{"目录":[{"abstractInfo":"","abstractInfoCn":"","abstractInfoEn":"","articleNo":"20200200","authorCnList":[],"authorEnList":[],"authorList":[],"authors":"","authorsCn":"","authorsEn":"","categoryName":"目录","categoryNameCn":"目录","categoryNameEn":"Content","citation":". 第41卷第2期目次. 催化学报, 2020, 41(2): 0-0.","citationCn":". 第41卷第2期目次. 催化学报, 2020, 41(2): 0-0.","citationEn":". Table of Contents for VOL.41 No.2. Chinese Journal of Catalysis, 2020, 41(2): 0-0.","doi":"","figContent":"","figList":[],"firstFig":"","fpage":"0","highCitedState":"","htmlCount":48,"htmlFile":"","id":"ade68b43-97f7-4622-9ac1-05e476fad30b","issnPpub":"0253-9837","issue":"2","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":8,"pdfSize":2506.54,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"第41卷第2期目次","titleCn":"第41卷第2期目次","titleEn":"Table of Contents for VOL.41 No.2","viewCount":1608,"volume":"41","year":2020}],"综述":[{"abstractInfo":"人类对不可再生化石能源的依赖导致了全球范围内的能源危机和环境污染.电化学能源转换技术由于具有清洁、高效、原料来源广泛及可再生等优点而受到广泛关注.电催化剂能加快反应动力学,提高目标产物选择性,在电化学能源转换技术中起着至关重要的作用.目前,Pt是多数重要的电化学反应(如电解水、氧还原以及一些小分子醇类和酸类的氧化反应)中使用最多和最有效的催化剂之一.然而Pt催化剂面临着价格昂贵、易中毒、易流失等问题,使其在大规模工业化应用中受到限制.为了提高Pt催化剂的利用率和稳定性,研究人员进行了大量工作.例如,制备尺寸小的Pt纳米颗粒,增加单位质量Pt表面积和Pt利用率;在Pt催化剂中加入Ru或Pd等其它金属,促进醇类和酸类氧化反应中间产物的氧化,减缓Pt中毒;选用抗腐蚀性能好的载体,增加Pt与载体间相互作用,从而抑制Pt颗粒在高电位、高湿度、高酸碱度电化学工作环境中的脱落和聚集.尽管如此,利用传统的方法仍然很难精确调控电催化剂的组成、尺寸和纳米结构,无法最大程度提高贵金属Pt的利用效率.原子层沉积(ALD)技术可在原子尺度控制物质生长,既能在多孔、复杂基体上沉积尺度均一的纳米薄膜或颗粒,也能精确调控、构筑各类纳米结构.本文总结了近年来利用ALD技术制备高性能电催化剂的代表性研究进展.
文章首先介绍了ALD反应机理、载体表面官能团对ALD生长的促进作用以及ALD制备方法对催化剂金属-载体相互作用的影响等基本原理和知识.总结了利用ALD技术制备高活性Pt催化剂的各种方法,包括制备超细纳米颗粒,纳米线、纳米薄膜、纳米管,纳米3D结构等不同形貌Pt催化剂等.介绍并探讨了利用ALD构筑纳米陷阱、包覆超薄多孔碳膜/氧化物膜、选择性修饰载体等提高Pt催化剂稳定性的策略.文章还介绍了如何通过调节ALD反应温度、前驱体种类,以及利用选择性沉积等方法,精确调控双贵金属电催化剂中金属的比例、尺寸、结构等以提高催化剂性能,并重点阐述了双金属核壳催化剂的制备方法.此外,文章还概述了ALD方法制备非贵金属催化剂的研究进展.最后,文章总结了ALD技术在设计、制备电催化剂领域的优势和不足,展望了ALD在该领域的发展和应用前景,为设计、制备高性能电催化剂提供了参考.","abstractInfoCn":"人类对不可再生化石能源的依赖导致了全球范围内的能源危机和环境污染.电化学能源转换技术由于具有清洁、高效、原料来源广泛及可再生等优点而受到广泛关注.电催化剂能加快反应动力学,提高目标产物选择性,在电化学能源转换技术中起着至关重要的作用.目前,Pt是多数重要的电化学反应(如电解水、氧还原以及一些小分子醇类和酸类的氧化反应)中使用最多和最有效的催化剂之一.然而Pt催化剂面临着价格昂贵、易中毒、易流失等问题,使其在大规模工业化应用中受到限制.为了提高Pt催化剂的利用率和稳定性,研究人员进行了大量工作.例如,制备尺寸小的Pt纳米颗粒,增加单位质量Pt表面积和Pt利用率;在Pt催化剂中加入Ru或Pd等其它金属,促进醇类和酸类氧化反应中间产物的氧化,减缓Pt中毒;选用抗腐蚀性能好的载体,增加Pt与载体间相互作用,从而抑制Pt颗粒在高电位、高湿度、高酸碱度电化学工作环境中的脱落和聚集.尽管如此,利用传统的方法仍然很难精确调控电催化剂的组成、尺寸和纳米结构,无法最大程度提高贵金属Pt的利用效率.原子层沉积(ALD)技术可在原子尺度控制物质生长,既能在多孔、复杂基体上沉积尺度均一的纳米薄膜或颗粒,也能精确调控、构筑各类纳米结构.本文总结了近年来利用ALD技术制备高性能电催化剂的代表性研究进展.
文章首先介绍了ALD反应机理、载体表面官能团对ALD生长的促进作用以及ALD制备方法对催化剂金属-载体相互作用的影响等基本原理和知识.总结了利用ALD技术制备高活性Pt催化剂的各种方法,包括制备超细纳米颗粒,纳米线、纳米薄膜、纳米管,纳米3D结构等不同形貌Pt催化剂等.介绍并探讨了利用ALD构筑纳米陷阱、包覆超薄多孔碳膜/氧化物膜、选择性修饰载体等提高Pt催化剂稳定性的策略.文章还介绍了如何通过调节ALD反应温度、前驱体种类,以及利用选择性沉积等方法,精确调控双贵金属电催化剂中金属的比例、尺寸、结构等以提高催化剂性能,并重点阐述了双金属核壳催化剂的制备方法.此外,文章还概述了ALD方法制备非贵金属催化剂的研究进展.最后,文章总结了ALD技术在设计、制备电催化剂领域的优势和不足,展望了ALD在该领域的发展和应用前景,为设计、制备高性能电催化剂提供了参考.","abstractInfoEn":"Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition (ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core-shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.","articleNo":"20200201","authorCnList":["杨慧敏"," 陈耀"," 覃勇"],"authorEnList":["Huimin Yang"," Yao Chen"," Yong Qin"],"authorList":["杨慧敏"," 陈耀"," 覃勇"],"authors":"杨慧敏, 陈耀, 覃勇","authorsCn":"杨慧敏, 陈耀, 覃勇","authorsEn":"Huimin Yang, Yao Chen, Yong Qin","categoryName":"综述","categoryNameCn":"综述","categoryNameEn":"Review","citation":"杨慧敏, 陈耀, 覃勇. 原子层沉积方法在设计制备高效电催化剂中的应用. 催化学报, 2020, 41(2): 227-241. doi: S1872-2067(19)63440-6.","citationCn":"杨慧敏, 陈耀, 覃勇. 原子层沉积方法在设计制备高效电催化剂中的应用. 催化学报, 2020, 41(2): 227-241. doi: S1872-2067(19)63440-6.","citationEn":"杨慧敏, 陈耀, 覃勇. Application of atomic layer deposition in fabricating high-efficiency electrocatalysts. Chinese Journal of Catalysis, 2020, 41(2): 227-241. doi: S1872-2067(19)63440-6.","doi":"S1872-2067(19)63440-6","figContent":"","figList":[],"firstFig":"","fpage":"227","highCitedState":"","htmlCount":137,"htmlFile":"","id":"63b3b4cd-255a-4da8-a161-1a43eac35801","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"原子层沉积, 电催化, 铂, 催化剂稳定性, 金属-载体相互作用","keywordCn":"原子层沉积, 电催化, 铂, 催化剂稳定性, 金属-载体相互作用","keywordCnList":["原子层沉积"," 电催化"," 铂"," 催化剂稳定性"," 金属-载体相互作用"],"keywordEn":"Atomic layer deposition, Electrocatalysis, Pt, Catalyst stability, Metal-support interaction","keywordEnList":["Atomic layer deposition"," Electrocatalysis"," Pt"," Catalyst stability"," Metal-support interaction"],"keywordList":["原子层沉积"," 电催化"," 铂"," 催化剂稳定性"," 金属-载体相互作用"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"241","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":11,"pdfSize":1940.63,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"原子层沉积方法在设计制备高效电催化剂中的应用","titleCn":"原子层沉积方法在设计制备高效电催化剂中的应用","titleEn":"Application of atomic layer deposition in fabricating high-efficiency electrocatalysts","viewCount":1787,"volume":"41","year":2020}],"快讯":[{"abstractInfo":"随着世界工业经济的发展,作为不可再生能源的化石燃料消耗日趋增大并带来严重的环境污染.氢能具有能量密度高、燃烧无污染等优点,被认为是替换传统化石燃料的理想能源之一.通过电化学方法实现水裂解制氢是既满足环境要求又符合氢气生产需要的一种潜在有效方法,受到人们广泛关注.基于铂、钌等贵金属的电催化剂在水裂解中具有很高的活性,然而其稀缺性和高成本是阻碍其大规模实际应用的重要因素.水裂解制氢包括二电子转移的质子还原和四电子转移的水氧化两个过程.相对于质子还原,水氧化反应动力学过程缓慢,是决定水裂解速率的关键.通常,质子还原反应倾向于在酸性条件下进行,而水氧化反应在碱性环境下更有利,反应条件的差异阻碍了水裂解制氢的发展.因此,制备在碱性环境下具有高催化性能、高稳定性和低成本的催化剂是促进水裂解制氢能源技术进一步发展的关键.金属有机骨架(MOF)衍生的复合催化剂具有良好的催化性能和广阔的应用前景,在催化反应中得到越来越多的重视.传统的催化剂组装方式是通过全氟磺酸聚合物等辅助剂将催化剂组装到工作电极上,这些辅助剂具有较强的酸性,而且会覆盖催化剂表面的催化活性位点,降低催化剂比表面积,阻碍催化剂活性的进一步提升.
本文通过电泳的方法,将ZIF-67负载到碳纸上,进一步通过碳化、部分磷化过程得到NC/Co/CoP/CP催化电极.研究发现,在碱性环境(1mol/LKOH)下,催化电流达到10mA/cm2<\/sup>的析氢过电位只有208mV,析氧反应的过电位为350mV,在二电极体系中所需的电压也只有1.72V,催化活性明显高于通过传统方法组装的电极.在长时间的电化学稳定性测试中,经过20h的电流测试和1000次的CV测试后,该电极的催化活性没有明显下降.我们报道了一种基于MOF材料的复合电极组装新方法,为MOF材料在能源储存与转化领域应用提供了新思路.","abstractInfoCn":"随着世界工业经济的发展,作为不可再生能源的化石燃料消耗日趋增大并带来严重的环境污染.氢能具有能量密度高、燃烧无污染等优点,被认为是替换传统化石燃料的理想能源之一.通过电化学方法实现水裂解制氢是既满足环境要求又符合氢气生产需要的一种潜在有效方法,受到人们广泛关注.基于铂、钌等贵金属的电催化剂在水裂解中具有很高的活性,然而其稀缺性和高成本是阻碍其大规模实际应用的重要因素.水裂解制氢包括二电子转移的质子还原和四电子转移的水氧化两个过程.相对于质子还原,水氧化反应动力学过程缓慢,是决定水裂解速率的关键.通常,质子还原反应倾向于在酸性条件下进行,而水氧化反应在碱性环境下更有利,反应条件的差异阻碍了水裂解制氢的发展.因此,制备在碱性环境下具有高催化性能、高稳定性和低成本的催化剂是促进水裂解制氢能源技术进一步发展的关键.金属有机骨架(MOF)衍生的复合催化剂具有良好的催化性能和广阔的应用前景,在催化反应中得到越来越多的重视.传统的催化剂组装方式是通过全氟磺酸聚合物等辅助剂将催化剂组装到工作电极上,这些辅助剂具有较强的酸性,而且会覆盖催化剂表面的催化活性位点,降低催化剂比表面积,阻碍催化剂活性的进一步提升.
本文通过电泳的方法,将ZIF-67负载到碳纸上,进一步通过碳化、部分磷化过程得到NC/Co/CoP/CP催化电极.研究发现,在碱性环境(1mol/L KOH)下,催化电流达到10mA/cm2<\/sup>的析氢过电位只有208mV,析氧反应的过电位为350mV,在二电极体系中所需的电压也只有1.72V,催化活性明显高于通过传统方法组装的电极.在长时间的电化学稳定性测试中,经过20 h的电流测试和1000次的CV测试后,该电极的催化活性没有明显下降.我们报道了一种基于MOF材料的复合电极组装新方法,为MOF材料在能源储存与转化领域应用提供了新思路.","abstractInfoEn":"High-performance and cost-effective catalysts for water splitting are key components of hydrogen-based energy technologies. Metal-organic framework (MOF)-derived metal phosphide composites have immense potential as highly active and stable electrocatalysts but suffer from the poor efficacy of available electrode assembly methods. In this study, an MOF-derived nitrogen-doped porous carbon/Co/CoP/carbon paper (NC/Co/CoP/CP) composite electrode was assembled by electrophoretic deposition and post-processing reactions. The binder-free electrode showed good catalytic activity, significantly higher than that of traditional electrodes. The electrode required overpotentials of 208 and 350 mV to achieve a current density of 10 mA/cm2<\/sup> for the hydrogen and oxygen evolution reactions, respectively. This facile synthetic method provides a promising route for designing metal-doped and multi-metal phase MOF-derived composite electrodes for energy storage and conversion devices.","articleNo":"20200202","authorCnList":["丛美钰"," 孙德帅"," 张林林"," 丁欣"],"authorEnList":["Meiyu Cong"," Deshuai Sun"," Linlin Zhang"," Xin Ding"],"authorList":["丛美钰"," 孙德帅"," 张林林"," 丁欣"],"authors":"丛美钰, 孙德帅, 张林林, 丁欣","authorsCn":"丛美钰, 孙德帅, 张林林, 丁欣","authorsEn":"Meiyu Cong, Deshuai Sun, Linlin Zhang, Xin Ding","categoryName":"快讯","categoryNameCn":"快讯","categoryNameEn":"Communication","citation":"丛美钰, 孙德帅, 张林林, 丁欣. 原位组装在碳纸上的有机金属骨架材料衍生的NC/Co/CoP催化剂用于碱性环境水分解. 催化学报, 2020, 41(2): 242-248. doi: S1872-2067(19)63410-8.","citationCn":"丛美钰, 孙德帅, 张林林, 丁欣. 原位组装在碳纸上的有机金属骨架材料衍生的NC/Co/CoP催化剂用于碱性环境水分解. 催化学报, 2020, 41(2): 242-248. doi: S1872-2067(19)63410-8.","citationEn":"丛美钰, 孙德帅, 张林林, 丁欣. In situ assembly of metal-organic framework-derived N-doped carbon/Co/CoP catalysts on carbon paper for water splitting in alkaline electrolytes. Chinese Journal of Catalysis, 2020, 41(2): 242-248. doi: S1872-2067(19)63410-8.","doi":"S1872-2067(19)63410-8","figContent":"","figList":[],"firstFig":"","fpage":"242","highCitedState":"","htmlCount":146,"htmlFile":"","id":"f6ade5c8-4106-4e0c-9647-e2bade92674e","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"水分解, 氢析出催化剂, 电泳沉积, 金属有机骨架","keywordCn":"水分解, 氢析出催化剂, 电泳沉积, 金属有机骨架","keywordCnList":["水分解"," 氢析出催化剂"," 电泳沉积"," 金属有机骨架"],"keywordEn":"Water splitting, Hydrogen evolution reaction catalyst, Electrophoretic deposition, Metal-organic framework","keywordEnList":["Water splitting"," Hydrogen evolution reaction catalyst"," Electrophoretic deposition"," Metal-organic framework"],"keywordList":["水分解"," 氢析出催化剂"," 电泳沉积"," 金属有机骨架"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"248","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":14,"pdfSize":3572.74,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"原位组装在碳纸上的有机金属骨架材料衍生的NC/Co/CoP催化剂用于碱性环境水分解","titleCn":"原位组装在碳纸上的有机金属骨架材料衍生的NC/Co/CoP催化剂用于碱性环境水分解","titleEn":"In situ assembly of metal-organic framework-derived N-doped carbon/Co/CoP catalysts on carbon paper for water splitting in alkaline electrolytes","viewCount":1828,"volume":"41","year":2020}],"论文":[{"abstractInfo":"二氧化钛,氧化锌,磷酸铋等传统的紫外光响应光催化剂虽然具有良好的光催化性能,但是对太阳能利用率很低(紫外光只占太阳光能量的4%左右).近年来,类石墨相氮化碳(g-C3<\/sub>N4<\/sub>)受到了广泛的关注.g-C3<\/sub>N4<\/sub>的带隙约2.7eV,它只能吸收460nm以下的光,对太阳能的利用率依然比较低.构筑异质结是一种有效的提高光催化活性的方法.BiOCl/g-C3<\/sub>N4<\/sub>,TiO2<\/sub>/g-C3<\/sub>N4<\/sub>,Bi2<\/sub>MoO6<\/sub>/g-C3<\/sub>N4<\/sub>,Al2<\/sub>O3<\/sub>/g-C3<\/sub>N4<\/sub>,Ag3<\/sub>PO4<\/sub>/g-C3<\/sub>N4<\/sub>等异质结光催化剂曾被广泛的报道.硫化铋是属于正交晶系的窄带隙半导体,它的带隙约1.3-1.7eV.由于其独特的电子结构和光学特性,硫化铋在光催化,光检测器和医药成像等领域有着广泛的应用.另外,硫化铋还具有优异的光热转换性能,在光热癌症治疗领域有显著的效果.微波辅助法,水热法,惰性气体下高温煅烧法等都曾被用来合成g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂.不同的文献也提出了不同的催化机理.如何使用更简单环保的方法来合成g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂?电子和空穴的转移路径是怎样的?本文利用简单的低温方法合成了硫化铋,利用超声法得到了g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂,分析了其微观形貌,结构,并探讨了光催化的反应机理和提高光催化性能的因素.
X射线衍射,傅里叶变换红外光谱,X射线光电子能谱和透射电子显微镜的结果表明,硫化铋纳米颗粒被成功地引入到g-C3<\/sub>N4<\/sub>中.使用亚甲基蓝为分子探针研究了所制材料在模拟太阳光下的光催化活性.结果发现,CN-BiS-2表现出最佳的光催化活性,是g-C3<\/sub>N4<\/sub>的2.05倍,是Bi2<\/sub>S3<\/sub>的4.42倍.利用液相色谱二级质谱联用分析了亚甲基蓝的降解路径.
