的CZTS/BWO异质结对有机污染物的降解具有优异的光催化性能，特别是当CZTS相对于异质结中BWO的质量分数为2%时.此外，加入过氧化氢（H<sub>2<\/sub>O<sub>2<\/sub>）可进一步提高染料和抗生素的降解效率.增强的光催化和光芬顿降解性能主要是由于BWO的引入，其提供了更多的活性位点，扩展了太阳光谱响应范围并加速了Cu（II）/Cu（I）的循环.催化剂的催化活性在经过四次循环实验后并没有显著降低.最终我们合理假设了光催化和光-芬顿催化机理.本项研究可为设计新型光-芬顿催化剂提供新的视角，即共同利用光催化活性和芬顿活性进行废水中残留有机物的净化.","abstractInfoCn":"高级氧化工艺（AOPs）是一种处理有机污染物的极具吸引力的技术.大量的前期研究工作集中在通过芬顿反应（Fenton）降解有机污染物.然而，芬顿反应需要在酸性条件下进行，必须在其过程中进行预处理.同时，反应后产生的含铁污泥需要进一步处理以满足排放要求，从而限制了芬顿反应的发展.作为另一种AOPs，光催化技术因反应条件温和、操作简单和选择性好等优点受到广泛关注.研究表明，各种铁基和铜半导体光催化材料形成光-芬顿（Photo-Fenton）系统，可有效解决芬顿反应中高价金属离子/低价金属离子的循环问题.为了充分利用芬顿氧化技术和光催化氧化技术在降解有机污染物方面的各自优势，构建具有宽太阳光谱响应的新型光芬顿催化剂具有重要意义.<br/>由于其独特的层状结构和优越的有机物光催化性能，Bi<sub>2<\/sub>WO<sub>6<\/sub>作为结构最为简单的钙钛矿型层状氧化物，其禁带宽度为2.6-2.8eV，可响应可见光，已成研究最多的光催化材料之一.研究表明，将Bi<sub>2<\/sub>WO<sub>6<\/sub>与合适的助催化剂耦合以构建异质结是提高光生载流子分离效率、拓宽Bi<sub>2<\/sub>WO<sub>6<\/sub>可见光响应范围的一种有效策略.在众多的窄带隙半导体助催化材料中，Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>作为一种p-型窄带隙半导体，可以响应可见光甚至近红外光.近年来，已经广泛报道了Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>可以作为与其他半导体光催化剂进行结合以提高光催化活性的有效助催化剂.<br/>在本文中，新型Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>（CZTS/BWO）异质结构通过简单的二次溶剂热法构建.异质结的成功形成得到了一系列表征方法的证实，比如XPS和HR-TEM.光催化活性结果表明，制备的CZTS/BWO异质结对有机污染物的降解具有优异的光催化性能，特别是当CZTS相对于异质结中BWO的质量分数为2%时.此外，加入过氧化氢（H<sub>2<\/sub>O<sub>2<\/sub>）可进一步提高染料和抗生素的降解效率.增强的光催化和光芬顿降解性能主要是由于BWO的引入，其提供了更多的活性位点，扩展了太阳光谱响应范围并加速了Cu（II）/Cu（I）的循环.催化剂的催化活性在经过四次循环实验后并没有显著降低.最终我们合理假设了光催化和光-芬顿催化机理.本项研究可为设计新型光-芬顿催化剂提供新的视角，即共同利用光催化活性和芬顿活性进行废水中残留有机物的净化.","abstractInfoEn":"In this work, a set of novel Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub> (CZTS/BWO) two-dimensional (2D)/two-dimensional (2D) type-II heterojunctions with different CZTS weight ratios (1%, 2%, and 5%) were successfully synthesized via a brief secondary solvothermal process. The successful formation of the heterojunctions was affirmed by characterization methods such as X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The photocatalytic activity results showed that the prepared CZTS/BWO heterojunctions had excellent photocatalytic behaviors for organic degradation, especially when the mass fraction of CZTS with respect to BWO in the composite was 2%. Moreover, the addition of hydrogen peroxide (H<sub>2<\/sub>O<sub>2<\/sub>) could further improve the dye and antibiotic degradation efficiencies. The reinforced photocatalytic and photo-Fenton degradation performance were primarily attributable to the introduction of BWO, which afforded increased active sites, expanded the solar spectral response range, and accelerated the cycle of