硫化铋的引入拓展了复合材料的吸收边,使其向可见光区红移,且在整个可见光区的光吸收能力都有明显的增强.光电流的增强和交流阻抗谱圆弧半径的减小,表明光生载流子的迁移与分离速率得到了增强.自由基捕获试验表明,最主要的活性物种是光生空穴,次之是羟基自由基和超氧自由基.在CN-BiS-2样品中羟基自由基和超氧自由基的电子顺磁共振信号都比g-C3<\/sub>N4<\/sub>有明显的增强,表明复合样品中能够产生更多的羟基自由基和超氧自由基.基于光电流,交流阻抗,荧光光谱,自由基捕获和电子顺磁共振的结果,我们提出了高能电子由硫化铋转移到g-C3<\/sub>N4<\/sub>,同时空穴由g-C3<\/sub>N4<\/sub>转移到硫化铋的电子空穴转移机制.此外,红外热成像的结果表明,g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结材料具有更强的光热转换能力,从而有利于加速光生载流子分离.","abstractInfoCn":"二氧化钛,氧化锌,磷酸铋等传统的紫外光响应光催化剂虽然具有良好的光催化性能,但是对太阳能利用率很低(紫外光只占太阳光能量的4%左右).近年来,类石墨相氮化碳(g-C3<\/sub>N4<\/sub>)受到了广泛的关注.g-C3<\/sub>N4<\/sub>的带隙约2.7eV,它只能吸收460 nm以下的光,对太阳能的利用率依然比较低.构筑异质结是一种有效的提高光催化活性的方法.BiOCl/g-C3<\/sub>N4<\/sub>,TiO2<\/sub>/g-C3<\/sub>N4<\/sub>,Bi2<\/sub>MoO6<\/sub>/g-C3<\/sub>N4<\/sub>,Al2<\/sub>O3<\/sub>/g-C3<\/sub>N4<\/sub>,Ag3<\/sub>PO4<\/sub>/g-C3<\/sub>N4<\/sub>等异质结光催化剂曾被广泛的报道.硫化铋是属于正交晶系的窄带隙半导体,它的带隙约1.3-1.7eV.由于其独特的电子结构和光学特性,硫化铋在光催化,光检测器和医药成像等领域有着广泛的应用.另外,硫化铋还具有优异的光热转换性能,在光热癌症治疗领域有显著的效果.微波辅助法,水热法,惰性气体下高温煅烧法等都曾被用来合成g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂.不同的文献也提出了不同的催化机理.如何使用更简单环保的方法来合成g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂?电子和空穴的转移路径是怎样的?本文利用简单的低温方法合成了硫化铋,利用超声法得到了g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结光催化剂,分析了其微观形貌,结构,并探讨了光催化的反应机理和提高光催化性能的因素.
X射线衍射,傅里叶变换红外光谱,X射线光电子能谱和透射电子显微镜的结果表明,硫化铋纳米颗粒被成功地引入到g-C3<\/sub>N4<\/sub>中.使用亚甲基蓝为分子探针研究了所制材料在模拟太阳光下的光催化活性.结果发现,CN-BiS-2表现出最佳的光催化活性,是g-C3<\/sub>N4<\/sub>的2.05倍,是Bi2<\/sub>S3<\/sub>的4.42倍.利用液相色谱二级质谱联用分析了亚甲基蓝的降解路径.
硫化铋的引入拓展了复合材料的吸收边,使其向可见光区红移,且在整个可见光区的光吸收能力都有明显的增强.光电流的增强和交流阻抗谱圆弧半径的减小,表明光生载流子的迁移与分离速率得到了增强.自由基捕获试验表明,最主要的活性物种是光生空穴,次之是羟基自由基和超氧自由基.在CN-BiS-2样品中羟基自由基和超氧自由基的电子顺磁共振信号都比g-C3<\/sub>N4<\/sub>有明显的增强,表明复合样品中能够产生更多的羟基自由基和超氧自由基.基于光电流,交流阻抗,荧光光谱,自由基捕获和电子顺磁共振的结果,我们提出了高能电子由硫化铋转移到g-C3<\/sub>N4<\/sub>,同时空穴由g-C3<\/sub>N4<\/sub>转移到硫化铋的电子空穴转移机制.此外,红外热成像的结果表明,g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub>异质结材料具有更强的光热转换能力,从而有利于加速光生载流子分离.","abstractInfoEn":"Employing photothermal conversion to improve the photocatalytic activity of g-C3<\/sub>N4<\/sub> is rarely reported previously. Herein, different ratios of g-C3<\/sub>N4<\/sub>/Bi2<\/sub>S3<\/sub> heterojunction materials are synthesized by a facile ultrasonic method. Advanced characterizations such as X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy are employed to analyze the morphology and structure of the prepared materials. Compared with sole counterparts, the heterojunction materials CN-BiS-2 exhibit significantly enhanced photocatalytic performance, which is 2.05-fold as g-C3<\/sub>N4<\/sub> and 4.42-fold as Bi2<\/sub>S3<\/sub>. A possible degradation pathway of methylene blue (MB) was proposed. Based on the photoproduced high-energy electrons and photothermal effect of Bi2<\/sub>S3<\/sub>, the transfer and separation of electron-hole pairs are greatly enhanced and more active species are produced. In addition, the relatively high utilization efficiency of solar energy has synergistic effect for the better photocatalytic performance.","articleNo":"20200203","authorCnList":["郝强"," 谢赐桉"," 黄永明"," 陈代梅"," 刘轶文"," 魏薇"," 倪丙杰"],"authorEnList":["Qiang Hao"," Ci'an Xie"," Yongming Huang"," Daimei Chen"," Yiwen Liu"," Wei Wei"," Bing-Jie Ni"],"authorList":["郝强"," 谢赐桉"," 黄永明"," 陈代梅"," 刘轶文"," 魏薇"," 倪丙杰"],"authors":"郝强, 谢赐桉, 黄永明, 陈代梅, 刘轶文, 魏薇, 倪丙杰","authorsCn":"郝强, 谢赐桉, 黄永明, 陈代梅, 刘轶文, 魏薇, 倪丙杰","authorsEn":"Qiang Hao, Ci'an Xie, Yongming Huang, Daimei Chen, Yiwen Liu, Wei Wei, Bing-Jie Ni","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"郝强, 谢赐桉, 黄永明, 陈代梅, 刘轶文, 魏薇, 倪丙杰. 利用硫化铋纳米颗粒增强类石墨相氮化碳的光生载流子分离效率和光催化活性. 催化学报, 2020, 41(2): 249-258. doi: S1872-2067(19)63450-9.","citationCn":"郝强, 谢赐桉, 黄永明, 陈代梅, 刘轶文, 魏薇, 倪丙杰. 利用硫化铋纳米颗粒增强类石墨相氮化碳的光生载流子分离效率和光催化活性. 催化学报, 2020, 41(2): 249-258. doi: S1872-2067(19)63450-9.","citationEn":"郝强, 谢赐桉, 黄永明, 陈代梅, 刘轶文, 魏薇, 倪丙杰. Accelerated separation of photogenerated charge carriers and enhanced photocatalytic performance of g-C3<\/sub>N4<\/sub> by Bi2<\/sub>S3<\/sub> nanoparticles. Chinese Journal of Catalysis, 2020, 41(2): 249-258. doi: S1872-2067(19)63450-9.","doi":"S1872-2067(19)63450-9","figContent":"","figList":[],"firstFig":"","fpage":"249","highCitedState":"","htmlCount":141,"htmlFile":"","id":"cde4f756-e70f-4262-9154-95e76c798aae","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"类石墨相氮化碳, 硫化铋, 光催化, 水处理, 高能电子","keywordCn":"类石墨相氮化碳, 硫化铋, 光催化, 水处理, 高能电子","keywordCnList":["类石墨相氮化碳"," 硫化铋"," 光催化"," 水处理"," 高能电子"],"keywordEn":"Graphitic carbon nitride, Bismuth sulfide, Photocatalyst, Wastewater treatment, High-energy electron","keywordEnList":["Graphitic carbon nitride"," Bismuth sulfide"," Photocatalyst"," Wastewater treatment"," High-energy electron"],"keywordList":["类石墨相氮化碳"," 硫化铋"," 光催化"," 水处理"," 高能电子"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"258","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":1705.58,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"利用硫化铋纳米颗粒增强类石墨相氮化碳的光生载流子分离效率和光催化活性","titleCn":"利用硫化铋纳米颗粒增强类石墨相氮化碳的光生载流子分离效率和光催化活性","titleEn":"Accelerated separation of photogenerated charge carriers and enhanced photocatalytic performance of g-C3<\/sub>N4<\/sub> by Bi2<\/sub>S3<\/sub> nanoparticles","viewCount":1757,"volume":"41","year":2020},{"abstractInfo":"随着环境污染和能源危机的日益严重,探索高效的非贵金属氧还原电催化剂来替代商业Pt/C迫在眉睫.其中,报道比较多的是具有钴基活性物种和氮掺杂碳的复合材料例如Co-Nx<\/i><\/sub>-C,Co3<\/sub>O4<\/sub>/GO,Co-N/CNT等,该复合材料具有高导电性、良好的稳定性和优异的催化活性.与其他钴基催化剂相比,磷酸钴由于其成本低廉,对环境友好,多功能的优良特性,已被广泛应用于催化、吸附、分离及储能等领域,在电催化方面也有极大的应用潜力.研究表明,磷酸基团不仅可以充当质子受体,也会诱导局部钴原子的几何结构发生扭曲,从而有利于水分子的吸附并促进析氧反应的发生.此外,磷酸钴也被证实具有一定的氧还原活性.尽管磷酸钴电催化剂的研究已经取得了一定进展,磷酸根有利于质子传输,但是其导电性很差,不利于电荷的转移和传输,使得其电催化活性不高.将磷酸钴和导电碳材料复合是解决问题的有效方法.而且,磷酸钴在碱性溶液中并不稳定,极大限制了其在电催化氧还原中的应用.金属有机膦酸盐是一类包含金属离子和有机膦酸配体的杂化材料,通过简单的焙烧便可以很容易地得到金属无机磷酸盐,并且在焙烧过程中氮掺杂的碳也会原位产生,并包覆在磷酸钴的表面,使得其导电性和催化活性大大提高.为此,本研究组制备了有机膦酸钴衍生的磷酸钴和氮磷掺杂的石墨烯的复合材料并用于电催化氧还原和析氧反应,所得到的材料导电性和稳定性良好,然而,该催化剂的表观活性与商业Pt/C相比仍有较大差距,且使用有机膦酸钴作为前驱体对活性的影响也不甚清楚.因此,本文采用含氮的有机膦酸配体乙二胺四亚甲基膦酸钠(EDTMPS)为磷源制备了氮掺杂的磷酸钴/碳纳米管杂化材料(CoPiC-N/CNT-3),其催化活性和稳定性良好,并进一步探讨了各种不同因素对电催化活性的影响.
XRD和TEM结果表明,用这种方法得到的磷酸钴(CoPiC)为Co2<\/sub>P2<\/sub>O7<\/sub>物相,与磷酸二氢钠为磷源制备得到的CoPi相比,CoPiC的表面有石墨化碳层的存在,EDS图谱表明,Co,P,C,N均匀地掺杂到复合材料的骨架结构中.Raman光谱结果表明,石墨化碳层的存在和适量的碳纳米管的引入均可以增强复合材料的石墨化程度并提高了导电性,而氮掺杂导致其缺陷位点增多.XPS结果进一步表明,有机膦酸钴可以作为前驱体可制得氮掺杂的磷酸钴/碳纳米管杂化材料.电催化反应测试表明,CoPiC-N/CNT-3的氧还原活性与商业Pt/C相当,其遵循的是4电子的反应路径,而且抗甲醇氧化能力和稳定性均优于Pt/C.原因主要归结于以下几点:(1)磷酸钴颗粒与氧化碳纳米管的协同作用可以显著增强氧还原催化活性,引入的碳纳米管可以克服磷酸钴导电性差的缺陷;(2)磷酸钴在复合材料中分散均匀,使得可以充分利用催化剂的活性位点;(3)氮掺杂可以调变材料的电子结构,从而改善催化活性;(4)石墨化碳层的存在可以改善材料的电子导电性和稳定性,有利于电子转移并可以保护磷酸钴颗粒在催化氧还原反应过程中不被电解液腐蚀.可见,所制有机膦酸衍生的氮掺杂的磷酸钴/碳纳米管杂化材料有望替代Pt/C催化剂,并推动清洁可再生能源领域的相关研究.","abstractInfoCn":"随着环境污染和能源危机的日益严重,探索高效的非贵金属氧还原电催化剂来替代商业Pt/C迫在眉睫.其中,报道比较多的是具有钴基活性物种和氮掺杂碳的复合材料例如Co-Nx<\/i><\/sub>-C,Co3<\/sub>O4<\/sub>/GO,Co-N/CNT等,该复合材料具有高导电性、良好的稳定性和优异的催化活性.与其他钴基催化剂相比,磷酸钴由于其成本低廉,对环境友好,多功能的优良特性,已被广泛应用于催化、吸附、分离及储能等领域,在电催化方面也有极大的应用潜力.研究表明,磷酸基团不仅可以充当质子受体,也会诱导局部钴原子的几何结构发生扭曲,从而有利于水分子的吸附并促进析氧反应的发生.此外,磷酸钴也被证实具有一定的氧还原活性.尽管磷酸钴电催化剂的研究已经取得了一定进展,磷酸根有利于质子传输,但是其导电性很差,不利于电荷的转移和传输,使得其电催化活性不高.将磷酸钴和导电碳材料复合是解决问题的有效方法.而且,磷酸钴在碱性溶液中并不稳定,极大限制了其在电催化氧还原中的应用.金属有机膦酸盐是一类包含金属离子和有机膦酸配体的杂化材料,通过简单的焙烧便可以很容易地得到金属无机磷酸盐,并且在焙烧过程中氮掺杂的碳也会原位产生,并包覆在磷酸钴的表面,使得其导电性和催化活性大大提高.为此,本研究组制备了有机膦酸钴衍生的磷酸钴和氮磷掺杂的石墨烯的复合材料并用于电催化氧还原和析氧反应,所得到的材料导电性和稳定性良好,然而,该催化剂的表观活性与商业Pt/C相比仍有较大差距,且使用有机膦酸钴作为前驱体对活性的影响也不甚清楚.因此,本文采用含氮的有机膦酸配体乙二胺四亚甲基膦酸钠(EDTMPS)为磷源制备了氮掺杂的磷酸钴/碳纳米管杂化材料(CoPiC-N/CNT-3),其催化活性和稳定性良好,并进一步探讨了各种不同因素对电催化活性的影响.
XRD和TEM结果表明,用这种方法得到的磷酸钴(CoPiC)为Co2<\/sub>P2<\/sub>O7<\/sub>物相,与磷酸二氢钠为磷源制备得到的CoPi相比,CoPiC的表面有石墨化碳层的存在,EDS图谱表明,Co,P,C,N均匀地掺杂到复合材料的骨架结构中.Raman光谱结果表明,石墨化碳层的存在和适量的碳纳米管的引入均可以增强复合材料的石墨化程度并提高了导电性,而氮掺杂导致其缺陷位点增多.XPS结果进一步表明,有机膦酸钴可以作为前驱体可制得氮掺杂的磷酸钴/碳纳米管杂化材料.电催化反应测试表明,CoPiC-N/CNT-3的氧还原活性与商业Pt/C相当,其遵循的是4电子的反应路径,而且抗甲醇氧化能力和稳定性均优于Pt/C.原因主要归结于以下几点:(1)磷酸钴颗粒与氧化碳纳米管的协同作用可以显著增强氧还原催化活性,引入的碳纳米管可以克服磷酸钴导电性差的缺陷;(2)磷酸钴在复合材料中分散均匀,使得可以充分利用催化剂的活性位点;(3)氮掺杂可以调变材料的电子结构,从而改善催化活性;(4)石墨化碳层的存在可以改善材料的电子导电性和稳定性,有利于电子转移并可以保护磷酸钴颗粒在催化氧还原反应过程中不被电解液腐蚀.可见,所制有机膦酸衍生的氮掺杂的磷酸钴/碳纳米管杂化材料有望替代Pt/C催化剂,并推动清洁可再生能源领域的相关研究.","abstractInfoEn":"The exploration of cost-effective non-noble-metal electrocatalysts is highly imperative to replace the state-of-the-art platinum-based catalysts for oxygen reduction reaction (ORR). Here, we prepared cobalt phosphonate-derived N-doped cobalt phosphate/carbon nanotube hybrids (CoPiC-N/CNTs) by hydrothermal treatment of N-containing cobalt phosphonate and oxidized carbon nanotubes (o<\/i>-CNT) followed by high-temperature calcination under nitrogen atmosphere. The resultant CoPiC-N/CNT exhibits a superior electrocatalytic performance for the ORR in alkaline media, which is equal to the commercial Pt/C catalyst in the aspect of half-wave potential, onset potential and diffuse limiting current density. Furthermore, the excellent tolerance to methanol and strong durability outperform those of commercial Pt/C. It is found that cobalt phosphonate-derived N-doped cobalt phosphate and the in-situ<\/i> formed graphitic carbons play key roles on the activity enhancement. Besides, introducing a suitable amount of CNTs enhances the electronic conductivity and further contributes to the improved ORR performance.","articleNo":"20200204","authorCnList":["赵挥"," 翁晨晨"," 任金涛"," 葛丽"," 刘玉萍"," 袁忠勇"],"authorEnList":["Hui Zhao"," Chen-Chen Weng"," Jin-Tao Ren"," Li Ge"," Yu-Ping Liu"," Zhong-Yong Yuan"],"authorList":["赵挥"," 翁晨晨"," 任金涛"," 葛丽"," 刘玉萍"," 袁忠勇"],"authors":"赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇","authorsCn":"赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇","authorsEn":"Hui Zhao, Chen-Chen Weng, Jin-Tao Ren, Li Ge, Yu-Ping Liu, Zhong-Yong Yuan","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇. 有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂. 催化学报, 2020, 41(2): 259-267. doi: S1872-2067(19)63455-8.","citationCn":"赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇. 有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂. 催化学报, 2020, 41(2): 259-267. doi: S1872-2067(19)63455-8.","citationEn":"赵挥, 翁晨晨, 任金涛, 葛丽, 刘玉萍, 袁忠勇. Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts. Chinese Journal of Catalysis, 2020, 41(2): 259-267. doi: S1872-2067(19)63455-8.","doi":"S1872-2067(19)63455-8","figContent":"","figList":[],"firstFig":"","fpage":"259","highCitedState":"","htmlCount":131,"htmlFile":"","id":"b9041826-365d-459e-b5bf-49614f672465","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"金属膦酸盐, 金属磷酸盐, 碳纳米管, 氧还原反应, 电催化剂","keywordCn":"金属膦酸盐, 金属磷酸盐, 碳纳米管, 氧还原反应, 电催化剂","keywordCnList":["金属膦酸盐"," 金属磷酸盐"," 碳纳米管"," 氧还原反应"," 电催化剂"],"keywordEn":"Metal phosphonate, Metal phosphate, Carbon nanotubes, Oxygen reduction reaction, Electrocatalysis","keywordEnList":["Metal phosphonate"," Metal phosphate"," Carbon nanotubes"," Oxygen reduction reaction"," Electrocatalysis"],"keywordList":["金属膦酸盐"," 金属磷酸盐"," 碳纳米管"," 氧还原反应"," 电催化剂"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"267","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":2913.4,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂","titleCn":"有机膦酸盐衍生的氮掺杂的磷酸钴/碳纳米管杂化材料作为高效氧还原电催化剂","titleEn":"Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts","viewCount":1718,"volume":"41","year":2020},{"abstractInfo":"电荷分离及转移是影响光催化效率的重要因素之一.本文采用简易的水热焙烧法,设计并构筑了Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>(BMO@BOC)异质结,促进了光生载流子的分离与迁移,并优化了异质结构中的BMO与BOC的组分比例,其中BMO@BOC-1样品展现了最高的光催化脱除NO效率(~35%),且具有优异的循环稳定性.SEM与TEM结果表明,BMO@BOC-1样品是由超薄纳米片构成,可以提供丰富的反应活性位点,从而促进光催化反应的发生.HRTEM,XRD及Raman充分证明已成功合成不同组分比例的BMO@BOC异质结.同时,Raman与XPS结果表明,BMO@BOC异质结由Bi,O,C及Mo组成,XPS图谱中拟合峰位置的偏移是由异质结组分不同所致.值得注意的是,UV-visDRS结果表明,BMO@BOC-4具有最好的光谱吸收性能,但它与BMO@BOC-2和BMO@BOC-1样品的吸收带边相近,而PL结果则表明BMO@BOC-1具有更好的电荷分离性能,以及合适的组分比例,在一定程度上可以促进光吸收,并能最大限度的促进光生载流子的分离.BMO@BOC-1样品的ESR测试结果说明,·OH与·O2<\/sub>-<\/sup>的含量随着光照时间的延长而增加,证实了它们是光催化NO氧化的活性中间物种.另外,光催反应机制的研究在高效光催化剂的研发及其商业化应用中具有深远意义.本文还利用原位红外实时动态监测手段,采用“连续流测试法”与“间歇流测试法”直观动态地研究了BMO@BOC异质结催化剂表面光催化NO脱除反应过程.结果表明,在开灯前的吸附阶段于催化剂表面形成了NO-<\/sup>,NO2<\/sub>-<\/sup>以及NO2<\/sub>等中间产物,开灯后的氧化阶段出现终产物(NO3<\/sub>-<\/sup>).进一步深入分析,中间产物NO-<\/sup>和NO2<\/sub>-<\/sup>在氧化阶段会被氧化活性物种进一步氧化成NO3<\/sub>-<\/sup>,而中间产物NO2<\/sub>可能作为一种毒副产物影响NO的完全氧化.综上所述,本文将为理解NO氧化过程提供直观且动态的研究方法,对光催化技术的发展具有重要的指导意义.","abstractInfoCn":"电荷分离及转移是影响光催化效率的重要因素之一.本文采用简易的水热焙烧法,设计并构筑了Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>(BMO@BOC)异质结,促进了光生载流子的分离与迁移,并优化了异质结构中的BMO与BOC的组分比例,其中BMO@BOC-1样品展现了最高的光催化脱除NO效率(~35%),且具有优异的循环稳定性.SEM与TEM结果表明,BMO@BOC-1样品是由超薄纳米片构成,可以提供丰富的反应活性位点,从而促进光催化反应的发生.HRTEM,XRD及Raman充分证明已成功合成不同组分比例的BMO@BOC异质结.同时,Raman与XPS结果表明,BMO@BOC异质结由Bi,O,C及Mo组成,XPS图谱中拟合峰位置的偏移是由异质结组分不同所致.值得注意的是,UV-vis DRS结果表明,BMO@BOC-4具有最好的光谱吸收性能,但它与BMO@BOC-2和BMO@BOC-1样品的吸收带边相近,而PL结果则表明BMO@BOC-1具有更好的电荷分离性能,以及合适的组分比例,在一定程度上可以促进光吸收,并能最大限度的促进光生载流子的分离.BMO@BOC-1样品的ESR测试结果说明,·OH与·O2<\/sub>-<\/sup>的含量随着光照时间的延长而增加,证实了它们是光催化NO氧化的活性中间物种.另外,光催反应机制的研究在高效光催化剂的研发及其商业化应用中具有深远意义.本文还利用原位红外实时动态监测手段,采用“连续流测试法”与“间歇流测试法”直观动态地研究了BMO@BOC异质结催化剂表面光催化NO脱除反应过程.结果表明,在开灯前的吸附阶段于催化剂表面形成了NO-<\/sup>,NO2<\/sub>-<\/sup>以及NO2<\/sub>等中间产物,开灯后的氧化阶段出现终产物(NO3<\/sub>-<\/sup>).进一步深入分析,中间产物NO-<\/sup>和NO2<\/sub>-<\/sup>在氧化阶段会被氧化活性物种进一步氧化成NO3<\/sub>-<\/sup>,而中间产物NO2<\/sub>可能作为一种毒副产物影响NO的完全氧化.综上所述,本文将为理解NO氧化过程提供直观且动态的研究方法,对光催化技术的发展具有重要的指导意义.","abstractInfoEn":"Charge separation and transformation are some of the key requirements for high-efficiency photocatalysis. The photocatalytic reaction mechanism provides a guideline for the development and commercialization of high-efficiency photocatalysts. In this study, we designed and favorably synthesized BMO@BOC heterojunctions via a facile solvothermal route and applied the heat treatment method for application in high-efficiency photocatalytic NO removal. More importantly, both continuous stream and intermittent stream methods with in situ<\/i> diffuse reflectance infrared Fourier transform spectroscopy were applied to intuitively and dynamically investigate the adsorption process and oxidation process of NO removal over the photocatalyst surface. The intermediate products (NO-<\/sup>, NO2<\/sub>-<\/sup>, and NO2<\/sub>) were explicitly detected in both the adsorption process and oxidation process, whilst the final product (NO3<\/sub>-<\/sup>) appeared only in the oxidation process, owing to the separation, migration, and conversion of photoinduced electron-hole pairs.","articleNo":"20200205","authorCnList":["霍旺晨"," 曹通"," 许伟娜"," 郭梓阳"," 刘晓英"," 要红昌"," 张育新"," 董帆"],"authorEnList":["Wangchen Huo"," Tong Cao"," Weina Xu"," Ziyang Guo"," Xiaoying Liu"," Hong-Chang Yao"," Yuxin Zhang"," Fan Dong"],"authorList":["霍旺晨"," 曹通"," 许伟娜"," 郭梓阳"," 刘晓英"," 要红昌"," 张育新"," 董帆"],"authors":"霍旺晨, 曹通, 许伟娜, 郭梓阳, 刘晓英, 要红昌, 张育新, 董帆","authorsCn":"霍旺晨, 曹通, 许伟娜, 郭梓阳, 刘晓英, 要红昌, 张育新, 董帆","authorsEn":"Wangchen Huo, Tong Cao, Weina Xu, Ziyang Guo, Xiaoying Liu, Hong-Chang Yao, Yuxin Zhang, Fan Dong","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"霍旺晨, 曹通, 许伟娜, 郭梓阳, 刘晓英, 要红昌, 张育新, 董帆. 简易构筑Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>异质结增强光催化脱除NO性能及其转化过程. 催化学报, 2020, 41(2): 268-275. doi: S1872-2067(19)63460-1.","citationCn":"霍旺晨, 曹通, 许伟娜, 郭梓阳, 刘晓英, 要红昌, 张育新, 董帆. 简易构筑Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>异质结增强光催化脱除NO性能及其转化过程. 催化学报, 2020, 41(2): 268-275. doi: S1872-2067(19)63460-1.","citationEn":"霍旺晨, 曹通, 许伟娜, 郭梓阳, 刘晓英, 要红昌, 张育新, 董帆. Facile construction of Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub> heterojunctions for enhanced photocatalytic efficiency toward NO removal and study of the conversion process. Chinese Journal of Catalysis, 2020, 41(2): 268-275. doi: S1872-2067(19)63460-1.","doi":"S1872-2067(19)63460-1","figContent":"","figList":[],"firstFig":"","fpage":"268","highCitedState":"","htmlCount":110,"htmlFile":"","id":"f669df87-e959-4cc8-931d-04cfc992b3da","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"异质结, NO脱除, 光催化, 原位红外, 反应过程","keywordCn":"异质结, NO脱除, 光催化, 原位红外, 反应过程","keywordCnList":["异质结"," NO脱除"," 光催化"," 原位红外"," 反应过程"],"keywordEn":"Heterojunction, NO removal, Photocatalysis, In situ DRIFTS, Reaction process","keywordEnList":["Heterojunction"," NO removal"," Photocatalysis"," In situ DRIFTS"," Reaction process"],"keywordList":["异质结"," NO脱除"," 光催化"," 原位红外"," 反应过程"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"275","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":3048.83,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"简易构筑Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>异质结增强光催化脱除NO性能及其转化过程","titleCn":"简易构筑Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub>异质结增强光催化脱除NO性能及其转化过程","titleEn":"Facile construction of Bi2<\/sub>Mo3<\/sub>O12<\/sub>@Bi2<\/sub>O2<\/sub>CO3<\/sub> heterojunctions for enhanced photocatalytic efficiency toward NO removal and study of the conversion process","viewCount":1729,"volume":"41","year":2020},{"abstractInfo":"丙烯是一种非常重要的化工基础原料,主要用来生产高价值的化学品,如丙烯腈,异丙醇和甘油等.丙烯的传统来源主要是石油的催化裂化反应,以及石脑油和轻柴油的裂解过程.随着石油资源的减少,丙烷直接脱氢制丙烯技术逐渐成为一条重要的丙烯生产渠道.V基催化剂在丙烷氧化脱氢反应中被广泛研究,但被用于丙烷直接脱氢反应的报道还较少,且V基催化剂在丙烷直接脱氢制丙烯中的活性位目前还没有统一定论,可能是由于V的活性物种与载体性质密切相关,因此研究V基催化剂在不同载体上的活性位具有重要意义.Beta沸石分子筛具有规则微孔结构,高的比表面积以及可调节的酸性,是一种理想的金属催化剂载体.本文采用脱铝后的Beta分子筛作为V催化剂载体,通过调节V的负载量探究丙烷直接脱氢活性和VOx<\/i><\/sub>结构的关系,以及催化剂的酸性对性能的影响.
活性测试结果显示,V负载量分别为3wt%,7wt%和10wt%时(催化剂分别命名为3VSiBeta,7VSiBeta和10VSiBeta),三者的催化活性十分接近,此外,这些催化剂还具有较好的循环利用性,但碳沉积,丙烯选择性以及失活率都是随着V负载量的升高而增加.XRD和N2<\/sub>吸附结果揭示,VOx<\/i><\/sub>在SiBeta上呈高度分散状态,并且当V负载量从3wt%升至10wt%时,表面V密度发生明显变化,VOx<\/i><\/sub>物种在3VSiBeta中可基本实现孤立的单分散状态.同时,DRUV-vis,H2<\/sub>-TPR以及Raman测试结果表明,VOx<\/i><\/sub>物种的聚合程度随V负载量的升高逐渐增加.NH3<\/sub>-TPD结果表明,Beta载体在脱铝后本身的酸性位完全消除,但是负载V后引入了新的酸性位,并且3VSiBeta,7VSiBeta和10VSiBeta三者的酸量基本相当.尽管XPS结果显示,不同VSiBeta催化剂上的V价态分布有差异,但是相似的催化活性说明VSiBeta催化剂的活性位与形成的酸性位数目密切相关,而受V初始价态的影响不大.本文指出,酸性位可能是与V-O-Si键直接相关,V负载量从3wt%增加到10wt%,会逐渐形成无催化活性的V-O-V键,导致活性不能进一步提升.因此,3VSiBeta催化剂中可实现孤立的VOx<\/i><\/sub>物种单层分散在SiBeta载体上,形成了大量的酸性V-O-Si键,从而显示出和高负载量的VSiBeta催化剂相当的活性以及较高的脱氢稳定性.","abstractInfoCn":"丙烯是一种非常重要的化工基础原料,主要用来生产高价值的化学品,如丙烯腈,异丙醇和甘油等.丙烯的传统来源主要是石油的催化裂化反应,以及石脑油和轻柴油的裂解过程.随着石油资源的减少,丙烷直接脱氢制丙烯技术逐渐成为一条重要的丙烯生产渠道.V基催化剂在丙烷氧化脱氢反应中被广泛研究,但被用于丙烷直接脱氢反应的报道还较少,且V基催化剂在丙烷直接脱氢制丙烯中的活性位目前还没有统一定论,可能是由于V的活性物种与载体性质密切相关,因此研究V基催化剂在不同载体上的活性位具有重要意义.Beta沸石分子筛具有规则微孔结构,高的比表面积以及可调节的酸性,是一种理想的金属催化剂载体.本文采用脱铝后的Beta分子筛作为V催化剂载体,通过调节V的负载量探究丙烷直接脱氢活性和VOx<\/i><\/sub>结构的关系,以及催化剂的酸性对性能的影响.