Cu(II)/Cu(I); after four cycling times, its catalytic activity did not decrease significantly. In addition, reasonable hypotheses of the photocatalytic and photo-Fenton catalytic mechanisms were formulated. This study is expected to provide a visual approach for designing a novel photo-Fenton catalyst to jointly utilize the photocatalytic and Fenton activities, which can be better applied to the purification of residual organics in wastewater.","articleNo":"20200313","authorCnList":["郭莉","  张开来","  韩宣宣","  赵强","  张媛媛","  戚勉","  王丹军","  付峰"],"authorEnList":["Li Guo","  Kailai Zhang","  Xuanxuan Han","  Qiang Zhao","  Yuanyuan Zhang","  Mian Qi","  Danjun Wang","  Feng Fu"],"authorList":["郭莉","  张开来","  韩宣宣","  赵强","  张媛媛","  戚勉","  王丹军","  付峰"],"authors":"郭莉,  张开来,  韩宣宣,  赵强,  张媛媛,  戚勉,  王丹军,  付峰","authorsCn":"郭莉,  张开来,  韩宣宣,  赵强,  张媛媛,  戚勉,  王丹军,  付峰","authorsEn":"Li Guo,  Kailai Zhang,  Xuanxuan Han,  Qiang Zhao,  Yuanyuan Zhang,  Mian Qi,  Danjun Wang,  Feng Fu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"郭莉,  张开来,  韩宣宣,  赵强,  张媛媛,  戚勉,  王丹军,  付峰. 具有可见光增强芬顿活性的II型2D/2D Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>异质结. 催化学报, 2020, 41(3): 503-513. doi: S1872-2067(19)63524-2.","citationCn":"郭莉,  张开来,  韩宣宣,  赵强,  张媛媛,  戚勉,  王丹军,  付峰. 具有可见光增强芬顿活性的II型2D/2D Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>异质结. 催化学报, 2020, 41(3): 503-513. doi: S1872-2067(19)63524-2.","citationEn":"郭莉,  张开来,  韩宣宣,  赵强,  张媛媛,  戚勉,  王丹军,  付峰. 2D/2D type-II Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub> heterojunctions to promote visible-light-driven photo-Fenton catalytic activity. Chinese Journal of Catalysis, 2020, 41(3): 503-513. doi: S1872-2067(19)63524-2.","doi":"S1872-2067(19)63524-2","figContent":"","figList":[],"firstFig":"","fpage":"503","highCitedState":"","htmlCount":38,"htmlFile":"","id":"1dba1b35-a048-4433-a697-7ec51df7bedc","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>, Bi<sub>2<\/sub>WO<sub>6<\/sub>, 2D/2D异质结, 光芬顿, 光催化","keywordCn":"Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>, Bi<sub>2<\/sub>WO<sub>6<\/sub>, 2D/2D异质结, 光芬顿, 光催化","keywordCnList":["Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>"," Bi<sub>2<\/sub>WO<sub>6<\/sub>"," 2D/2D异质结"," 光芬顿"," 光催化"],"keywordEn":"Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>, Bi<sub>2<\/sub>WO<sub>6<\/sub>, 2D/2D type-II heterojunction, Photo-Fenton, Photocatalysis","keywordEnList":["Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>"," Bi<sub>2<\/sub>WO<sub>6<\/sub>"," 2D/2D type-II heterojunction"," Photo-Fenton"," Photocatalysis"],"keywordList":["Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>"," Bi<sub>2<\/sub>WO<sub>6<\/sub>"," 2D/2D异质结"," 光芬顿"," 光催化"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"513","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":2,"pdfSize":1680.34,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"具有可见光增强芬顿活性的II型2D/2D Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>异质结","titleCn":"具有可见光增强芬顿活性的II型2D/2D Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub>异质结","titleEn":"2D/2D type-II Cu<sub>2<\/sub>ZnSnS<sub>4<\/sub>/Bi<sub>2<\/sub>WO<sub>6<\/sub> heterojunctions to promote visible-light-driven photo-Fenton catalytic activity","viewCount":1125,"volume":"41","year":2020},{"abstractInfo":"作为温室效应的主要气体CO<sub>2<\/sub>浓度持续上升，已经成为全球环境问题.将CO<sub>2<\/sub>光催化还原成可再生能源不仅可以解决CO<sub>2<\/sub>带来的温室效应，而且可以将太阳能转化为燃料物质而取代传统意义上的化石能源.实际上光催化的研究可以追溯到1979年，自从Inoue首次报道了光催化CO<sub>2<\/sub>和水制取甲酸、甲烷等有机物，人们一直在努力开发高效的CO<sub>2<\/sub>转化光催化剂.近年来，随着光催化技术的快速稳定发展，各种半导体光催化剂，如Zn<sub>2<\/sub>GeO<sub>4<\/sub>，CdS，Fe<sub>3<\/sub>O<sub>4<\/sub>，g-C<sub>3<\/sub>N<sub>4<\/sub>和SrTiO<sub>3<\/sub>等，已被开发用于光催化还原二氧化碳.在这些半导体中，有的材料具有较大的带隙导致较低的可见光活性，有的材料具有毒性引起额外的环境问题.因此，寻求具有适度带隙且环境友好的半导体材料是解决全球变暖问题的关键.<br/>近年来，g-C<sub>3<\/sub>N<sub>4<\/sub>因其带隙（约2.7eV）较窄，具有一定的可见光吸收性能，无污染，以及化学和热稳定性良好等特点，被视为理想的可见光响应光催化材料之一.但是，g-C<sub>3<\/sub>N<sub>4<\/sub>光吸收有限、光生电子空穴复合率较高等缺点严重限制了其光催化活性.为了进一步提高g-C<sub>3<\/sub>N<sub>4<\/sub>的CO<sub>2<\/sub>可见光催化还原活性，国内外研究者开发了许多方法来提高电荷分离效率，进而提高g-C<sub>3<\/sub>N<sub>4<\/sub>光催化剂的总体活性.在这些策略中，将g-C<sub>3<\/sub>N<sub>4<\/sub>与具有合适导带位置的其他材料偶联以促进电子空穴分离是提高光催化性能的有效方法之一.由于Co-MOF具有较窄的带隙且导带位置与g-C<sub>3<\/sub>N<sub>4<\/sub>匹配，我们选择Co-MOF与g-C<sub>3<\/sub>N<sub>4<\/sub>复合来克服g-C<sub>3<\/sub>N<sub>4<\/sub>的缺点，进而达到提高其光催化活性的目的.<br/>作为电子供体的Co-MOF能够将最低未占分子轨道（LUMO）上的光生电子转移到g-C<sub>3<\/sub>N<sub>4<\/sub>的导带以促进电荷分离，同时水被g-C<sub>3<\/sub>N<sub>4<\/sub>价带上的空穴氧化，最终生成氧气，从而提高光催化还原CO<sub>2<\/sub>的性能.制备的Co-MOF/g-C<sub>3<\/sub>N<sub>4<\/sub>纳米复合材料在可见光照射下具有优异的光催化还原CO<sub>2<\/sub>性能，约为纯g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化活性的2倍.一系列分析表明，Co-MOF的引入不仅拓宽了可见光的吸收范围，而且促进了电荷分离，有利于提高g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化活性.特别是在590nm单波长照射下进行的羟基自由基实验进一步证明了Co-MOF的LUMO上的光生电子可以转移到g-C<sub>3<\/sub>N<sub>4<\/sub>.该研究结果为基于g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化体系的合理构建提供了新思路.","abstractInfoCn":"作为温室效应的主要气体CO<sub>2<\/sub>浓度持续上升，已经成为全球环境问题.将CO<sub>2<\/sub>光催化还原成可再生能源不仅可以解决CO<sub>2<\/sub>带来的温室效应，而且可以将太阳能转化为燃料物质而取代传统意义上的化石能源.实际上光催化的研究可以追溯到1979年，自从Inoue首次报道了光催化CO<sub>2<\/sub>和水制取甲酸、甲烷等有机物，人们一直在努力开发高效的CO<sub>2<\/sub>转化光催化剂.