活性测试结果显示,V负载量分别为3 wt%,7 wt%和10 wt%时(催化剂分别命名为3VSiBeta,7VSiBeta和10VSiBeta),三者的催化活性十分接近,此外,这些催化剂还具有较好的循环利用性,但碳沉积,丙烯选择性以及失活率都是随着V负载量的升高而增加.XRD和N2<\/sub>吸附结果揭示,VOx<\/i><\/sub>在SiBeta上呈高度分散状态,并且当V负载量从3 wt%升至10 wt%时,表面V密度发生明显变化,VOx<\/i><\/sub>物种在3VSiBeta中可基本实现孤立的单分散状态.同时,DR UV-vis,H2<\/sub>-TPR以及Raman测试结果表明,VOx<\/i><\/sub>物种的聚合程度随V负载量的升高逐渐增加.NH3<\/sub>-TPD结果表明,Beta载体在脱铝后本身的酸性位完全消除,但是负载V后引入了新的酸性位,并且3VSiBeta,7VSiBeta和10VSiBeta三者的酸量基本相当.尽管XPS结果显示,不同VSiBeta催化剂上的V价态分布有差异,但是相似的催化活性说明VSiBeta催化剂的活性位与形成的酸性位数目密切相关,而受V初始价态的影响不大.本文指出,酸性位可能是与V-O-Si键直接相关,V负载量从3 wt%增加到10 wt%,会逐渐形成无催化活性的V-O-V键,导致活性不能进一步提升.因此,3VSiBeta催化剂中可实现孤立的VOx<\/i><\/sub>物种单层分散在SiBeta载体上,形成了大量的酸性V-O-Si键,从而显示出和高负载量的VSiBeta催化剂相当的活性以及较高的脱氢稳定性.","abstractInfoEn":"The VOx<\/i><\/sub> catalysts supported on dealuminated Beta zeolite (SiBeta) with varying V loadings (from 0.5 to 10 wt%) are prepared and tested for their catalytic activities in the reaction of direct dehydrogenation of propane to propylene (PDH). It is characterized that the VSiBeta catalysts possess different kinds of vanadium species on the SiBeta support, including monomeric or isolated VOx<\/i><\/sub> species at a low V loading, and polynuclear VOx<\/i><\/sub> species in different polymerization degrees at higher V loadings. The 3VSiBeta catalyst (V loading is 3 wt%), containing isolated VOx<\/i><\/sub> species in monolayer, shows around 40% of propane conversion with 90% of propylene selectivity (reaction conditions:600 ℃, 4000 mL g-1<\/sup> h-1<\/sup>) which are comparable to VSiBeta catalysts with higher V loadings. The catalytic activity exhibits a good linear relationship with the amount of generated acidic sites, which are derived from the interaction sites between VOx<\/i><\/sub> species and SiBeta support, and keeps stable after several regeneration cycles. Thus, as the VOx<\/i><\/sub> species directly contact with SiBeta support via V-O-Si bonds, a reactivity enhancement can be achieved. While, the initial valence state of V does not seem to influence the catalytic performance. Moreover, the aggregation degree of VOx<\/i><\/sub> species determines the propylene selectivity and deactivation rate, both of which increase as raising the V loading amount.","articleNo":"20200206","authorCnList":["陈冲"," 孙明磊"," 胡忠攀"," 刘玉萍"," 张守民"," 袁忠勇"],"authorEnList":["Chong Chen"," Minglei Sun"," Zhongpan Hu"," Yuping Liu"," Shoumin Zhang"," Zhong-Yong Yuan"],"authorList":["陈冲"," 孙明磊"," 胡忠攀"," 刘玉萍"," 张守民"," 袁忠勇"],"authors":"陈冲, 孙明磊, 胡忠攀, 刘玉萍, 张守民, 袁忠勇","authorsCn":"陈冲, 孙明磊, 胡忠攀, 刘玉萍, 张守民, 袁忠勇","authorsEn":"Chong Chen, Minglei Sun, Zhongpan Hu, Yuping Liu, Shoumin Zhang, Zhong-Yong Yuan","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"陈冲, 孙明磊, 胡忠攀, 刘玉萍, 张守民, 袁忠勇. SiBeta负载的VOx<\/i><\/sub>催化剂在丙烷直接脱氢制丙烯中的活性位. 催化学报, 2020, 41(2): 276-285. doi: S1872-2067(19)63444-3.","citationCn":"陈冲, 孙明磊, 胡忠攀, 刘玉萍, 张守民, 袁忠勇. SiBeta负载的VOx<\/i><\/sub>催化剂在丙烷直接脱氢制丙烯中的活性位. 催化学报, 2020, 41(2): 276-285. doi: S1872-2067(19)63444-3.","citationEn":"陈冲, 孙明磊, 胡忠攀, 刘玉萍, 张守民, 袁忠勇. Nature of active phase of VOx<\/i><\/sub> catalysts supported on SiBeta for direct dehydrogenation of propane to propylene. Chinese Journal of Catalysis, 2020, 41(2): 276-285. doi: S1872-2067(19)63444-3.","doi":"S1872-2067(19)63444-3","figContent":"","figList":[],"firstFig":"","fpage":"276","highCitedState":"","htmlCount":73,"htmlFile":"","id":"49794c4c-1654-47a6-9031-f326ee658167","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"丙烷脱氢, 丙烯, VOx<\/i><\/sub>物种, SiBeta载体, 活性位","keywordCn":"丙烷脱氢, 丙烯, VOx<\/i><\/sub>物种, SiBeta载体, 活性位","keywordCnList":["丙烷脱氢"," 丙烯"," VOx<\/i><\/sub>物种"," SiBeta载体"," 活性位"],"keywordEn":"Propane dehydrogenation, Propylene, VOx<\/i><\/sub> species, SiBeta support, Active sites","keywordEnList":["Propane dehydrogenation"," Propylene"," VOx<\/i><\/sub> species"," SiBeta support"," Active sites"],"keywordList":["丙烷脱氢"," 丙烯"," VOx<\/i><\/sub>物种"," SiBeta载体"," 活性位"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"285","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":837.49,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"SiBeta负载的VOx<\/i><\/sub>催化剂在丙烷直接脱氢制丙烯中的活性位","titleCn":"SiBeta负载的VOx<\/i><\/sub>催化剂在丙烷直接脱氢制丙烯中的活性位","titleEn":"Nature of active phase of VOx<\/i><\/sub> catalysts supported on SiBeta for direct dehydrogenation of propane to propylene","viewCount":1646,"volume":"41","year":2020},{"abstractInfo":"在传统热催化材料的研究领域中,光照技术已经得到了广泛的应用,从而使传统热催化剂的催化反应活性和选择性得到优化.然而,在光热协同催化反应过程中,光照因素对催化反应过程的影响尚未得到很好地研究和理解.本文通过浸渍法制得Pt/Al2<\/sub>O3<\/sub>催化剂,并应用于光热协同催化CO2<\/sub>加氢反应.结果证明,在光热协同CO2<\/sub>加氢催化反应中,Pt/Al2<\/sub>O3<\/sub>催化剂表现出光热协同效应.本文结合原位漫反射红外光谱(operandoDRIFTS)和密度泛函理论计算(DFT)对光照因素对该催化反应过程的作用机制进行了进一步深入研究.结果表明,CO气体分子从Pt纳米颗粒上的脱附过程为CO2<\/sub>加氢反应的重要步骤;CO气体分子在Pt纳米颗粒上脱附的位置包含台阶位置(Ptstep<\/sub>)和平台位置(Ptterrace<\/sub>).结果表明,反应过程中CO气体分子从Pt表面的脱附有利于催化剂暴露出Pt反应活性位点.值得注意的是,在光热协同催化CO2<\/sub>加氢反应过程中,光照和温度因素对CO气体分子的脱附过程具有不同影响.吸附能的计算结果证明,CO气体分子吸附在Ptstep<\/sub>和Ptterrace<\/sub>上的吸附能分别为-1.24和-1.43eV.由此可见,CO气体分子与Pt纳米颗粒上的Ptstep<\/sub>吸附位点之间相互作用更强.在无光照作用的条件下对催化剂进行加热,CO气体分子更容易从Ptterrace<\/sub>吸附位点发生脱附;但是在对应的温度下加入光照作用后,吸附在Ptstep<\/sub>位点上的CO气体分子会先转移到Ptterrace<\/sub>吸附位点上,随后脱附,从而促进CO2<\/sub>加氢反应的进行.","abstractInfoCn":"在传统热催化材料的研究领域中,光照技术已经得到了广泛的应用,从而使传统热催化剂的催化反应活性和选择性得到优化.然而,在光热协同催化反应过程中,光照因素对催化反应过程的影响尚未得到很好地研究和理解.本文通过浸渍法制得Pt/Al2<\/sub>O3<\/sub>催化剂,并应用于光热协同催化CO2<\/sub>加氢反应.结果证明,在光热协同CO2<\/sub>加氢催化反应中,Pt/Al2<\/sub>O3<\/sub>催化剂表现出光热协同效应.本文结合原位漫反射红外光谱(operando DRIFTS)和密度泛函理论计算(DFT)对光照因素对该催化反应过程的作用机制进行了进一步深入研究.结果表明,CO气体分子从Pt纳米颗粒上的脱附过程为CO2<\/sub>加氢反应的重要步骤; CO气体分子在Pt纳米颗粒上脱附的位置包含台阶位置(Ptstep<\/sub>)和平台位置(Ptterrace<\/sub>).结果表明,反应过程中CO气体分子从Pt表面的脱附有利于催化剂暴露出Pt反应活性位点.值得注意的是,在光热协同催化CO2<\/sub>加氢反应过程中,光照和温度因素对CO气体分子的脱附过程具有不同影响.吸附能的计算结果证明,CO气体分子吸附在Ptstep<\/sub>和Ptterrace<\/sub>上的吸附能分别为-1.24和-1.43eV.由此可见,CO气体分子与Pt纳米颗粒上的Ptstep<\/sub>吸附位点之间相互作用更强.在无光照作用的条件下对催化剂进行加热,CO气体分子更容易从Ptterrace<\/sub>吸附位点发生脱附;但是在对应的温度下加入光照作用后,吸附在Ptstep<\/sub>位点上的CO气体分子会先转移到Ptterrace<\/sub>吸附位点上,随后脱附,从而促进CO2<\/sub>加氢反应的进行.","abstractInfoEn":"Light illumination has been widely used to promote activity and selectivity of traditional thermal catalysts. Nevertheless, the role of light irradiation during catalytic reactions is not well understood. In this work, Pt/Al2<\/sub>O3<\/sub> prepared by wet impregnation was used for photothermal CO2<\/sub> hydrogenation, and it showed a photothermal effect. Hence, operando diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculations were conducted on Pt/Al2<\/sub>O3<\/sub> to gain insights into the reaction mechanism. The results indicated that CO desorption from Pt sites including step sites (Ptstep<\/sub>) or/and terrace site (Ptterrace<\/sub>) is an important step during CO2<\/sub> hydrogenation to free the active Pt sites. Notably, visible light illumination and temperature affected the CO desorption in different ways. The calculated adsorption energy of CO on Ptstep<\/sub> and Ptterrace<\/sub> sites was -1.24 and -1.43 eV, respectively. Hence, CO is more strongly bound to the Ptstep<\/sub> sites. During heating in the dark, CO preferentially desorbs from the Ptterrace<\/sub> site. However, the additional light irradiation facilitates transfer of CO from the Ptstep<\/sub> to Ptterrace<\/sub> sites and its subsequent desorption from the Ptterrace<\/sub> sites, thus promoting the CO2<\/sub> hydrogenation.","articleNo":"20200207","authorCnList":["赵梓俨"," Dmitry E. Doronkin"," 叶英浩"," Jan-Dierk Grunwaldt"," 黄泽皑"," 周莹"],"authorEnList":["Ziyan Zhao"," Dmitry E. Doronkin"," Yinghao Ye"," Jan-Dierk Grunwaldt"," Zeai Huang"," Ying Zhou"],"authorList":["赵梓俨"," Dmitry E. Doronkin"," 叶英浩"," Jan-Dierk Grunwaldt"," 黄泽皑"," 周莹"],"authors":"赵梓俨, Dmitry E. Doronkin, 叶英浩, Jan-Dierk Grunwaldt, 黄泽皑, 周莹","authorsCn":"赵梓俨, Dmitry E. Doronkin, 叶英浩, Jan-Dierk Grunwaldt, 黄泽皑, 周莹","authorsEn":"Ziyan Zhao, Dmitry E. Doronkin, Yinghao Ye, Jan-Dierk Grunwaldt, Zeai Huang, Ying Zhou","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"赵梓俨, Dmitry E. Doronkin, 叶英浩, Jan-Dierk Grunwaldt, 黄泽皑, 周莹. 光照对Pt/Al2<\/sub>O3<\/sub>光热CO2<\/sub>加氢反应的增强作用. 催化学报, 2020, 41(2): 286-293. doi: S1872-2067(19)63445-5.","citationCn":"赵梓俨, Dmitry E. Doronkin, 叶英浩, Jan-Dierk Grunwaldt, 黄泽皑, 周莹. 光照对Pt/Al2<\/sub>O3<\/sub>光热CO2<\/sub>加氢反应的增强作用. 催化学报, 2020, 41(2): 286-293. doi: S1872-2067(19)63445-5.","citationEn":"赵梓俨, Dmitry E. Doronkin, 叶英浩, Jan-Dierk Grunwaldt, 黄泽皑, 周莹. Visible light-enhanced photothermal CO2<\/sub> hydrogenation over Pt/Al2<\/sub>O3<\/sub> catalyst. Chinese Journal of Catalysis, 2020, 41(2): 286-293. doi: S1872-2067(19)63445-5.","doi":"S1872-2067(19)63445-5","figContent":"","figList":[],"firstFig":"","fpage":"286","highCitedState":"","htmlCount":124,"htmlFile":"","id":"7adfc82f-458b-4326-923c-80154340c283","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"二氧化碳加氢, 光热催化, 铂/三氧化二铝, 原位漫反射红外光谱, 密度泛函理论","keywordCn":"二氧化碳加氢, 光热催化, 铂/三氧化二铝, 原位漫反射红外光谱, 密度泛函理论","keywordCnList":["二氧化碳加氢"," 光热催化"," 铂/三氧化二铝"," 原位漫反射红外光谱"," 密度泛函理论"],"keywordEn":"CO2<\/sub> hydrogenation, Photothermal catalysis, Pt/Al2<\/sub>O3<\/sub> Operando diffuse reflectance infrared, Fourier transform spectroscopy, Density functional theory","keywordEnList":["CO2<\/sub> hydrogenation"," Photothermal catalysis"," Pt/Al2<\/sub>O3<\/sub> Operando diffuse reflectance infrared"," Fourier transform spectroscopy"," Density functional theory"],"keywordList":["二氧化碳加氢"," 光热催化"," 铂/三氧化二铝"," 原位漫反射红外光谱"," 密度泛函理论"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"293","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":14,"pdfSize":1272.64,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"光照对Pt/Al2<\/sub>O3<\/sub>光热CO2<\/sub>加氢反应的增强作用","titleCn":"光照对Pt/Al2<\/sub>O3<\/sub>光热CO2<\/sub>加氢反应的增强作用","titleEn":"Visible light-enhanced photothermal CO2<\/sub> hydrogenation over Pt/Al2<\/sub>O3<\/sub> catalyst","viewCount":1712,"volume":"41","year":2020},{"abstractInfo":"在非均相催化加氢反应中,氢气(H2<\/sub>)一直被公认为是通过两步基元步骤参加还原反应的,包括第一步的分子解离和之后的反应物与原子氢键合,即所谓的Horiuti-Polanyi(HP)机理.直到我们研究组在Ag或Au催化丙烯醛加氢还原反应理论研究中发现非HP机理加氢路径存在时,新的机理才被提出,并引起广大研究者的浓厚兴趣.考虑到表面羟基(OH)和氧(O)在非均相催化体系中广泛存在,如常见的过渡金属催化的费托合成、甲烷重整、水汽转化及氨氧化等反应,基于第一性原理的密度泛函理论计算方法,我们对OH/O在一系列过渡金属催化作用下还原生成水的微观机理进行了系统全面的探究.
研究发现,不同金属对应于不同的催化氢化反应活性,以及不同的催化反应机理.在某些金属上H2<\/sub>以分子形式进攻反应物种的非HP机理有利,而在其它金属上经典的H2<\/sub>解离后参与氢化还原反应的HP机理更容易发生.详细分析显示,H2<\/sub>的解离活性决定了反应机理的种类:在对H2<\/sub>解离具有催化活性的金属(如Pt、Ni)表面,不论是(211)台阶面还是(111)平面,H2<\/sub>解离几乎都是无能垒过程,且伴随氢原子的强吸附,反应放热明显,导致活泼金属上HP机理更容易发生;与之相反,在不活泼的催化剂表面,H2<\/sub>解离很难发生,原子吸附也相当微弱,相比于断键裂解,H2<\/sub>更倾向于发生分子氢化的非HP机理.
另外,本文还定义了一个新的结构描述符(η<\/i>)来帮助理解两种机理发生的结构因素差异.η<\/i>是衡量分子氢化过渡态结构(TS)中H-H键解离程度的参数,根据其定义上下限数值分别设定为H2<\/sub>在各催化剂表面解离过渡态的键长(D<\/i>dis<\/sub>)和游离分子态的键长(D<\/i>H2<\/sub>).结果显示,易发生非HP机理的催化剂表面的TS结构对应的η<\/i>参数普遍低于0.4,即H-H原子对的确是以近分子形式参与氢化反应;相反发生经典HP机理的催化剂表面,η<\/i>参数普遍在0.5-0.8,即H-H即使以分子形式参与反应也是处于近解离状态,这预示了以解离吸附氢参与反应的优选性.","abstractInfoCn":"在非均相催化加氢反应中,氢气(H2<\/sub>)一直被公认为是通过两步基元步骤参加还原反应的,包括第一步的分子解离和之后的反应物与原子氢键合,即所谓的Horiuti-Polanyi (HP)机理.直到我们研究组在Ag或Au催化丙烯醛加氢还原反应理论研究中发现非HP机理加氢路径存在时,新的机理才被提出,并引起广大研究者的浓厚兴趣.考虑到表面羟基(OH)和氧(O)在非均相催化体系中广泛存在,如常见的过渡金属催化的费托合成、甲烷重整、水汽转化及氨氧化等反应,基于第一性原理的密度泛函理论计算方法,我们对OH/O在一系列过渡金属催化作用下还原生成水的微观机理进行了系统全面的探究.
研究发现,不同金属对应于不同的催化氢化反应活性,以及不同的催化反应机理.在某些金属上H2<\/sub>以分子形式进攻反应物种的非HP机理有利,而在其它金属上经典的H2<\/sub>解离后参与氢化还原反应的HP机理更容易发生.详细分析显示,H2<\/sub>的解离活性决定了反应机理的种类:在对H2<\/sub>解离具有催化活性的金属(如Pt、Ni)表面,不论是(211)台阶面还是(111)平面,H2<\/sub>解离几乎都是无能垒过程,且伴随氢原子的强吸附,反应放热明显,导致活泼金属上HP机理更容易发生;与之相反,在不活泼的催化剂表面,H2<\/sub>解离很难发生,原子吸附也相当微弱,相比于断键裂解,H2<\/sub>更倾向于发生分子氢化的非HP机理.
另外,本文还定义了一个新的结构描述符(η<\/i>)来帮助理解两种机理发生的结构因素差异.η<\/i>是衡量分子氢化过渡态结构(TS)中H-H键解离程度的参数,根据其定义上下限数值分别设定为H2<\/sub>在各催化剂表面解离过渡态的键长(D<\/i>dis<\/sub>)和游离分子态的键长(D<\/i>H2<\/sub>).结果显示,易发生非HP机理的催化剂表面的TS结构对应的η<\/i>参数普遍低于0.4,即H-H原子对的确是以近分子形式参与氢化反应;相反发生经典HP机理的催化剂表面,η<\/i>参数普遍在0.5-0.8,即H-H即使以分子形式参与反应也是处于近解离状态,这预示了以解离吸附氢参与反应的优选性.","abstractInfoEn":"It is generally acknowledged in heterogeneous catalysis that hydrogenation follows the so-called Horiuti-Polanyi (HP) mechanism. In this work, a thorough investigation of the mechanism of hydrogenation of hydroxyl groups and O catalyzed by a series of transition metals was carried out through density functional theory calculations, as surface hydroxyls and O are very common species in many catalytic systems. It is found that different metal catalysts exhibit different mechanisms. On some metal catalysts, the non-HP mechanism is preferred, whereas the classic HP mechanism is favored on other catalysts. Detailed analyses of the metal-dependent mechanism shows that the activity toward the dissociation of H2<\/sub> decides which mechanism is preferred. On active catalysts, such as Ni and Pt, H2<\/sub> prefers to dissociate with strong H adsorption energies, which lead to the classic HP mechanism being favored. On inactive surfaces, on the other hand, the adsorption of H is weak, which results in the non-HP mechanism being preferred. The parameter η<\/i>, which is a structural descriptor, was defined to understand the different mechanisms.","articleNo":"20200208","authorCnList":["孙希彤"," 陈建富"," 胡培君"],"authorEnList":["Xitong Sun"," Jianfu Chen"," P. Hu"],"authorList":["孙希彤"," 陈建富"," 胡培君"],"authors":"孙希彤, 陈建富, 胡培君","authorsCn":"孙希彤, 陈建富, 胡培君","authorsEn":"Xitong Sun, Jianfu Chen, P. Hu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"孙希彤, 陈建富, 胡培君. 过渡金属表面上水生成经典Horiuti-Polanyi机理与非Horiuti-Polanyi机理选择的总体趋势. 催化学报, 2020, 41(2): 294-301. doi: S1872-2067(19)63434-0.","citationCn":"孙希彤, 陈建富, 胡培君. 过渡金属表面上水生成经典Horiuti-Polanyi机理与非Horiuti-Polanyi机理选择的总体趋势. 催化学报, 2020, 41(2): 294-301. doi: S1872-2067(19)63434-0.","citationEn":"孙希彤, 陈建富, 胡培君. General trends in Horiuti-Polanyi mechanism vs non-Horiuti-Polanyi mechanism for water formation on transition metal surfaces. Chinese Journal of Catalysis, 2020, 41(2): 294-301. doi: S1872-2067(19)63434-0.","doi":"S1872-2067(19)63434-0","figContent":"","figList":[],"firstFig":"","fpage":"294","highCitedState":"","htmlCount":271,"htmlFile":"","id":"e05ec35c-202c-4870-aa42-a463acc6daff","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"氢化反应, Horiuti-Polanyi机理, 水的形成, 过渡金属, 密度泛函理论","keywordCn":"氢化反应, Horiuti-Polanyi机理, 水的形成, 过渡金属, 密度泛函理论","keywordCnList":["氢化反应"," Horiuti-Polanyi机理"," 水的形成"," 过渡金属"," 密度泛函理论"],"keywordEn":"Hydrogenation, Horiuti-Polanyi mechanism, Water formation, Transition metal, Density functional theory","keywordEnList":["Hydrogenation"," Horiuti-Polanyi mechanism"," Water formation"," Transition metal"," Density functional theory"],"keywordList":["氢化反应"," Horiuti-Polanyi机理"," 水的形成"," 过渡金属"," 密度泛函理论"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"301","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":13,"pdfSize":2686.5,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"过渡金属表面上水生成经典Horiuti-Polanyi机理与非Horiuti-Polanyi机理选择的总体趋势","titleCn":"过渡金属表面上水生成经典Horiuti-Polanyi机理与非Horiuti-Polanyi机理选择的总体趋势","titleEn":"General trends in Horiuti-Polanyi mechanism vs non-Horiuti-Polanyi mechanism for water formation on transition metal surfaces","viewCount":1996,"volume":"41","year":2020},{"abstractInfo":"光电催化(PEC)氧化法是一种使用半导体电极材料在光和电的共同作用下处理水中有机污染的有效方法.在PEC工艺中,施加偏压不仅可以利用电催化对有机污染物进行降解,而且在偏压作用下,光生电子-空穴对能够得到有效的分离和传输,从而大大提高了机物污染物的去除速率.尽管PEC技术已经取得了许多重要的突破,但是能量转换效率仍然无法满足实际应用.因此,开发具有优异性能,良好稳定性和低成本的光电极材料是一项具有挑战性的研究工作.