近年来，随着光催化技术的快速稳定发展，各种半导体光催化剂，如Zn<sub>2<\/sub>GeO<sub>4<\/sub>，CdS，Fe<sub>3<\/sub>O<sub>4<\/sub>，g-C<sub>3<\/sub>N<sub>4<\/sub>和SrTiO<sub>3<\/sub>等，已被开发用于光催化还原二氧化碳.在这些半导体中，有的材料具有较大的带隙导致较低的可见光活性，有的材料具有毒性引起额外的环境问题.因此，寻求具有适度带隙且环境友好的半导体材料是解决全球变暖问题的关键.<br/>近年来，g-C<sub>3<\/sub>N<sub>4<\/sub>因其带隙（约2.7 eV）较窄，具有一定的可见光吸收性能，无污染，以及化学和热稳定性良好等特点，被视为理想的可见光响应光催化材料之一.但是，g-C<sub>3<\/sub>N<sub>4<\/sub>光吸收有限、光生电子空穴复合率较高等缺点严重限制了其光催化活性.为了进一步提高g-C<sub>3<\/sub>N<sub>4<\/sub>的CO<sub>2<\/sub>可见光催化还原活性，国内外研究者开发了许多方法来提高电荷分离效率，进而提高g-C<sub>3<\/sub>N<sub>4<\/sub>光催化剂的总体活性.在这些策略中，将g-C<sub>3<\/sub>N<sub>4<\/sub>与具有合适导带位置的其他材料偶联以促进电子空穴分离是提高光催化性能的有效方法之一.由于Co-MOF具有较窄的带隙且导带位置与g-C<sub>3<\/sub>N<sub>4<\/sub>匹配，我们选择Co-MOF与g-C<sub>3<\/sub>N<sub>4<\/sub>复合来克服g-C<sub>3<\/sub>N<sub>4<\/sub>的缺点，进而达到提高其光催化活性的目的.<br/>作为电子供体的Co-MOF能够将最低未占分子轨道（LUMO）上的光生电子转移到g-C<sub>3<\/sub>N<sub>4<\/sub>的导带以促进电荷分离，同时水被g-C<sub>3<\/sub>N<sub>4<\/sub>价带上的空穴氧化，最终生成氧气，从而提高光催化还原CO<sub>2<\/sub>的性能.制备的Co-MOF/g-C<sub>3<\/sub>N<sub>4<\/sub>纳米复合材料在可见光照射下具有优异的光催化还原CO<sub>2<\/sub>性能，约为纯g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化活性的2倍.一系列分析表明，Co-MOF的引入不仅拓宽了可见光的吸收范围，而且促进了电荷分离，有利于提高g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化活性.特别是在590 nm单波长照射下进行的羟基自由基实验进一步证明了Co-MOF的LUMO上的光生电子可以转移到g-C<sub>3<\/sub>N<sub>4<\/sub>.该研究结果为基于g-C<sub>3<\/sub>N<sub>4<\/sub>的光催化体系的合理构建提供了新思路.","abstractInfoEn":"A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride (g-C<sub>3<\/sub>N<sub>4<\/sub>) nanosheets for CO<sub>2<\/sub> reduction via coupling with the electron donor Co-metal-organic framework (MOF) is proposed in this study. Specifically, Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital (LUMO) to the conduction band of g-C<sub>3<\/sub>N<sub>4<\/sub> to facilitate charge separation. As expected, the prepared Co-MOF/g-C<sub>3<\/sub>N<sub>4<\/sub> nanocomposites display excellent visible-light-driven photocatalytic CO<sub>2<\/sub> reduction activities. The CO production rate of 6.75 &micro;mol g<sup>-1<\/sup> h<sup>-1<\/sup> and CH<sub>4<\/sub> evolution rate of 5.47 &micro;mol g<sup>-1<\/sup> h<sup>-1<\/sup> are obtained, which are approximately 2 times those obtained with the original g-C<sub>3<\/sub>N<sub>4<\/sub> under the same conditions. Based on a series of analyses, it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation, which improves the photocatalytic activity of g-C<sub>3<\/sub>N<sub>4<\/sub> to a higher level. In particular, the hydroxyl radical (&#183;OH) experiment was operated under 590 nm (single-wavelength) irradiation, which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C<sub>3<\/sub>N<sub>4<\/sub>. This work may provide an important strategy for the design of highly efficient g-C<sub>3<\/sub>N<sub>4<\/sub>-based photocatalysts for CO<sub>2<\/sub> reduction.","articleNo":"20200314","authorCnList":["陈秋雨","  李思佳","  许宏一","  王国凤","  曲阳","  朱培芬","  王定胜"],"authorEnList":["Qiuyu Chen","  Sijia Li","  Hongyi Xu","  Guofeng Wang","  Yang Qu","  Peifen Zhu","  Dingsheng Wang"],"authorList":["陈秋雨","  李思佳","  许宏一","  王国凤","  曲阳","  朱培芬","  王定胜"],"authors":"陈秋雨,  李思佳,  许宏一,  王国凤,  曲阳,  朱培芬,  王定胜","authorsCn":"陈秋雨,  李思佳,  许宏一,  王国凤,  曲阳,  朱培芬,  王定胜","authorsEn":"Qiuyu Chen,  Sijia Li,  Hongyi Xu,  Guofeng Wang,  Yang Qu,  Peifen Zhu,  Dingsheng Wang","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"陈秋雨,  李思佳,  许宏一,  王国凤,  曲阳,  朱培芬,  王定胜. Co-MOF作为电子供体用于提高g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片的可见光催化还原CO<sub>2<\/sub>性能. 催化学报, 2020, 41(3): 514-523. doi: S1872-2067(19)63497-2.","citationCn":"陈秋雨,  李思佳,  许宏一,  王国凤,  曲阳,  朱培芬,  王定胜. Co-MOF作为电子供体用于提高g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片的可见光催化还原CO<sub>2<\/sub>性能. 催化学报, 2020, 41(3): 514-523. doi: S1872-2067(19)63497-2.","citationEn":"陈秋雨,  李思佳,  许宏一,  王国凤,  曲阳,  朱培芬,  王定胜. Co-MOF as an electron donor for promoting visible-light photoactivities of g-C<sub>3<\/sub>N<sub>4<\/sub> nanosheets for CO<sub>2<\/sub> reduction. Chinese Journal of Catalysis, 2020, 41(3): 514-523. doi: S1872-2067(19)63497-2.","doi":"S1872-2067(19)63497-2","figContent":"","figList":[],"firstFig":"","fpage":"514","highCitedState":"","htmlCount":540,"htmlFile":"","id":"f61b2a1d-2bf3-424c-a1cb-9013ef21d88a","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"Co-MOF, g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片, 电荷分离, 可见光活性, 光催化还原二氧化碳","keywordCn":"Co-MOF, g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片, 电荷分离, 可见光活性, 光催化还原二氧化碳","keywordCnList":["Co-MOF"," g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片"," 电荷分离"," 可见光活性"," 光催化还原二氧化碳"],"keywordEn":"Co-MOF, g-C<sub>3<\/sub>N<sub>4<\/sub> nanosheets, Charge separation, Visible-light photoactivity, Photocatalytic CO<sub>2<\/sub> conversion","keywordEnList":["Co-MOF"," g-C<sub>3<\/sub>N<sub>4<\/sub> nanosheets"," Charge separation"," Visible-light photoactivity"," Photocatalytic CO<sub>2<\/sub> conversion"],"keywordList":["Co-MOF"," g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片"," 电荷分离"," 可见光活性"," 