本文采用两步电沉积法制备了BiPO4<\/sub>纳米棒/还原氧化石墨烯/FTO复合光电极(BiPO4<\/sub>/rGO/FTO).电镜结果表明,电沉积制得的纳米棒状磷酸铋均匀负载在石墨烯纳米片层表面.采用甲基橙为模型体系,考察了复合光电极的光电催化活性.BiPO4<\/sub>/rGO/FTO复合电极的光电催化降解速率是BiPO4<\/sub>/FTO光电极的2.8倍,显示出优良的光电催化活性.实验进一步研究了工作电压和BiPO4<\/sub>沉积时间对甲基橙光电降解性能的影响.最佳的BiPO4<\/sub>沉积时间为45min,最佳工作电压为1.2V.捕获实验和ESR实验表明羟基自由基(·OH)和超氧化物自由基(·O2<\/sub>-<\/sup>)是该电极的主要活性物种.BiPO4<\/sub>/rGO/FTO复合电极经过四次循环实验后其降解甲基橙效率保持不变,显示出高稳定性,采用光电流,交流阻抗及其荧光测试对其光催化机理进行推测.结果表明该复合光电极具有高PEC活性的主要原因是:石墨烯的引入加快了BiPO4<\/sub>的电子空穴的分离,拓宽了石墨烯的可见光吸收范围;同时,石墨烯诱导产生的BiPO4<\/sub>混合相也进一步促进了光生电子空穴的分离,提高了光电降解活性.","abstractInfoCn":"光电催化(PEC)氧化法是一种使用半导体电极材料在光和电的共同作用下处理水中有机污染的有效方法.在PEC工艺中,施加偏压不仅可以利用电催化对有机污染物进行降解,而且在偏压作用下,光生电子-空穴对能够得到有效的分离和传输,从而大大提高了机物污染物的去除速率.尽管PEC技术已经取得了许多重要的突破,但是能量转换效率仍然无法满足实际应用.因此,开发具有优异性能,良好稳定性和低成本的光电极材料是一项具有挑战性的研究工作.
本文采用两步电沉积法制备了BiPO4<\/sub>纳米棒/还原氧化石墨烯/FTO复合光电极(BiPO4<\/sub>/rGO/FTO).电镜结果表明,电沉积制得的纳米棒状磷酸铋均匀负载在石墨烯纳米片层表面.采用甲基橙为模型体系,考察了复合光电极的光电催化活性.BiPO4<\/sub>/rGO/FTO复合电极的光电催化降解速率是BiPO4<\/sub>/FTO光电极的2.8倍,显示出优良的光电催化活性.实验进一步研究了工作电压和BiPO4<\/sub>沉积时间对甲基橙光电降解性能的影响.最佳的BiPO4<\/sub>沉积时间为45min,最佳工作电压为1.2V.捕获实验和ESR实验表明羟基自由基(·OH)和超氧化物自由基(·O2<\/sub>-<\/sup>)是该电极的主要活性物种.BiPO4<\/sub>/rGO/FTO复合电极经过四次循环实验后其降解甲基橙效率保持不变,显示出高稳定性,采用光电流,交流阻抗及其荧光测试对其光催化机理进行推测.结果表明该复合光电极具有高PEC活性的主要原因是:石墨烯的引入加快了BiPO4<\/sub>的电子空穴的分离,拓宽了石墨烯的可见光吸收范围;同时,石墨烯诱导产生的BiPO4<\/sub>混合相也进一步促进了光生电子空穴的分离,提高了光电降解活性.","abstractInfoEn":"In this work, a two-step electrodeposition method was employed to prepare BiPO4<\/sub> nanorod/reduced graphene oxide/FTO composite electrodes (BiPO4<\/sub>/rGO/FTO). The BiPO4<\/sub>/rGO/FTO composite electrode showed the higher photoelectrocatalytic (PEC) activity for the removal of methyl orange than pure BiPO4<\/sub>, which was 2.8 times higher than that of BiPO4<\/sub>/FTO electrode. The effects of working voltage and BiPO4<\/sub> deposition time on the degradation efficiency of methyl orange were investigated. The optimum BiPO4<\/sub> deposition time was 45 min and the optimum working voltage was 1.2 V. The trapping experiments showed that hydroxyl radicals (·<\/sup>OH) and superoxide radicals (·<\/sup>O2<\/sub>-<\/sup>) were the major reactive species in PEC degradation process. The BiPO4<\/sub>/rGO/FTO composite electrode showed the high stability and its methyl orange removal efficiency remained unchanged after four testing cycles. The reasons for the enhanced PEC efficiency of the BiPO4<\/sub>/rGO/FTO composite electrode was ascribed to the broad visible-light absorption range, the rapid transmission of photogenerated charges, and the mixed BiPO4<\/sub> phase by the introduction of rGO in the composite electrode films.","articleNo":"20200209","authorCnList":["和泽田"," 刘森"," 钟义"," 陈代梅"," 丁浩"," 王佼"," 杜高翔"," 杨光"," 郝强"],"authorEnList":["Zetian He"," Sen Liu"," Yi Zhong"," Daimei Chen"," Hao Ding"," Jiao Wang"," Gaoxiang Du"," Guang Yang"," Qiang Hao"],"authorList":["和泽田"," 刘森"," 钟义"," 陈代梅"," 丁浩"," 王佼"," 杜高翔"," 杨光"," 郝强"],"authors":"和泽田, 刘森, 钟义, 陈代梅, 丁浩, 王佼, 杜高翔, 杨光, 郝强","authorsCn":"和泽田, 刘森, 钟义, 陈代梅, 丁浩, 王佼, 杜高翔, 杨光, 郝强","authorsEn":"Zetian He, Sen Liu, Yi Zhong, Daimei Chen, Hao Ding, Jiao Wang, Gaoxiang Du, Guang Yang, Qiang Hao","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"和泽田, 刘森, 钟义, 陈代梅, 丁浩, 王佼, 杜高翔, 杨光, 郝强. BiPO4<\/sub>/石墨烯光电极的制备及其光电催化性能. 催化学报, 2020, 41(2): 302-311. doi: S1872-2067(19)63520-5.","citationCn":"和泽田, 刘森, 钟义, 陈代梅, 丁浩, 王佼, 杜高翔, 杨光, 郝强. BiPO4<\/sub>/石墨烯光电极的制备及其光电催化性能. 催化学报, 2020, 41(2): 302-311. doi: S1872-2067(19)63520-5.","citationEn":"和泽田, 刘森, 钟义, 陈代梅, 丁浩, 王佼, 杜高翔, 杨光, 郝强. Preparation of BiPO4<\/sub>/graphene photoelectrode and its photoelectrocatalyitic performance. Chinese Journal of Catalysis, 2020, 41(2): 302-311. doi: S1872-2067(19)63520-5.","doi":"S1872-2067(19)63520-5","figContent":"","figList":[],"firstFig":"","fpage":"302","highCitedState":"","htmlCount":91,"htmlFile":"","id":"3f0381c4-1984-4f27-a2f4-8689be0a9dbf","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"还原氧化石墨烯, BiPO4<\/sub>, FTO, 电沉积, 光电催化, 甲基橙","keywordCn":"还原氧化石墨烯, BiPO4<\/sub>, FTO, 电沉积, 光电催化, 甲基橙","keywordCnList":["还原氧化石墨烯"," BiPO4<\/sub>"," FTO"," 电沉积"," 光电催化"," 甲基橙"],"keywordEn":"Reduced graphene oxide, BiPO4<\/sub>, Fluorine-doped tin oxide, Electrodeposition, Photoelectrocatalysis, Methyl orange","keywordEnList":["Reduced graphene oxide"," BiPO4<\/sub>"," Fluorine-doped tin oxide"," Electrodeposition"," Photoelectrocatalysis"," Methyl orange"],"keywordList":["还原氧化石墨烯"," BiPO4<\/sub>"," FTO"," 电沉积"," 光电催化"," 甲基橙"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"311","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":9,"pdfSize":4078.83,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"BiPO4<\/sub>/石墨烯光电极的制备及其光电催化性能","titleCn":"BiPO4<\/sub>/石墨烯光电极的制备及其光电催化性能","titleEn":"Preparation of BiPO4<\/sub>/graphene photoelectrode and its photoelectrocatalyitic performance","viewCount":1637,"volume":"41","year":2020},{"abstractInfo":"双氧水(H2<\/sub>O2<\/sub>)是一种重要的绿色氧化剂,广泛应用于纺织、医疗、废水处理、军事等重要领域.目前,H2<\/sub>O2<\/sub>的工业生产以蒽醌法为主,该法设备投资大、运行成本高,同时工艺涉及大量的有机溶液,活性中间体蒽醌也会发生缓慢降解,产生有毒副产物.与蒽醌法相比,通过负载型贵金属催化剂催化H2<\/sub>与O2<\/sub>反应直接合成H2<\/sub>O2<\/sub>,过程绿色环保且生产工艺简单,引起了各界广泛关注.然而,从热力学上分析,H2<\/sub>和O2<\/sub>更容易反应生成H2<\/sub>O,H2<\/sub>O2<\/sub>只是该反应的中间产物,会继续发生加氢和直接分解反应生成H2<\/sub>O,导致H2<\/sub>和O2<\/sub>的低效利用,开发高H2<\/sub>O2<\/sub>选择性且高反应效率的催化剂已成为氢氧直接合成H2<\/sub>O2<\/sub>研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H2<\/sub>O2<\/sub>的副反应,进而提升H2<\/sub>O2<\/sub>的选择性和反应效率;尽管已取得了良好的进展,但仍需发展新的调控策略来满足工业应用的要求.
本课题组前期研究表明,促使H2<\/sub>O2<\/sub>从催化剂上脱附可以有效地提升H2<\/sub>O2<\/sub>的选择性和产率.相比于针对反应中心的调控,不稳定的H2<\/sub>O2<\/sub>从催化剂上快速脱附同样起到抑制H2<\/sub>O2<\/sub>参与副反应的作用.为此,本文提出一种炭量可控的非均一界面改性方法,以常规的Pd/TiO2<\/sub>作为研究对象,借助各种结构表征,发现炭物种在TiO2<\/sub>表面呈非均一分散状态,而且改性对于催化剂的几何结构影响较小;另外,催化剂表面的疏水性会随着碳含量的增加而增加,导致其与H2<\/sub>O2<\/sub>间的吸附能相应变小.反应结果显示,表面非均一的炭化改性技术可以显著提升Pd/TiO2<\/sub>催化剂的H2<\/sub>O2<\/sub>选择性和产率.通过构效关系分析,可知这种改性技术可以保持Pd颗粒与TiO2<\/sub>间相互作用的同时,还可以促进H2<\/sub>O2<\/sub>的快速脱附,进而提升改性Pd/TiO2<\/sub>催化剂的H2<\/sub>O2<\/sub>直接合成效率.该改性方法简单、易控,可拓展应用到其他类型催化剂的H2<\/sub>O2<\/sub>直接合成性能调控与改进.","abstractInfoCn":"双氧水(H2<\/sub>O2<\/sub>)是一种重要的绿色氧化剂,广泛应用于纺织、医疗、废水处理、军事等重要领域.目前,H2<\/sub>O2<\/sub>的工业生产以蒽醌法为主,该法设备投资大、运行成本高,同时工艺涉及大量的有机溶液,活性中间体蒽醌也会发生缓慢降解,产生有毒副产物.与蒽醌法相比,通过负载型贵金属催化剂催化H2<\/sub>与O2<\/sub>反应直接合成H2<\/sub>O2<\/sub>,过程绿色环保且生产工艺简单,引起了各界广泛关注.然而,从热力学上分析,H2<\/sub>和O2<\/sub>更容易反应生成H2<\/sub>O,H2<\/sub>O2<\/sub>只是该反应的中间产物,会继续发生加氢和直接分解反应生成H2<\/sub>O,导致H2<\/sub>和O2<\/sub>的低效利用,开发高H2<\/sub>O2<\/sub>选择性且高反应效率的催化剂已成为氢氧直接合成H2<\/sub>O2<\/sub>研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H2<\/sub>O2<\/sub>的副反应,进而提升H2<\/sub>O2<\/sub>的选择性和反应效率;尽管已取得了良好的进展,但仍需发展新的调控策略来满足工业应用的要求.
本课题组前期研究表明,促使H2<\/sub>O2<\/sub>从催化剂上脱附可以有效地提升H2<\/sub>O2<\/sub>的选择性和产率.相比于针对反应中心的调控,不稳定的H2<\/sub>O2<\/sub>从催化剂上快速脱附同样起到抑制H2<\/sub>O2<\/sub>参与副反应的作用.为此,本文提出一种炭量可控的非均一界面改性方法,以常规的Pd/TiO2<\/sub>作为研究对象,借助各种结构表征,发现炭物种在TiO2<\/sub>表面呈非均一分散状态,而且改性对于催化剂的几何结构影响较小;另外,催化剂表面的疏水性会随着碳含量的增加而增加,导致其与H2<\/sub>O2<\/sub>间的吸附能相应变小.反应结果显示,表面非均一的炭化改性技术可以显著提升Pd/TiO2<\/sub>催化剂的H2<\/sub>O2<\/sub>选择性和产率.通过构效关系分析,可知这种改性技术可以保持Pd颗粒与TiO2<\/sub>间相互作用的同时,还可以促进H2<\/sub>O2<\/sub>的快速脱附,进而提升改性Pd/TiO2<\/sub>催化剂的H2<\/sub>O2<\/sub>直接合成效率.该改性方法简单、易控,可拓展应用到其他类型催化剂的H2<\/sub>O2<\/sub>直接合成性能调控与改进.","abstractInfoEn":"Series of heterogeneous interfacial engineered TiO2<\/sub> (C-TiO2<\/sub>) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO2<\/sub> were used as catalytic supports to load Pd nanoparticles for H2<\/sub>O2<\/sub> direct synthesis from H2<\/sub> and O2<\/sub>. The as-prepared samples were systematically studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), air isothermal microcalorimeter, temperature-programmed reduction of H2<\/sub> (H2<\/sub>-TPR), and so on. The catalytic results showed that H2<\/sub>O2<\/sub> productivity and H2<\/sub>O2<\/sub> selectivity of Pd/C-TiO2<\/sub> firstly rose with increasing carbon content and then declined. Pd/C-TiO2<\/sub> catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H2<\/sub>O2<\/sub>/gPd<\/sub>/h of productivity, which were significantly better than those of pristine Pd/TiO2<\/sub> (45.2% and 1827 mmol H2<\/sub>O2<\/sub>/gPd<\/sub>/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO2<\/sub> surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO2<\/sub> was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H2<\/sub>O2<\/sub> with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO2<\/sub> and simultaneously accelerate the H2<\/sub>O2<\/sub> desorption. Both factors further determined the excellent H2<\/sub>O2<\/sub> direct synthesis performance of Pd/C-TiO2<\/sub>.","articleNo":"20200210","authorCnList":["严伟"," 孙睿"," 李蒙"," 李力成"," 杨祝红"," 花泽林"," 陆小华"," 刘畅"],"authorEnList":["Wei Yan"," Rui Sun"," Meng Li"," Licheng Li"," Zhuhong Yang"," Zelin Hua"," Xiaohua Lu"," Chang Liu"],"authorList":["严伟"," 孙睿"," 李蒙"," 李力成"," 杨祝红"," 花泽林"," 陆小华"," 刘畅"],"authors":"严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅","authorsCn":"严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅","authorsEn":"Wei Yan, Rui Sun, Meng Li, Licheng Li, Zhuhong Yang, Zelin Hua, Xiaohua Lu, Chang Liu","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅. 可控碳改性Pd/TiO2<\/sub>用于直接合成双氧水:非均相界面对催化性能的影响. 催化学报, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1.","citationCn":"严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅. 可控碳改性Pd/TiO2<\/sub>用于直接合成双氧水:非均相界面对催化性能的影响. 催化学报, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1.","citationEn":"严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅. Heterogeneous interfacial engineering of Pd/TiO2<\/sub> with controllable carbon content for improved direct synthesis efficiency of H2<\/sub>O2<\/sub>. Chinese Journal of Catalysis, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1.","doi":"S1872-2067(19)63412-1","figContent":"","figList":[],"firstFig":"","fpage":"312","highCitedState":"","htmlCount":62,"htmlFile":"","id":"ad981c00-a9d8-45f8-a052-8a45cb6dc818","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"H2<\/sub>O2<\/sub>直接合成, 二氧化钛, 炭, 非均一界面改性, 钯","keywordCn":"H2<\/sub>O2<\/sub>直接合成, 二氧化钛, 炭, 非均一界面改性, 钯","keywordCnList":["H2<\/sub>O2<\/sub>直接合成"," 二氧化钛"," 炭"," 非均一界面改性"," 钯"],"keywordEn":"Direct synthesis of H2<\/sub>O2<\/sub>, TiO2<\/sub>, Carbon, Heterogeneous interfacial engineering, Pd","keywordEnList":["Direct synthesis of H2<\/sub>O2<\/sub>"," TiO2<\/sub>"," Carbon"," Heterogeneous interfacial engineering"," Pd"],"keywordList":["H2<\/sub>O2<\/sub>直接合成"," 二氧化钛"," 炭"," 非均一界面改性"," 钯"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"321","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":1034.06,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"可控碳改性Pd/TiO2<\/sub>用于直接合成双氧水:非均相界面对催化性能的影响","titleCn":"可控碳改性Pd/TiO2<\/sub>用于直接合成双氧水:非均相界面对催化性能的影响","titleEn":"Heterogeneous interfacial engineering of Pd/TiO2<\/sub> with controllable carbon content for improved direct synthesis efficiency of H2<\/sub>O2<\/sub>","viewCount":1554,"volume":"41","year":2020},{"abstractInfo":"近几年过一硫酸盐(PMS)活化技术备受关注,其中利用太阳能活化PMS具有可持续和环保的优势,但PMS本身不吸收可见光.因此,本文提出利用具有可见光响应的石墨相氮化碳(g-C3<\/sub>N4<\/sub>)激发产生光电子进而活化PMS.首先利用三聚氰胺前驱体通过热缩聚法制备g-C3<\/sub>N4<\/sub>,通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外-可见光漫反射(UV-Vis)、荧光光谱(PL)、透射电镜(TEM)、N2<\/sub>吸附脱附测试(BET)、电化学等一系列方法对g-C3<\/sub>N4<\/sub>进行表征,研究其表面性质及光学性能.结果显示,g-C3<\/sub>N4<\/sub>具有典型的片层结构和可见光活性,禁带宽度为2.7eV.本文选取光惰性的内分泌干扰物邻苯二甲酸二甲酯(DMP)为目标污染物,系统地研究了其降解动力学和降解机理.研究发现,在短波紫外光(254和300nm)照射下,直接光解和·OH参与的反应机理能实现DMP的光降解,而在可见光照射下g-C3<\/sub>N4<\/sub>介导的光催化过程不能使DMP分解;但当添加PMS时,体系主导自由基由·O2<\/sub>-<\/sup>转化为SO4<\/sub>·-<\/sup>和·OH,从而实现DMP的有效降解和矿化.研究还发现,高浓度的PMS和高剂量的g-C3<\/sub>N4<\/sub>均可以提高PMS的活化量和相应的DMP降解效率,但提高催化剂剂量的方式能更充分的利用PMS.