光催化还原二氧化碳"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"523","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":30,"pdfSize":1174.42,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"Co-MOF作为电子供体用于提高g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片的可见光催化还原CO<sub>2<\/sub>性能","titleCn":"Co-MOF作为电子供体用于提高g-C<sub>3<\/sub>N<sub>4<\/sub>纳米片的可见光催化还原CO<sub>2<\/sub>性能","titleEn":"Co-MOF as an electron donor for promoting visible-light photoactivities of g-C<sub>3<\/sub>N<sub>4<\/sub> nanosheets for CO<sub>2<\/sub> reduction","viewCount":2464,"volume":"41","year":2020},{"abstractInfo":"单原子催化剂具有独特的结构位点，能最大化利用贵金属原子，在一系列化学转化反应中具有优异的活性和选择性.但单原子的稳定性是单原子催化剂应用的一个挑战，特别是还原气氛下单原子的稳定性，这极大地限制了单原子催化剂在加氢、脱氢和氢解反应中的应用.理解还原气氛下单原子的稳定机制和单原子催化剂活化氢气的反应机理对于扩大单原子催化剂的应用非常重要.Pt/WO<sub><i>x<\/i><\/sub>（2<<i>x<\/i><3）是一种典型的金属-载体强相互作用体系，在甘油氢解制1，3-丙二醇等一系列含氢反应中具有优异的活性和选择性.但原子层面的催化反应机理，如Pt单原子在表面的位置、Pt单原子的稳定机理以及氢气在单原子上活化产生原位Br&#248;nsted酸的机制仍不清楚.<br/>在本研究中，我们结合密度泛函理论（DFT）和实验表征研究了WO<sub><i>x<\/i><\/sub>负载Pt、Pd、Au三种单原子的稳定性和解离氢气的活性.DFT计算结果表明，在还原气氛下Pt单原子能促进氧化钨表面形成桥式氧空位.WO<sub><i>x<\/i><\/sub>表面的氧空位对于Pt单原子的稳定非常重要，氧空位通过转移部分电子给Pt，使Pt单原子带部分负电从而高效地稳定Pt单原子.不同于带正电单原子的非均相解离氢气，带部分负电的Pt单原子保持一定的金属性，能类似金属表面均相解离H<sub>2<\/sub>产生金属氢物种（Pt-H）.同时Pt解离的H原子能容易地扩散到氧化钨载体上形成原位Br&#248;nsted酸，从而使Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化剂具有双功能催化性质.考察了Pt、Pd、Au三种单原子在WO<sub><i>x<\/i><\/sub>（001）表面的稳定性，三种单原子的稳定性顺序为Pt>Pd>Au.氢气能在Pd和WO<sub><i>x<\/i><\/sub>界面非均相解离，而Au/WO<sub><i>x<\/i><\/sub>不能活化、解离氢气.<br/>我们进一步采用实验表征验证了DFT理论计算的结果.实验合成了WO<sub><i>x<\/i><\/sub>负载的Pt、Pd、Au三种催化剂，X射线衍射（XRD）和透射电子显微镜（TEM）结果表明，Pt能在WO<sub><i>x<\/i><\/sub>表面原子级分散和稳定，而Pd在WO<sub><i>x<\/i><\/sub>表面形成较小的纳米颗粒，Au形成较大的纳米颗粒.采用氢气化学吸附研究了三种催化剂对氢气的活化能力，结果表明三种催化剂的氢气活化能力顺序为Pt/WO<sub><i>x<\/i><\/sub>（137μmol/g-Pt）>Pd/WO<sub><i>x<\/i><\/sub>（43μmol/g-Pd）>>Au/WO<sub><i>x<\/i><\/sub>（4μmol/g-Au）.将三种催化剂用于甘油选择性氢解制备1，3-丙二醇的反应中，只有Pt/WO<sub><i>x<\/i><\/sub>催化剂对甘油氢解具有优异的活性和选择性.从而实验证实了氢气气氛下原位产生的Br&#248;nsted酸具有关键作用和Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化剂具有双功能催化性质.<br/>我们的研究不仅解释了还原气氛下金属单原子在氧化物表面的稳定机理，而且对单原子催化剂活化解离氢气提供了新的认识.","abstractInfoCn":"单原子催化剂具有独特的结构位点，能最大化利用贵金属原子，在一系列化学转化反应中具有优异的活性和选择性.但单原子的稳定性是单原子催化剂应用的一个挑战，特别是还原气氛下单原子的稳定性，这极大地限制了单原子催化剂在加氢、脱氢和氢解反应中的应用.理解还原气氛下单原子的稳定机制和单原子催化剂活化氢气的反应机理对于扩大单原子催化剂的应用非常重要.Pt/WO<sub><i>x<\/i><\/sub>（2 < <i>x<\/i> < 3）是一种典型的金属-载体强相互作用体系，在甘油氢解制1，3-丙二醇等一系列含氢反应中具有优异的活性和选择性.但原子层面的催化反应机理，如Pt单原子在表面的位置、Pt单原子的稳定机理以及氢气在单原子上活化产生原位Br&#248;nsted酸的机制仍不清楚.<br/>在本研究中，我们结合密度泛函理论（DFT）和实验表征研究了WO<sub><i>x<\/i><\/sub>负载Pt、Pd、Au三种单原子的稳定性和解离氢气的活性.DFT计算结果表明，在还原气氛下Pt单原子能促进氧化钨表面形成桥式氧空位.WO<sub><i>x<\/i><\/sub>表面的氧空位对于Pt单原子的稳定非常重要，氧空位通过转移部分电子给Pt，使Pt单原子带部分负电从而高效地稳定Pt单原子.不同于带正电单原子的非均相解离氢气，带部分负电的Pt单原子保持一定的金属性，能类似金属表面均相解离H<sub>2<\/sub>产生金属氢物种（Pt-H）.同时Pt解离的H原子能容易地扩散到氧化钨载体上形成原位Br&#248;nsted酸，从而使Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化剂具有双功能催化性质.考察了Pt、Pd、Au三种单原子在WO<sub><i>x<\/i><\/sub>（001）表面的稳定性，三种单原子的稳定性顺序为Pt>Pd>Au.氢气能在Pd和WO<sub><i>x<\/i><\/sub>界面非均相解离，而Au/WO<sub><i>x<\/i><\/sub>不能活化、解离氢气.<br/>我们进一步采用实验表征验证了DFT理论计算的结果.实验合成了WO<sub><i>x<\/i><\/sub>负载的Pt、Pd、Au三种催化剂，X射线衍射（XRD）和透射电子显微镜（TEM）结果表明，Pt能在WO<sub><i>x<\/i><\/sub>表面原子级分散和稳定，而Pd在WO<sub><i>x<\/i><\/sub>表面形成较小的纳米颗粒，Au形成较大的纳米颗粒.采用氢气化学吸附研究了三种催化剂对氢气的活化能力，结果表明三种催化剂的氢气活化能力顺序为Pt/WO<sub><i>x<\/i><\/sub>（137μmol/g-Pt）> Pd/WO<sub><i>x<\/i><\/sub>（43μmol/g-Pd）>> Au/WO<sub><i>x<\/i><\/sub>（4μmol/g-Au）.将三种催化剂用于甘油选择性氢解制备1，3-丙二醇的反应中，只有Pt/WO<sub><i>x<\/i><\/sub>催化剂对甘油氢解具有优异的活性和选择性.从而实验证实了氢气气氛下原位产生的Br&#248;nsted酸具有关键作用和Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化剂具有双功能催化性质.<br/>我们的研究不仅解释了还原气氛下金属单原子在氧化物表面的稳定机理，而且对单原子催化剂活化解离氢气提供了新的认识.","abstractInfoEn":"Owing to the atomic dispersion of active sites via electronic interaction with supports, single-atom catalysts (SACs) grant maximum utilization of metals with unique activity and/or selectivity in various catalytic processes. However, the stability of single atoms under oxygen-poor conditions, and the mechanism of hydrogen activation on SACs remain elusive. Here, through a combination of theoretical calculation and experiments, the stabilization of metal single atoms on tungsten oxide and its catalytic properties in H<sub>2<\/sub> activation are investigated. Our calculation results indicate that the oxygen defects on the WO<sub>3<\/sub>(001) surface play a vital role in the stabilization of single metal atoms through electron transfer from the oxygen vacancies to the metal atoms. In comparison with Pd and Au, Pt single atoms possess greatly enhanced stability on the WO<sub><i>x<\/i><\/sub>(001) surface and carry negative charge, facilitating the dissociation of H<sub>2<\/sub> to metal-H species (H<sup><i>δ<\/i>-<\/sup>) via homolytic cleavage of H<sub>2<\/sub> similar to that occurring in metal ensembles. More importantly, the facile diffusion of Pt-H to the WO<sub><i>x<\/i><\/sub> support results in the formation of Br&oslash;nsted acid sites (H<sup><i>δ<\/i>+<\/sup>), imparting bifunctionality to Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>. The dynamic formation of Br&oslash;nsted acid sites in hydrogen atmosphere proved to be the key to chemoselective hydrogenolysis of glycerol into 1,3-propanediol, which was experimentally demonstrated on the Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub> catalyst.","articleNo":"20200315","authorCnList":["周茂祥","  