尽管高浓度的DMP阻碍了PMS和光催化剂g-C3<\/sub>N4<\/sub>的有效接触,但可以提高PMS的利用率.当pH低于零电荷点(5.4)时,DMP的降解效率较高.此外,使用两种淬灭剂(乙醇和叔丁醇)与DMP进行竞争性实验,结合电子自旋共振检测,表明SO4<\/sub>·-<\/sup>和·OH都是体系主要的自由基.此外,还对g-C3<\/sub>N4<\/sub>的可持续性能进行考察,四次循环实验结果显示,该催化剂具有良好的可重复利用性.对DMP降解进行总有机碳测定,发现降低了19%.最后,利用液相色谱质谱联用对DMP降解产物进行定性定量分析,发现DMP主要通过SO4<\/sub>·-<\/sup>和·OH对苯环的攻击以及脂肪族链的氧化断键这两种途径进行降解.综上可见,利用可见光激发g-C3<\/sub>N4<\/sub>产生的光电子能有效活化PMS降解顽固型有机污染物,可为实现太阳能活化PMS技术提供有力的技术参考.","abstractInfoCn":"近几年过一硫酸盐(PMS)活化技术备受关注,其中利用太阳能活化PMS具有可持续和环保的优势,但PMS本身不吸收可见光.因此,本文提出利用具有可见光响应的石墨相氮化碳(g-C3<\/sub>N4<\/sub>)激发产生光电子进而活化PMS.首先利用三聚氰胺前驱体通过热缩聚法制备g-C3<\/sub>N4<\/sub>,通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外-可见光漫反射(UV-Vis)、荧光光谱(PL)、透射电镜(TEM)、N2<\/sub>吸附脱附测试(BET)、电化学等一系列方法对g-C3<\/sub>N4<\/sub>进行表征,研究其表面性质及光学性能.结果显示,g-C3<\/sub>N4<\/sub>具有典型的片层结构和可见光活性,禁带宽度为2.7eV.本文选取光惰性的内分泌干扰物邻苯二甲酸二甲酯(DMP)为目标污染物,系统地研究了其降解动力学和降解机理.研究发现,在短波紫外光(254和300nm)照射下,直接光解和·OH参与的反应机理能实现DMP的光降解,而在可见光照射下g-C3<\/sub>N4<\/sub>介导的光催化过程不能使DMP分解;但当添加PMS时,体系主导自由基由·O2<\/sub>-<\/sup>转化为SO4<\/sub>·-<\/sup>和·OH,从而实现DMP的有效降解和矿化.研究还发现,高浓度的PMS和高剂量的g-C3<\/sub>N4<\/sub>均可以提高PMS的活化量和相应的DMP降解效率,但提高催化剂剂量的方式能更充分的利用PMS.尽管高浓度的DMP阻碍了PMS和光催化剂g-C3<\/sub>N4<\/sub>的有效接触,但可以提高PMS的利用率.当pH低于零电荷点(5.4)时,DMP的降解效率较高.此外,使用两种淬灭剂(乙醇和叔丁醇)与DMP进行竞争性实验,结合电子自旋共振检测,表明SO4<\/sub>·-<\/sup>和·OH都是体系主要的自由基.此外,还对g-C3<\/sub>N4<\/sub>的可持续性能进行考察,四次循环实验结果显示,该催化剂具有良好的可重复利用性.对DMP降解进行总有机碳测定,发现降低了19%.最后,利用液相色谱质谱联用对DMP降解产物进行定性定量分析,发现DMP主要通过SO4<\/sub>·-<\/sup>和·OH对苯环的攻击以及脂肪族链的氧化断键这两种途径进行降解.综上可见,利用可见光激发g-C3<\/sub>N4<\/sub>产生的光电子能有效活化PMS降解顽固型有机污染物,可为实现太阳能活化PMS技术提供有力的技术参考.","abstractInfoEn":"Excitation of metal-free graphitic carbon nitride (g-C3<\/sub>N4<\/sub>) under visible light can successfully achieve efficient activation of peroxymonosulfate (PMS). Synergistic effects and involved mechanism were systematically investigated using a light-inert endocrine disrupting compound, dimethyl phthalate (DMP), as the target pollutant. Under visible light irradiation, DMP could not be degraded by direct g-C3<\/sub>N4<\/sub>-mediated photocatalysis, while in the presence of PMS, the dominant radicals were converted from ·O2<\/sub> to SO4<\/sub>·-<\/sup> and ·OH, resulting in effective DMP degradation and mineralization. Results showed that higher dosage of PMS or g-C3<\/sub>N4<\/sub> could increase the activation amount of PMS and corresponding DMP degradation efficiency, but the latter approach was more productive in terms of making the most of PMS. High DMP concentration hindered effective contact between PMS and g-C3<\/sub>N4<\/sub>, but could provide efficient use of PMS. Higher DMP degradation efficiency was achieved at pH lower than the point of zero charge (5.4). Based on intermediates identification, the DMP degradation was found mainly through radical attack (·OH and SO4<\/sub>·-<\/sup>) of the benzene ring and oxidation of the aliphatic chains.","articleNo":"20200211","authorCnList":["徐立杰"," 戚蓝月"," 孙阳"," 公晗"," 陈一良"," 裴纯"," 甘露"],"authorEnList":["Lijie Xu"," Lanyue Qi"," Yang Sun"," Han Gong"," Yiliang Chen"," Chun Pei"," Lu Gan"],"authorList":["徐立杰"," 戚蓝月"," 孙阳"," 公晗"," 陈一良"," 裴纯"," 甘露"],"authors":"徐立杰, 戚蓝月, 孙阳, 公晗, 陈一良, 裴纯, 甘露","authorsCn":"徐立杰, 戚蓝月, 孙阳, 公晗, 陈一良, 裴纯, 甘露","authorsEn":"Lijie Xu, Lanyue Qi, Yang Sun, Han Gong, Yiliang Chen, Chun Pei, Lu Gan","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"徐立杰, 戚蓝月, 孙阳, 公晗, 陈一良, 裴纯, 甘露. 石墨相氮化碳可见光下活化过一硫酸盐氧化降解光惰性邻苯二甲酸二甲酯的机理研究. 催化学报, 2020, 41(2): 322-332. doi: S1872-2067(19)63447-9.","citationCn":"徐立杰, 戚蓝月, 孙阳, 公晗, 陈一良, 裴纯, 甘露. 石墨相氮化碳可见光下活化过一硫酸盐氧化降解光惰性邻苯二甲酸二甲酯的机理研究. 催化学报, 2020, 41(2): 322-332. doi: S1872-2067(19)63447-9.","citationEn":"徐立杰, 戚蓝月, 孙阳, 公晗, 陈一良, 裴纯, 甘露. Mechanistic studies on peroxymonosulfate activation by g-C3<\/sub>N4<\/sub> under visible light for enhanced oxidation of light-inert dimethyl phthalate. Chinese Journal of Catalysis, 2020, 41(2): 322-332. doi: S1872-2067(19)63447-9.","doi":"S1872-2067(19)63447-9","figContent":"","figList":[],"firstFig":"","fpage":"322","highCitedState":"","htmlCount":90,"htmlFile":"","id":"2590a13d-ae4b-4ce3-8884-e1a36fb10338","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"石墨相氮化碳, 可见光, 过一硫酸盐, 邻苯二甲酸二甲酯, 活化, 降解","keywordCn":"石墨相氮化碳, 可见光, 过一硫酸盐, 邻苯二甲酸二甲酯, 活化, 降解","keywordCnList":["石墨相氮化碳"," 可见光"," 过一硫酸盐"," 邻苯二甲酸二甲酯"," 活化"," 降解"],"keywordEn":"Graphitic carbon nitride, Visible light, Peroxymonosulfate, Dimethyl phthalate, Activation, Degradation","keywordEnList":["Graphitic carbon nitride"," Visible light"," Peroxymonosulfate"," Dimethyl phthalate"," Activation"," Degradation"],"keywordList":["石墨相氮化碳"," 可见光"," 过一硫酸盐"," 邻苯二甲酸二甲酯"," 活化"," 降解"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"332","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":6,"pdfSize":940.74,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"石墨相氮化碳可见光下活化过一硫酸盐氧化降解光惰性邻苯二甲酸二甲酯的机理研究","titleCn":"石墨相氮化碳可见光下活化过一硫酸盐氧化降解光惰性邻苯二甲酸二甲酯的机理研究","titleEn":"Mechanistic studies on peroxymonosulfate activation by g-C3<\/sub>N4<\/sub> under visible light for enhanced oxidation of light-inert dimethyl phthalate","viewCount":1619,"volume":"41","year":2020},{"abstractInfo":"化石燃料的快速消耗导致了严重的环境问题,特别是全球变暖和雾霾.寻找替代传统化石能源的清洁能源是当务之急.光催化水分解技术被认为是将太阳能转化为绿色可再生能源的一种很有前景的方法.作为一种用于光催化的半导体材料,需要满足三个条件:(1)带隙要高于水分解的电压(1.23eV);(2)带边缘位置应跨越氢还原电位和氧氧化电位;(3)在光催化过程中,光催化材料应具有抗光腐蚀的稳定性.然而,水氧化的半反应是非常困难的,主要是涉及到复杂的四电子氧化过程和O-O键形成的高激活能量.TiO2<\/sub>是光催化剂中最重要的材料之一,因为它具有成本低,无毒,光稳定性好等优点。但TiO2<\/sub>的可见光利用率低,载流子复合率高,光催化效率受到严重限制.通过H2<\/sub>还原可以引入Ti3+<\/sup>,还原得到的TiO2<\/sub>带隙变窄,具有较好的可见光催化产氧活性.
由于贵金属纳米粒子具有表面等离子体共振(SPR)效应,将贵金属(如金或者银)与TiO2<\/sub>结合是将光催化剂的光吸收边扩展到更长的波长一种有效途径.然而,贵金属的价格限制了它们的商业化,因此需要低成本的金属作为替代品.最近,金属铋(Bi)被证明是贵金属的理想替代品,具有明显的SPR效应,在可见光甚至近红外范围具有优异的光吸收性能.通过光还原,化学还原,水热还原等还原方法,可以方便地获得金属Bi.然而,通过原位沉积的方法将金属Bi纳米粒子直接沉积到半导体表面仍然是一个很大的挑战.
本文采用双金属有机骨架衍生的合成策略,通过调节合成温度,将金属Bi原位沉积到还原TiO2<\/sub>微球表面(Bi@R-TiO2<\/sub>).采用X射线衍射,扫描电镜,透射电镜,X射线光电子能谱,漫反射光谱,光致发光光谱,阻抗,光电流响应等表征技术对制备样品的结构和光学性能进行了研究.结果表明,通过乙二醇可以将Ti4+<\/sup>还原为Ti3+<\/sup>得到还原的TiOx<\/i><\/sub>,Bi3+<\/sup>同时也被还原为金属Bi.当退火温度控制在300℃时,相应的Bi@R-TiO2<\/sub>-300表现出最高的全光谱光催化产氧活性(4728.709μmolh-1<\/sup>g-1<\/sup>),分别是的纯TiO2<\/sub>和Bi-Ti双金属有机框架的5.9和9.5倍.这可归因于以下三点:(1)金属Bi作为“电子受体”,加速了TiO2<\/sub>向Bi的载流子转移;(2)负载到还原TiO2<\/sub>表面的金属Bi具有SPR效应可以增强可见光和近红外光的吸收能力;(3)Ti3+<\/sup>的产生进一步减小TiO2<\/sub>的禁带宽度.","abstractInfoCn":"化石燃料的快速消耗导致了严重的环境问题,特别是全球变暖和雾霾.寻找替代传统化石能源的清洁能源是当务之急.光催化水分解技术被认为是将太阳能转化为绿色可再生能源的一种很有前景的方法.作为一种用于光催化的半导体材料,需要满足三个条件:(1)带隙要高于水分解的电压(1.23eV);(2)带边缘位置应跨越氢还原电位和氧氧化电位;(3)在光催化过程中,光催化材料应具有抗光腐蚀的稳定性.然而,水氧化的半反应是非常困难的,主要是涉及到复杂的四电子氧化过程和O-O键形成的高激活能量.TiO2<\/sub>是光催化剂中最重要的材料之一,因为它具有成本低,无毒,光稳定性好等优点。但TiO2<\/sub>的可见光利用率低,载流子复合率高,光催化效率受到严重限制.通过H2<\/sub>还原可以引入Ti3+<\/sup>,还原得到的TiO2<\/sub>带隙变窄,具有较好的可见光催化产氧活性.
由于贵金属纳米粒子具有表面等离子体共振(SPR)效应,将贵金属(如金或者银)与TiO2<\/sub>结合是将光催化剂的光吸收边扩展到更长的波长一种有效途径.然而,贵金属的价格限制了它们的商业化,因此需要低成本的金属作为替代品.最近,金属铋(Bi)被证明是贵金属的理想替代品,具有明显的SPR效应,在可见光甚至近红外范围具有优异的光吸收性能.通过光还原,化学还原,水热还原等还原方法,可以方便地获得金属Bi.然而,通过原位沉积的方法将金属Bi纳米粒子直接沉积到半导体表面仍然是一个很大的挑战.
本文采用双金属有机骨架衍生的合成策略,通过调节合成温度,将金属Bi原位沉积到还原TiO2<\/sub>微球表面(Bi@R-TiO2<\/sub>).采用X射线衍射,扫描电镜,透射电镜,X射线光电子能谱,漫反射光谱,光致发光光谱,阻抗,光电流响应等表征技术对制备样品的结构和光学性能进行了研究.结果表明,通过乙二醇可以将Ti4+<\/sup>还原为Ti3+<\/sup>得到还原的TiOx<\/i><\/sub>,Bi3+<\/sup>同时也被还原为金属Bi.当退火温度控制在300℃时,相应的Bi@R-TiO2<\/sub>-300表现出最高的全光谱光催化产氧活性(4728.709μmol h-1<\/sup> g-1<\/sup>),分别是的纯TiO2<\/sub>和Bi-Ti双金属有机框架的5.9和9.5倍.这可归因于以下三点:(1)金属Bi作为“电子受体”,加速了TiO2<\/sub>向Bi的载流子转移;(2)负载到还原TiO2<\/sub>表面的金属Bi具有SPR效应可以增强可见光和近红外光的吸收能力;(3) Ti3+<\/sup>的产生进一步减小TiO2<\/sub>的禁带宽度.","abstractInfoEn":"Herein, novel plasmonic Bi metal in situ<\/i> deposited in reduced TiO2<\/sub> microspheres (Bi@R-TiO2<\/sub>) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different characterization techniques, including XRD, SEM, TEM, XPS, DRS, PL, EIS, and photocurrent generation, are performed to investigate the structural and optical properties of the as-prepared samples. The results indicate that the Bi particles are generated inside and outside of reduced TiO2<\/sub> microspheres via the reduction of Ti4+<\/sup> and Bi3+<\/sup> by ethylene glycol. When the annealing temperature is controlled at 300 ℃, the corresponding Bi@R-TiO2<\/sub>-300 sample with an appropriate amount of Bi nanoparticles exhibits the highest full solar spectrum photocatalytic oxygen evolution activity (4728.709 μmol h-1<\/sup> g-1<\/sup>), which is 5.9 and 9.5 times higher than that of pure TiO2<\/sub> and Bi-Ti bimetal organic frameworks (Bi-Ti-MOFs). Several reasons are suggested for the above results:(1) Bi metal behaves as an \"electron acceptor\" to accelerate the charge carrier transfer from TiO2<\/sub> to Bi; (2) The surface plasmon resonance effect of loaded metallic Bi particles can enhance the visible and NIR light absorption capacity; (3) The generation of Ti3+<\/sup> further narrows the band gap of TiO2<\/sub>.","articleNo":"20200212","authorCnList":["赵行"," 梁嫜倩"," 刘香"," 邱鹏源"," 崔洪芝"," 田健"],"authorEnList":["Hang Zhao"," Zhangqian Liang"," Xiang Liu"," Pengyuan Qiu"," Hongzhi Cui"," Jian Tian"],"authorList":["赵行"," 梁嫜倩"," 刘香"," 邱鹏源"," 崔洪芝"," 田健"],"authors":"赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健","authorsCn":"赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健","authorsEn":"Hang Zhao, Zhangqian Liang, Xiang Liu, Pengyuan Qiu, Hongzhi Cui, Jian Tian","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健. 具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO2<\/sub>微米球及其高效全光谱光催化产氧. 催化学报, 2020, 41(2): 333-340. doi: S1872-2067(19)63428-5.","citationCn":"赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健. 具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO2<\/sub>微米球及其高效全光谱光催化产氧. 催化学报, 2020, 41(2): 333-340. doi: S1872-2067(19)63428-5.","citationEn":"赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健. Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO2<\/sub> microspheres for efficient full solar spectrum photocatalytic oxygen evolution. Chinese Journal of Catalysis, 2020, 41(2): 333-340. doi: S1872-2067(19)63428-5.","doi":"S1872-2067(19)63428-5","figContent":"","figList":[],"firstFig":"","fpage":"333","highCitedState":"","htmlCount":144,"htmlFile":"","id":"5939d725-f228-4b87-b097-acc015c09091","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"铋纳米颗粒, 全光谱, 产氧, 光催化, 多孔微米球","keywordCn":"铋纳米颗粒, 全光谱, 产氧, 光催化, 多孔微米球","keywordCnList":["铋纳米颗粒"," 全光谱"," 产氧"," 光催化"," 多孔微米球"],"keywordEn":"Bi nanoparticles, Full solar spectrum, O2<\/sub> evolution, Photocatalysis, Porous microspheres","keywordEnList":["Bi nanoparticles"," Full solar spectrum"," O2<\/sub> evolution"," Photocatalysis"," Porous microspheres"],"keywordList":["铋纳米颗粒"," 全光谱"," 产氧"," 光催化"," 多孔微米球"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"340","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":9,"pdfSize":2382.18,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO2<\/sub>微米球及其高效全光谱光催化产氧","titleCn":"具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO2<\/sub>微米球及其高效全光谱光催化产氧","titleEn":"Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO2<\/sub> microspheres for efficient full solar spectrum photocatalytic oxygen evolution","viewCount":1711,"volume":"41","year":2020},{"abstractInfo":"苯甲醛是一种用途广泛的重要化学品,通过O2<\/sub>氧化甲苯制取苯甲醛是最佳生产途径,也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可,对该反应的多相催化过程也已经研究了几十年,但其性能仍远远低于工业要求.当前的工业过程主要有甲苯氯化水解法和甲苯均相氧化法两种,但都存在严重的环境污染和腐蚀问题,且产品中含有少量卤素,阻碍了其在诸如香水或食品中的高端应用.近年来,以O2<\/sub>作为氧化剂及Pd,Au,Pt,Ag,Ru等贵金属或它们间的合金为催化剂的甲苯液相氧化反应研究取得了一些很好的进展,但仍然不能在高甲苯转化率下高选择性地得到苯甲醛.本课题组曾报道了一种高效的混相催化体系,以O2<\/sub>作为氧化剂将甲苯专一地催化氧化为苯甲醛,其中十六烷基膦酸-氧化铁(HDPA-FeOx<\/i><\/sub>)纳米颗粒处在甲苯和水的界面上,稳定了该O/W类皮克林乳液(Pickering).为了进一步提高催化剂晶格氧的移动性以提升催化活性,本文采用Mn,Co,Ni,Cu,Cr,Mo,V和Ti等一系列金属氧化物对催化剂HDPA-FeOx<\/i><\/sub>进行掺杂,同时使用一种特殊的纳米Al2<\/sub>O3<\/sub>作为载体,大大地增加了催化剂制备的便捷性和保证了催化剂在实际应用中的稳定性.