杨曼","  杨小峰","  赵晓晨","  孙磊","  邓伟侨","  王爱琴","  李隽","  张涛"],"authorEnList":["Maoxiang Zhou","  Man Yang","  Xiaofeng Yang","  Xiaochen Zhao","  Lei Sun","  Weiqiao Deng","  Aiqin Wang","  Jun Li","  Tao Zhang"],"authorList":["周茂祥","  杨曼","  杨小峰","  赵晓晨","  孙磊","  邓伟侨","  王爱琴","  李隽","  张涛"],"authors":"周茂祥,  杨曼,  杨小峰,  赵晓晨,  孙磊,  邓伟侨,  王爱琴,  李隽,  张涛","authorsCn":"周茂祥,  杨曼,  杨小峰,  赵晓晨,  孙磊,  邓伟侨,  王爱琴,  李隽,  张涛","authorsEn":"Maoxiang Zhou,  Man Yang,  Xiaofeng Yang,  Xiaochen Zhao,  Lei Sun,  Weiqiao Deng,  Aiqin Wang,  Jun Li,  Tao Zhang","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"周茂祥,  杨曼,  杨小峰,  赵晓晨,  孙磊,  邓伟侨,  王爱琴,  李隽,  张涛. 单原子催化剂活化氢气:Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化氢解反应. 催化学报, 2020, 41(3): 524-532. doi: S1872-2067(19)63517-5.","citationCn":"周茂祥,  杨曼,  杨小峰,  赵晓晨,  孙磊,  邓伟侨,  王爱琴,  李隽,  张涛. 单原子催化剂活化氢气:Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化氢解反应. 催化学报, 2020, 41(3): 524-532. doi: S1872-2067(19)63517-5.","citationEn":"周茂祥,  杨曼,  杨小峰,  赵晓晨,  孙磊,  邓伟侨,  王爱琴,  李隽,  张涛. On the mechanism of H<sub>2<\/sub> activation over single-atom catalyst: An understanding of Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub> in the hydrogenolysis reaction. Chinese Journal of Catalysis, 2020, 41(3): 524-532. doi: S1872-2067(19)63517-5.","doi":"S1872-2067(19)63517-5","figContent":"","figList":[],"firstFig":"","fpage":"524","highCitedState":"","htmlCount":256,"htmlFile":"","id":"c6edc8b8-bc49-44ae-aefd-d34bd51a7b93","issnPpub":"0253-9837","issue":"3","journalPublishId":"chxb","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"单原子催化剂, 铂, 密度泛函理论, 氢解离, 氧化钨","keywordCn":"单原子催化剂, 铂, 密度泛函理论, 氢解离, 氧化钨","keywordCnList":["单原子催化剂"," 铂"," 密度泛函理论"," 氢解离"," 氧化钨"],"keywordEn":"Single-atom catalyst, Pt, Density function theory, Hydrogen dissociation, Tungsten oxide","keywordEnList":["Single-atom catalyst"," Pt"," Density function theory"," Hydrogen dissociation"," Tungsten oxide"],"keywordList":["单原子催化剂"," 铂"," 密度泛函理论"," 氢解离"," 氧化钨"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"532","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":21,"pdfSize":3487.39,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"单原子催化剂活化氢气:Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化氢解反应","titleCn":"单原子催化剂活化氢气:Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub>催化氢解反应","titleEn":"On the mechanism of H<sub>2<\/sub> activation over single-atom catalyst: An understanding of Pt<sub>1<\/sub>/WO<sub><i>x<\/i><\/sub> in the hydrogenolysis reaction","viewCount":1723,"volume":"41","year":2020}]}