TEM和XRD结果表明,Al2<\/sub>O3<\/sub>负载了金属氧化物后,其形貌仍为纳米棒状结构,并只能观察到Al2<\/sub>O3<\/sub>的晶相衍射峰,表明金属氧化物均匀地负载在其表面.BET结果表明,负载后的催化剂的孔结构与载体Al2<\/sub>O3<\/sub>类似.FT-IR结果表明,HDPA很好地吸附在了催化剂表面.TG结果表明,催化剂中HDPA含量与加入量相符,质量分数为~5%.结合前期工作可知,HDPA能够调整FeM纳米棒表面催化性质,且以1HDPA/nm2<\/sup>的密度为最佳,此时,甲苯液相氧化为苯甲醛的催化性能最佳.
催化性能测试结果表明,催化剂吸附了HDPA后,甲苯的转化率显著增加,且只生成苯甲醛.在所考察的第二种掺杂金属中,以Ni的效果为最好.该催化剂在最佳反应条件下,甲苯转化率为83%(TOF=0.027nm-2<\/sup>·s-1<\/sup>),苯甲醛选择性为~100%.而Cr,Mo,V和Ti等高价金属则抑制了该反应,这也说明通过掺杂第二种金属调变晶格氧的活动性可影响反应性能.经过优化后,最佳反应条件为:pH值为2.5,反应温度为180℃.原位FT-IR结果表明,180℃下,甲苯在吸附有HDPA的催化剂表面能够发生化学吸附,苄基C-H键解离并与晶格氧产生结合,形成了C6<\/sub>H5<\/sub>-CH2<\/sub>-O-Fe中间物种,该物种脱附即得苯甲醛.该温度下,表面HDPA对甲苯的化学吸附不可缺.","abstractInfoCn":"苯甲醛是一种用途广泛的重要化学品,通过O2<\/sub>氧化甲苯制取苯甲醛是最佳生产途径,也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可,对该反应的多相催化过程也已经研究了几十年,但其性能仍远远低于工业要求.当前的工业过程主要有甲苯氯化水解法和甲苯均相氧化法两种,但都存在严重的环境污染和腐蚀问题,且产品中含有少量卤素,阻碍了其在诸如香水或食品中的高端应用.近年来,以O2<\/sub>作为氧化剂及Pd,Au,Pt,Ag,Ru等贵金属或它们间的合金为催化剂的甲苯液相氧化反应研究取得了一些很好的进展,但仍然不能在高甲苯转化率下高选择性地得到苯甲醛.本课题组曾报道了一种高效的混相催化体系,以O2<\/sub>作为氧化剂将甲苯专一地催化氧化为苯甲醛,其中十六烷基膦酸-氧化铁(HDPA-FeOx<\/i><\/sub>)纳米颗粒处在甲苯和水的界面上,稳定了该O/W类皮克林乳液(Pickering).为了进一步提高催化剂晶格氧的移动性以提升催化活性,本文采用Mn,Co,Ni,Cu,Cr,Mo,V和Ti等一系列金属氧化物对催化剂HDPA-FeOx<\/i><\/sub>进行掺杂,同时使用一种特殊的纳米Al2<\/sub>O3<\/sub>作为载体,大大地增加了催化剂制备的便捷性和保证了催化剂在实际应用中的稳定性.
TEM和XRD结果表明,Al2<\/sub>O3<\/sub>负载了金属氧化物后,其形貌仍为纳米棒状结构,并只能观察到Al2<\/sub>O3<\/sub>的晶相衍射峰,表明金属氧化物均匀地负载在其表面.BET结果表明,负载后的催化剂的孔结构与载体Al2<\/sub>O3<\/sub>类似.FT-IR结果表明,HDPA很好地吸附在了催化剂表面.TG结果表明,催化剂中HDPA含量与加入量相符,质量分数为~5%.结合前期工作可知,HDPA能够调整FeM纳米棒表面催化性质,且以1 HDPA/nm2<\/sup>的密度为最佳,此时,甲苯液相氧化为苯甲醛的催化性能最佳.
催化性能测试结果表明,催化剂吸附了HDPA后,甲苯的转化率显著增加,且只生成苯甲醛.在所考察的第二种掺杂金属中,以Ni的效果为最好.该催化剂在最佳反应条件下,甲苯转化率为83%(TOF=0.027 nm-2<\/sup>·s-1<\/sup>),苯甲醛选择性为~100%.而Cr,Mo,V和Ti等高价金属则抑制了该反应,这也说明通过掺杂第二种金属调变晶格氧的活动性可影响反应性能.经过优化后,最佳反应条件为:pH值为2.5,反应温度为180℃.原位FT-IR结果表明,180℃下,甲苯在吸附有HDPA的催化剂表面能够发生化学吸附,苄基C-H键解离并与晶格氧产生结合,形成了C6<\/sub>H5<\/sub>-CH2<\/sub>-O-Fe中间物种,该物种脱附即得苯甲醛.该温度下,表面HDPA对甲苯的化学吸附不可缺.","abstractInfoEn":"A series of hexadecylphosphate acid (HDPA) terminated mixed-oxide nanoparticles have been investigated to catalyze the oxidation of toluene exclusive to benzaldehyde under mild conditions in an emulsion of toluene/water with the catalysts as stabilizers. With the HDPA-Fe2<\/sub>O3<\/sub>/Al2<\/sub>O3<\/sub> as the basic catalyst, a series of transition metals, such as Mn, Co, Ni, Cu, Cr, Mo, V, and Ti, was respectively doped to the basic catalyst to modify the performance of the catalytic system, in expectation of influencing the mobility of the lattice oxygen species in the oxide catalysts. Under normally working conditions of the catalytic system, the nanoparticles of catalysts located themselves at the interface between the oil and water phases, constituting the Pickering emulsion. Both the doped iron oxide and its surface adsorbed hexadecylphosphate molecules were essential to the catalytic system for excellent performances with high toluene conversions as well as the exclusive selectivity to benzaldehyde. Under optimal conditions,~83% of toluene conversion and >99% selectivity to benzaldehyde were obtained, using molecular oxygen as oxidant and HDPA-(Fe2<\/sub>O3<\/sub>-NiO)/Al2<\/sub>O3<\/sub> as the catalyst. This process is green and low cost to produce high quality benzaldehyde from O2<\/sub> oxidation of toluene.","articleNo":"20200213","authorCnList":["邓长顺"," 许孟霞"," 董珍"," 李磊"," 杨金月"," 郭学峰"," 彭路明"," 薛念华"," 祝艳"," 丁维平"],"authorEnList":["Changshun Deng"," Mengxia Xu"," Zhen Dong"," Lei Li"," Jinyue Yang"," Xuefeng Guo"," Luming Peng"," Nianhua Xue"," Yan Zhu"," Weiping Ding"],"authorList":["邓长顺"," 许孟霞"," 董珍"," 李磊"," 杨金月"," 郭学峰"," 彭路明"," 薛念华"," 祝艳"," 丁维平"],"authors":"邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平","authorsCn":"邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平","authorsEn":"Changshun Deng, Mengxia Xu, Zhen Dong, Lei Li, Jinyue Yang, Xuefeng Guo, Luming Peng, Nianhua Xue, Yan Zhu, Weiping Ding","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平. 十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛. 催化学报, 2020, 41(2): 341-349. doi: S1872-2067(19)63417-0.","citationCn":"邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平. 十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛. 催化学报, 2020, 41(2): 341-349. doi: S1872-2067(19)63417-0.","citationEn":"邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平. Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles. Chinese Journal of Catalysis, 2020, 41(2): 341-349. doi: S1872-2067(19)63417-0.","doi":"S1872-2067(19)63417-0","figContent":"","figList":[],"firstFig":"","fpage":"341","highCitedState":"","htmlCount":69,"htmlFile":"","id":"1af2e50c-a47b-48a5-8447-7b6a6338a93f","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"甲苯氧化, 苯甲醛, 十六烷基膦酸, 分子氧, 皮克林","keywordCn":"甲苯氧化, 苯甲醛, 十六烷基膦酸, 分子氧, 皮克林","keywordCnList":["甲苯氧化"," 苯甲醛"," 十六烷基膦酸"," 分子氧"," 皮克林"],"keywordEn":"Toluene oxidation, Benzaldehyde, Hexadecylphosphate acid, Molecular oxygen, Pickering","keywordEnList":["Toluene oxidation"," Benzaldehyde"," Hexadecylphosphate acid"," Molecular oxygen"," Pickering"],"keywordList":["甲苯氧化"," 苯甲醛"," 十六烷基膦酸"," 分子氧"," 皮克林"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"349","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":4,"pdfSize":3232.1,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛","titleCn":"十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛","titleEn":"Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles","viewCount":1565,"volume":"41","year":2020},{"abstractInfo":"负载型金催化剂在CO氧化反应中具有良好的低温活性,受到了研究者的广泛关注,其催化性能与载体的性质密切相关.氧化铝具有廉价易得、比表面积大和热稳定性好等优点.然而,作为一种非还原性载体,氧化铝提供活性氧物种的能力差,与还原性载体相比催化剂的CO氧化活性较低.理论计算和实验结果表明,在金催化剂中引入过渡金属镍能够有效促进氧分子在催化剂表面的吸附和活化,从而提升金催化剂活性.此外,过渡金属的存在能够提高金的分散度,增加活性位数目,防止在高温预处理过程中金颗粒的烧结,从而提高催化剂的活性和稳定性.
基于上述考虑,本文在氧化铝纳米片合成过程中原位引入硝酸镍,以实现对氧化铝载体的改性,然后负载金并应用于CO氧化反应.结果表明,当载体中的Ni/Al摩尔比为0.05,金负载量为1wt%时,采用还原性气氛对催化剂进行预处理可以得到具有CO氧化性能优良的金催化剂,20℃下CO转化率即可达100%.预处理气氛能够显著影响催化活性,采用还原性气氛预处理后催化剂活性明显优于氧化性气氛预处理.
采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)、氢气程序升温还原(H2<\/sub>-TPR)、氧气程序升温脱附(O2<\/sub>-TPD)、CO吸附原位红外光谱(CO-DRIFT)和X射线光电子能谱(XPS)等表征手段进一步研究了镍掺杂对Au/Al2<\/sub>O3<\/sub>催化剂上CO氧化反应的促进作用机制.XRD测试未观察到明显的金或镍衍射峰,表明金或镍物种均为高分散.HRTEM结果进一步证实,引入镍物种后金颗粒的粒径由3.6nm减小为2.4nm,表明镍掺杂有助于提高金的分散度.而XPS结果显示,镍掺杂催化剂中金与镍存在电子转移,而镍仍以NiO为主.H2<\/sub>-TPR结果表明,镍掺杂的催化剂前驱体中的金物种更容易被还原.O2<\/sub>-TPD结果证实,镍掺杂催化剂能够引入更多的氧空位,促进氧分子的吸附和活化,从而促进CO氧化反应的进行.CO-DRIFT结果表明,相比于氧化性气氛,采用还原性气氛预处理后金物种的电子云密度增加,CO吸附增强.而对于镍掺杂的催化剂,金物种吸附CO分子的能力进一步提高,有利于CO氧化反应的进行.综上,镍掺杂能够有效提高催化剂中金的分散度,增强催化剂对CO的吸附,促进氧气分子的吸附和活化,从而提高了催化剂的CO氧化活性.","abstractInfoCn":"负载型金催化剂在CO氧化反应中具有良好的低温活性,受到了研究者的广泛关注,其催化性能与载体的性质密切相关.氧化铝具有廉价易得、比表面积大和热稳定性好等优点.然而,作为一种非还原性载体,氧化铝提供活性氧物种的能力差,与还原性载体相比催化剂的CO氧化活性较低.理论计算和实验结果表明,在金催化剂中引入过渡金属镍能够有效促进氧分子在催化剂表面的吸附和活化,从而提升金催化剂活性.此外,过渡金属的存在能够提高金的分散度,增加活性位数目,防止在高温预处理过程中金颗粒的烧结,从而提高催化剂的活性和稳定性.
基于上述考虑,本文在氧化铝纳米片合成过程中原位引入硝酸镍,以实现对氧化铝载体的改性,然后负载金并应用于CO氧化反应.结果表明,当载体中的Ni/Al摩尔比为0.05,金负载量为1 wt%时,采用还原性气氛对催化剂进行预处理可以得到具有CO氧化性能优良的金催化剂,20℃下CO转化率即可达100%.预处理气氛能够显著影响催化活性,采用还原性气氛预处理后催化剂活性明显优于氧化性气氛预处理.
采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)、氢气程序升温还原(H2<\/sub>-TPR)、氧气程序升温脱附(O2<\/sub>-TPD)、CO吸附原位红外光谱(CO-DRIFT)和X射线光电子能谱(XPS)等表征手段进一步研究了镍掺杂对Au/Al2<\/sub>O3<\/sub>催化剂上CO氧化反应的促进作用机制.XRD测试未观察到明显的金或镍衍射峰,表明金或镍物种均为高分散.HRTEM结果进一步证实,引入镍物种后金颗粒的粒径由3.6nm减小为2.4nm,表明镍掺杂有助于提高金的分散度.而XPS结果显示,镍掺杂催化剂中金与镍存在电子转移,而镍仍以NiO为主.H2<\/sub>-TPR结果表明,镍掺杂的催化剂前驱体中的金物种更容易被还原.O2<\/sub>-TPD结果证实,镍掺杂催化剂能够引入更多的氧空位,促进氧分子的吸附和活化,从而促进CO氧化反应的进行.CO-DRIFT结果表明,相比于氧化性气氛,采用还原性气氛预处理后金物种的电子云密度增加,CO吸附增强.而对于镍掺杂的催化剂,金物种吸附CO分子的能力进一步提高,有利于CO氧化反应的进行.综上,镍掺杂能够有效提高催化剂中金的分散度,增强催化剂对CO的吸附,促进氧气分子的吸附和活化,从而提高了催化剂的CO氧化活性.","abstractInfoEn":"Supported gold catalysts show high activity toward CO oxidation, and the nature of the support significantly affects the catalytic activity. Herein, serial Ni doping of thin porous Al2<\/sub>O3<\/sub> nanosheets was performed via a precipitation-hydrothermal method by varying the amount of Ni during the precipitation step. The prepared nanosheets were subsequently used as supports for the deposition of Au nanoparticles (NPs). The obtained Au/Nix<\/i><\/sub>Al catalysts were studied in the context of CO oxidation to determine the effect of Ni doping on the supports. Enhanced catalytic performances were obtained for the Au/Nix<\/i><\/sub>Al catalysts compared with those of the Au supported on bare Al2<\/sub>O3<\/sub>. The Ni content and pretreatment atmosphere were both shown to influence the catalytic activity. Pretreatment under a reducing atmosphere was beneficial for improving catalytic activity. The highest activity was observed for the catalysts with a Ni/Al molar ratio of 0.05, achieving complete CO conversion at 20℃ with a gold loading of 1 wt%. The in-situ FTIR results showed that the introduction of Ni strengthened CO adsorption on the Au NPs. The H2<\/sub>-TPR and O2<\/sub>-TPD results indicated that the introduction of Ni produced new oxygen vacancies and allowed the oxygen molecules to be adsorbed and activated more easily. The improved catalytic performance after doping Ni was attributed to the smaller size of the Au NPs and more active oxygen species.","articleNo":"20200214","authorCnList":["路饶"," 贺雷"," 王阳"," 高新芊"," 李文翠"],"authorEnList":["Rao Lu"," Lei He"," Yang Wang"," Xin-Qian Gao"," Wen-Cui Li"],"authorList":["路饶"," 贺雷"," 王阳"," 高新芊"," 李文翠"],"authors":"路饶, 贺雷, 王阳, 高新芊, 李文翠","authorsCn":"路饶, 贺雷, 王阳, 高新芊, 李文翠","authorsEn":"Rao Lu, Lei He, Yang Wang, Xin-Qian Gao, Wen-Cui Li","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"路饶, 贺雷, 王阳, 高新芊, 李文翠. 镍掺杂对氧化铝纳米片负载金催化剂在CO氧化反应中的促进作用. 催化学报, 2020, 41(2): 350-356. doi: S1872-2067(19)63439-X.","citationCn":"路饶, 贺雷, 王阳, 高新芊, 李文翠. 镍掺杂对氧化铝纳米片负载金催化剂在CO氧化反应中的促进作用. 催化学报, 2020, 41(2): 350-356. doi: S1872-2067(19)63439-X.","citationEn":"路饶, 贺雷, 王阳, 高新芊, 李文翠. Promotion effects of nickel-doped Al2<\/sub>O3<\/sub>-nanosheet-supported Au catalysts for CO oxidation. Chinese Journal of Catalysis, 2020, 41(2): 350-356. doi: S1872-2067(19)63439-X.","doi":"S1872-2067(19)63439-X","figContent":"","figList":[],"firstFig":"","fpage":"350","highCitedState":"","htmlCount":130,"htmlFile":"","id":"5fb4e5c3-54ee-4b88-bdc9-d9b3c277ef6a","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"氧化铝, 金催化剂, 镍掺杂, 一氧化碳氧化, 氧物种活化","keywordCn":"氧化铝, 金催化剂, 镍掺杂, 一氧化碳氧化, 氧物种活化","keywordCnList":["氧化铝"," 金催化剂"," 镍掺杂"," 一氧化碳氧化"," 氧物种活化"],"keywordEn":"Alumina, Gold catalyst, Nickel doping, CO oxidation, Oxygen activation","keywordEnList":["Alumina"," Gold catalyst"," Nickel doping"," CO oxidation"," Oxygen activation"],"keywordList":["氧化铝"," 金催化剂"," 镍掺杂"," 一氧化碳氧化"," 氧物种活化"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"356","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":15,"pdfSize":2077.1,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"镍掺杂对氧化铝纳米片负载金催化剂在CO氧化反应中的促进作用","titleCn":"镍掺杂对氧化铝纳米片负载金催化剂在CO氧化反应中的促进作用","titleEn":"Promotion effects of nickel-doped Al2<\/sub>O3<\/sub>-nanosheet-supported Au catalysts for CO oxidation","viewCount":1752,"volume":"41","year":2020},{"abstractInfo":"芳基硼酸酯作为一种重要的有机中间体,在C-C,C-N和C-O键的构筑以及C-X键的转换中有着广泛的应用,其传统合成方法主要是用格氏试剂或有机锂试剂,但该方法的官能团耐受性较差,且对反应环境敏感.在均相催化体系下,过渡金属催化芳烃的C-H和C-X键硼化反应成为合成芳基硼酸酯化合物的重要途径,虽然活性和选择性很高,但催化剂难于分离,且多数反应需要昂贵的配体,限制了其在工业上的大规模应用.多相催化剂体系虽然解决了分离回收的问题,但是催化效率大多较低.近年来,由于光催化能够有效利用太阳能,在温和条件下促使反应进行,并且能够定向的选择性合成目标产物,提高目标产物的产率,因此其在有机合成中的应用引起了广泛的关注.
本文以具有分级结构且能够响应可见光的SiC纳米线为载体,并通过液相还原法制备负载量为3wt%的Pd/SiC催化剂.TEM照片可以看出,Pd纳米颗粒均地分散在SiC表面,平均粒径为3.7nm.UV-Vis图谱表明,SiC负载Pd以后可明显提高其对可见光的吸收.Pd/SiC在可见光(400-800nm)照射下,在30℃和常压Ar氛围下即可实现碘苯脱碘硼化,苯硼酸频哪醇酯的收率高达95%.Pd/SiC在可见光作用下,对其它碘苯类和溴苯类化合物的光催化硼化均具有较好的的普适性.在暗反应条件下,苯硼酸频哪醇酯的收率仅为5%.并且,转化率能够随着光强度的增强而增加.同时,不同的波长范围对光反应的贡献率也不同,400-450,450-500,500-550,550-600和600-800nm的光反应贡献率分别为34%,22%,16%,13%和5%,这与催化剂的紫外可见吸收光谱相一致,充分说明反应主要为光驱动反应.Pd/SiC催化剂也具有较好的可重复使用性,经过5次循环使用后,催化活性依然保持在较高的水平.
光反应和暗反应活化能的显著差别,说明二者的机理不同.理论研究发现,SiC的功函为4.0eV,低于Pd(5.12eV),当Pd负载在SiC表面时,能够形成Mott-Schottky接触,使SiC吸收可见光生成的光生电子能够迅速的传递到Pd活性位.XPS表征显示,Pd在Pd/SiC催化剂中以金属态Pd0<\/sup>的形式存在,并向低结合能方向移动,说明SiC中的电子向Pd迁移,增加了Pd原子周围的电子云密度.同时,光致发光光谱中,Pd/SiC位于400-550nm的特征峰与SiC相比,强度明显减弱,说明光生电子和空穴的分离效率增强.据此我们推断,光生电子迅速从SiC传递到Pd使Pd活性位表面富电子化,进而快速活化和断裂芳基卤化物中的C-I或C-Br键,有效提高催化活性.","abstractInfoCn":"芳基硼酸酯作为一种重要的有机中间体,在C-C,C-N和C-O键的构筑以及C-X键的转换中有着广泛的应用,其传统合成方法主要是用格氏试剂或有机锂试剂,但该方法的官能团耐受性较差,且对反应环境敏感.在均相催化体系下,过渡金属催化芳烃的C-H和C-X键硼化反应成为合成芳基硼酸酯化合物的重要途径,虽然活性和选择性很高,但催化剂难于分离,且多数反应需要昂贵的配体,限制了其在工业上的大规模应用.多相催化剂体系虽然解决了分离回收的问题,但是催化效率大多较低.近年来,由于光催化能够有效利用太阳能,在温和条件下促使反应进行,并且能够定向的选择性合成目标产物,提高目标产物的产率,因此其在有机合成中的应用引起了广泛的关注.
本文以具有分级结构且能够响应可见光的SiC纳米线为载体,并通过液相还原法制备负载量为3 wt%的Pd/SiC催化剂.TEM照片可以看出,Pd纳米颗粒均地分散在SiC表面,平均粒径为3.7nm.UV-Vis图谱表明,SiC负载Pd以后可明显提高其对可见光的吸收.Pd/SiC在可见光(400-800nm)照射下,在30℃和常压Ar氛围下即可实现碘苯脱碘硼化,苯硼酸频哪醇酯的收率高达95%.Pd/SiC在可见光作用下,对其它碘苯类和溴苯类化合物的光催化硼化均具有较好的的普适性.在暗反应条件下,苯硼酸频哪醇酯的收率仅为5%.并且,转化率能够随着光强度的增强而增加.同时,不同的波长范围对光反应的贡献率也不同,400-450,450-500,500-550,550-600和600-800nm的光反应贡献率分别为34%,22%,16%,13%和5%,这与催化剂的紫外可见吸收光谱相一致,充分说明反应主要为光驱动反应.Pd/SiC催化剂也具有较好的可重复使用性,经过5次循环使用后,催化活性依然保持在较高的水平.
光反应和暗反应活化能的显著差别,说明二者的机理不同.理论研究发现,SiC的功函为4.0eV,低于Pd (5.12eV),当Pd负载在SiC表面时,能够形成Mott-Schottky接触,使SiC吸收可见光生成的光生电子能够迅速的传递到Pd活性位.XPS表征显示,Pd在Pd/SiC催化剂中以金属态Pd0<\/sup>的形式存在,并向低结合能方向移动,说明SiC中的电子向Pd迁移,增加了Pd原子周围的电子云密度.同时,光致发光光谱中,Pd/SiC位于400-550nm的特征峰与SiC相比,强度明显减弱,说明光生电子和空穴的分离效率增强.据此我们推断,光生电子迅速从SiC传递到Pd使Pd活性位表面富电子化,进而快速活化和断裂芳基卤化物中的C-I或C-Br键,有效提高催化活性.","abstractInfoEn":"Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X=Br, I) borylation of aryl halides at 30℃. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.","articleNo":"20200215","authorCnList":["焦志锋"," 赵吉晓"," 郭晓宁"," 郭向云"],"authorEnList":["Zhi-Feng Jiao"," Ji-Xiao Zhao"," Xiao-Ning Guo"," Xiang-Yun Guo"],"authorList":["焦志锋"," 赵吉晓"," 郭晓宁"," 郭向云"],"authors":"焦志锋, 赵吉晓, 郭晓宁, 郭向云","authorsCn":"焦志锋, 赵吉晓, 郭晓宁, 郭向云","authorsEn":"Zhi-Feng Jiao, Ji-Xiao Zhao, Xiao-Ning Guo, Xiang-Yun Guo","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"焦志锋, 赵吉晓, 郭晓宁, 郭向云. 具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应. 催化学报, 2020, 41(2): 357-363. doi: S1872-2067(19)63449-2.","citationCn":"焦志锋, 赵吉晓, 郭晓宁, 郭向云. 具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应. 催化学报, 2020, 41(2): 357-363. doi: S1872-2067(19)63449-2.","citationEn":"焦志锋, 赵吉晓, 郭晓宁, 郭向云. Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles. Chinese Journal of Catalysis, 2020, 41(2): 357-363. doi: S1872-2067(19)63449-2.","doi":"S1872-2067(19)63449-2","figContent":"","figList":[],"firstFig":"","fpage":"357","highCitedState":"","htmlCount":82,"htmlFile":"","id":"954ff3c4-0ab2-488a-b8e0-987cf8d31c59","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"芳基硼酸酯, C-X键硼化, SiC, Pd纳米颗粒, 光催化","keywordCn":"芳基硼酸酯, C-X键硼化, SiC, Pd纳米颗粒, 光催化","keywordCnList":["芳基硼酸酯"," C-X键硼化"," SiC"," Pd纳米颗粒"," 光催化"],"keywordEn":"Boronate esters, Carbon-halogen activation, Hierarchical SiC nanowires, Pd nanoparticles, Photocatalysis","keywordEnList":["Boronate esters"," Carbon-halogen activation"," Hierarchical SiC nanowires"," Pd nanoparticles"," Photocatalysis"],"keywordList":["芳基硼酸酯"," C-X键硼化"," SiC"," Pd纳米颗粒"," 光催化"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"363","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":8,"pdfSize":1139.05,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应","titleCn":"具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应","titleEn":"Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles","viewCount":1638,"volume":"41","year":2020},{"abstractInfo":"近年来,以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中,氮氧化物(NOx<\/i><\/sub>)的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原(NH3<\/sub>-SCR)是目前消除氮氧化物的主流技术,低温NH3<\/sub>-SCR更是广泛应用于钢铁、焦化、水泥、玻璃、陶瓷和垃圾焚烧等行业的烟气排放治理.传统的V2<\/sub>O5<\/sub>-WO3<\/sub>/TiO2<\/sub>催化剂活性温度高(300-400℃)且钒具有生物毒性,因此亟待开发环境友好的低温非钒基脱硝催化剂.
最近,CeTiOx<\/i><\/sub>基催化剂由于在中高温段(250-400℃)表现出优异的脱硝性能而得到广泛关注.然而,该催化剂仍面临低温活性差及抗硫性能差的问题,制约了其工业化应用.研究显示,添加过渡金属可提高CeTiOx<\/i><\/sub>基催化剂的脱硝活性和抗硫中毒性能,这主要是因为过渡金属的添加可以有效改善催化剂的氧化还原性能和表面酸性.MoO3<\/sub>作为一种可以提供大量酸性位的氧化物,常被用作助剂改善钒钨钛催化剂的活性.研究显示,MoO3<\/sub>的引入可以促进催化剂中钒物种的分散度以及提高表面酸性.基于此,我们制备了一系列不同Mo含量的MoO3<\/sub>/CeTiOx<\/i><\/sub>催化剂,以期提高CeTiOx<\/i><\/sub>催化剂的低温脱硝性能及抗SO2<\/sub>中毒能力,并着重研究表面Mo的修饰对CeTiOx<\/i><\/sub>催化剂物理化学性质的影响.
研究发现,表面Mo修饰可以显著提高CeTiOx<\/i><\/sub>的低温催化活性,其脱硝效率在150℃即可达到80%,同时抗SO2<\/sub>中毒能力也得到增强.进一步借助X射线衍射、比表面积测定、氢气程序升温还原、氨气程序升温脱附和X射线光电子能谱等方法对催化剂进行了全面表征分析.结果显示,表面Mo修饰对CeTiOx<\/i><\/sub>催化剂物理化学性质的影响与其脱硝性能有着密不可分的关系.首先,钼物种主要是以MoO3<\/sub>的形式存在于CeTiOx<\/i><\/sub>表面,其最佳的负载量为4wt.%.其次,表面Mo的沉积显著提高了催化剂的表面酸量,尤其是Brönsted酸位的数量,而表面酸位的增加有利于催化剂吸附与活化反应物种NH3<\/sub>;同时,表面Mo修饰还减弱了硝酸盐在催化剂表面的吸附,进一步促使NH3<\/sub>-SCR反应按照Eley-Rideal机理顺利进行.最后,该催化剂在H2<\/sub>O和SO2<\/sub>存在的条件下仍具有最佳的脱硝性能,因而有望用于实际含SO2<\/sub>的低温烟气脱硝.","abstractInfoCn":"近年来,以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中,氮氧化物(NOx<\/i><\/sub>)的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原(NH3<\/sub>-SCR)是目前消除氮氧化物的主流技术,低温NH3<\/sub>-SCR更是广泛应用于钢铁、焦化、水泥、玻璃、陶瓷和垃圾焚烧等行业的烟气排放治理.传统的V2<\/sub>O5<\/sub>-WO3<\/sub>/TiO2<\/sub>催化剂活性温度高(300-400℃)且钒具有生物毒性,因此亟待开发环境友好的低温非钒基脱硝催化剂.
最近,CeTiOx<\/i><\/sub>基催化剂由于在中高温段(250-400℃)表现出优异的脱硝性能而得到广泛关注.然而,该催化剂仍面临低温活性差及抗硫性能差的问题,制约了其工业化应用.研究显示,添加过渡金属可提高CeTiOx<\/i><\/sub>基催化剂的脱硝活性和抗硫中毒性能,这主要是因为过渡金属的添加可以有效改善催化剂的氧化还原性能和表面酸性.MoO3<\/sub>作为一种可以提供大量酸性位的氧化物,常被用作助剂改善钒钨钛催化剂的活性.研究显示,MoO3<\/sub>的引入可以促进催化剂中钒物种的分散度以及提高表面酸性.基于此,我们制备了一系列不同Mo含量的MoO3<\/sub>/CeTiOx<\/i><\/sub>催化剂,以期提高CeTiOx<\/i><\/sub>催化剂的低温脱硝性能及抗SO2<\/sub>中毒能力,并着重研究表面Mo的修饰对CeTiOx<\/i><\/sub>催化剂物理化学性质的影响.
研究发现,表面Mo修饰可以显著提高CeTiOx<\/i><\/sub>的低温催化活性,其脱硝效率在150℃即可达到80%,同时抗SO2<\/sub>中毒能力也得到增强.进一步借助X射线衍射、比表面积测定、氢气程序升温还原、氨气程序升温脱附和X射线光电子能谱等方法对催化剂进行了全面表征分析.结果显示,表面Mo修饰对CeTiOx<\/i><\/sub>催化剂物理化学性质的影响与其脱硝性能有着密不可分的关系.首先,钼物种主要是以MoO3<\/sub>的形式存在于CeTiOx<\/i><\/sub>表面,其最佳的负载量为4 wt.%.其次,表面Mo的沉积显著提高了催化剂的表面酸量,尤其是Brönsted酸位的数量,而表面酸位的增加有利于催化剂吸附与活化反应物种NH3<\/sub>;同时,表面Mo修饰还减弱了硝酸盐在催化剂表面的吸附,进一步促使NH3<\/sub>-SCR反应按照Eley-Rideal机理顺利进行.最后,该催化剂在H2<\/sub>O和SO2<\/sub>存在的条件下仍具有最佳的脱硝性能,因而有望用于实际含SO2<\/sub>的低温烟气脱硝.","abstractInfoEn":"The effect of molybdenum oxide on the activity and durability of CeO2<\/sub>-TiO2<\/sub> catalyst for NO reduction by NH3<\/sub> was examined. It was found that the introduction of Mo could improve the low-temperature NH3<\/sub>-SCR activity and SO2<\/sub>/H2<\/sub>O durability of the CeO2<\/sub>-TiO2<\/sub> catalyst and an optimal loading of Mo was 4 wt.%. The best MoO3<\/sub>/CeO2<\/sub>-TiO2<\/sub> catalyst displayed over 90% NO conversion from 200℃ to 400℃ and obtained 4-fold increase in NO conversion compared to CeO2<\/sub>-TiO2<\/sub> at 150℃. The characterization results revealed that the number of Brönsted acid sites over MoO3<\/sub>/CeO2<\/sub>-TiO2<\/sub> was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of MoO3<\/sub>, which were favorable for the high NH3<\/sub>-SCR performance. It is believed that the MoO3<\/sub>/CeO2<\/sub>-TiO2<\/sub> catalyst is a suitable substitute for the NH3<\/sub>-SCR reaction.","articleNo":"20200216","authorCnList":["李露露"," 李佩晓"," 谭伟"," 马凯莉"," 邹伟欣"," 汤常金"," 董林"],"authorEnList":["Lulu Li"," Peixiao Li"," Wei Tan"," Kaili Ma"," Weixin Zou"," Changjin Tang"," Lin Dong"],"authorList":["李露露"," 李佩晓"," 谭伟"," 马凯莉"," 邹伟欣"," 汤常金"," 董林"],"authors":"李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林","authorsCn":"李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林","authorsEn":"Lulu Li, Peixiao Li, Wei Tan, Kaili Ma, Weixin Zou, Changjin Tang, Lin Dong","categoryName":"论文","categoryNameCn":"论文","categoryNameEn":"Articles","citation":"李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林. 表面Mo修饰提高CeTiOx<\/i><\/sub>催化剂低温脱硝性能. 催化学报, 2020, 41(2): 364-373. doi: S1872-2067(19)63437-6.","citationCn":"李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林. 表面Mo修饰提高CeTiOx<\/i><\/sub>催化剂低温脱硝性能. 催化学报, 2020, 41(2): 364-373. doi: S1872-2067(19)63437-6.","citationEn":"李露露, 李佩晓, 谭伟, 马凯莉, 邹伟欣, 汤常金, 董林. Enhanced low-temperature NH3<\/sub>-SCR performance of CeTiOx<\/i><\/sub> catalyst via surface Mo modification. Chinese Journal of Catalysis, 2020, 41(2): 364-373. doi: S1872-2067(19)63437-6.","doi":"S1872-2067(19)63437-6","figContent":"","figList":[],"firstFig":"","fpage":"364","highCitedState":"","htmlCount":91,"htmlFile":"","id":"90d71476-d5ed-4fb1-b7d7-75db8d4c394a","issnPpub":"0253-9837","issue":"2","journalPublishId":"CHXB","journalReferenceCodeType":0,"journalTitleCn":"催化学报","journalTitleEn":"Chinese Journal of Catalysis","keyword":"氮氧化物消除, 氧化铈-氧化钛催化剂, 氧化钼表面修饰, 二氧化硫中毒, 表面酸性","keywordCn":"氮氧化物消除, 氧化铈-氧化钛催化剂, 氧化钼表面修饰, 二氧化硫中毒, 表面酸性","keywordCnList":["氮氧化物消除"," 氧化铈-氧化钛催化剂"," 氧化钼表面修饰"," 二氧化硫中毒"," 表面酸性"],"keywordEn":"DeNOx<\/i><\/sub>, CeO2<\/sub>-TiO2<\/sub> catalyst, MoO3<\/sub> modification, SO2<\/sub> poisoning, Surface acidity","keywordEnList":["DeNOx<\/i><\/sub>"," CeO2<\/sub>-TiO2<\/sub> catalyst"," MoO3<\/sub> modification"," SO2<\/sub> poisoning"," Surface acidity"],"keywordList":["氮氧化物消除"," 氧化铈-氧化钛催化剂"," 氧化钼表面修饰"," 二氧化硫中毒"," 表面酸性"],"language":"","latestInfo":"","latestState":"","latestStateEn":"","lpage":"373","oldUrl":"http://www.cjcatal.org/fileup/HTML","pdfDownCount":14,"pdfSize":1021.06,"pubDate":"","recommendState":"","releaseState":"1","secCount":0,"title":"表面Mo修饰提高CeTiOx<\/i><\/sub>催化剂低温脱硝性能","titleCn":"表面Mo修饰提高CeTiOx<\/i><\/sub>催化剂低温脱硝性能","titleEn":"Enhanced low-temperature NH3<\/sub>-SCR performance of CeTiOx<\/i><\/sub> catalyst via surface Mo modification","viewCount":1596,"volume":"41","year":2020}]}