首页 > 期刊 > 无机化学学报
栏目

  

Articles
Self-assembly of [Pd6(L)4]8+-type macrocyclic complexes for fluorescent sensing of HSO3-
Xiaofei NIU, Ke WANG, Fengyan SONG, Shuyan YU
2024, 40(7): 1233-1242  doi: 10.11862/CJIC.20240057
[摘要]  (11) [HTML全文] (11) [PDF 14713KB] (0)
摘要:
In this study, parallelogram-like macrocyclic supramolecular metallacycles [Pd6(bpy)6(L1)4](PF6)8 (1a) and [Pd6(bpy)6(L2)4](PF6)8 (2a), where HL1=1-(1H-pyrazole-4-yl)-4-(4-pyridyl)benzene, HL2=9-(1H-pyrazole-4-yl)-10-(4-pyridyl)anthracene, and bpy=2, 2'-bipyridine, are synthesized by reacting aryl pyrazole pyridine ligands with dipalla-dium corners in aqueous solutions via metal-directed hierarchical self-assembly. The structures of the supramolecular Pd parallelograms are confirmed through single-crystal X-ray diffraction. Notably, the two parallelogram metallacycles can be used as"turn-on"fluorescence sensors to detect HSO3- through a disassembly mechanism. In addition, the 1a-based sensor shows selective detection of HSO3- without interference from other anions. The detection limit was as low as 0.131 μmol·L-1. Furthermore, complex 1a presented the semiquantitative visual detection ability for HSO3- in the test trip mode via fluorescence changes.
Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials
Huirong LIU, Hao XU, Dunru ZHU, Junyong ZHANG, Chunhua GONG, Jingli XIE
2024, 40(7): 1368-1376  doi: 10.11862/CJIC.20240066
[摘要]  (15) [HTML全文] (15) [PDF 12936KB] (0)
摘要:
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2W10O40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
Construction of two metal-organic frameworks by rigid bis(triazole) and carboxylate mixed-ligands and their catalytic properties for CO2 cycloaddition reaction
Weichen WANG, Chunhua GONG, Junyong ZHANG, Yanfeng BI, Hao XU, Jingli XIE
2024, 40(7): 1377-1386  doi: 10.11862/CJIC.20230415
[摘要]  (16) [HTML全文] (16) [PDF 8082KB] (0)
摘要:
Two metal-organic frameworks (MOFs) containing rigid bis(triazole) ligand, namely {[Zn2(L)(TP)2(H2O)·H2O]}n (1) and [Zn(L)(HTMA)]n (2), where L=4, 4'-(3, 3'-dimethyl-(1, 1'-biphenyl)-4, 4'-diyl)bis(4H-1, 2, 4-triazole), H2TP=terephthalic acid, H3TMA=1, 3, 5-benzenetricarboxylic acid, were synthesized by using acid-base mixed ligands strategy and structurally characterized by X-ray single-crystal diffraction. Structural analysis reveals that MOF 1 displays a 3, 6-connected 2D structure with a new topological point symbol of (42·6)2(48·66·8), while MOF 2 presents a 2D sql topology structure. The catalytic studies reveal that 2 exhibits excellent catalytic activity for the cycloaddition reaction of CO2 with epoxides under mild conditions. Furthermore, 2 can be reused at least three times while maintaining its catalytic ability.
A(NH2SO3) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response
Cuiwu MO, Gangmin ZHANG, Chao WU, Zhipeng HUANG, Chi ZHANG
2024, 40(7): 1387-1396  doi: 10.11862/CJIC.20240045
[摘要]  (16) [HTML全文] (16) [PDF 11125KB] (0)
摘要:
Two alkali-metal sulfamates nonlinear optical (NLO) crystals, Li(NH2SO3) and Na(NH2SO3), have been obtained through the facile evaporation method. Li(NH2SO3) crystallizes in the polar space group Pca21 (No.29). The structure of Li(NH2SO3) can be described as a 3D network formed by [LiO4]7- polyhedral connecting with NH2SO3- tetrahedra through corner-sharing. Na(NH2SO3) crystallizes in the polar space group P212121 (No.19). The structure of Na(NH2SO3) can be described as a 3D network formed by distorted [NaO6]11- octahedral connecting with NH2SO3- tetrahedra through corner-sharing. The UV-Vis-near-infrared spectra demonstrate that Li(NH2SO3) and Na(NH2SO3) possessed large optical band gaps of 5.25 and 4.81 eV, respectively. Powder second-harmonic generation (SHG) measurements demonstrate that the SHG intensity of Li(NH2SO3) and Na(NH2SO3) were 0.32 times and 0.31 times that of KH2PO4, respectively. First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.
Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid
Kaimin WANG, Xiong GU, Na DENG, Hongmei YU, Yanqin YE, Yulu MA
2024, 40(7): 1397-1408  doi: 10.11862/CJIC.20240009
[摘要]  (12) [HTML全文] (12) [PDF 21172KB] (0)
摘要:
5-(dimethylamino) isophthalic acid (H2dia) and 1H-imidazole (mdz) were used as ligands to react with Zn(Ⅱ) or Cu(Ⅱ) metal salts to generate three new transition metal complexes [Zn(dia)(mdz)2]·2H2O (1), [Cu(dia)(mdz)2 (DMF)] (2) and [Cu(dia)(mdz)2]·H2O (3). Their structures were characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analyses, and Hirshfeld surface analyses. The results revealed that complexes 1 and 2 possess 1D linear chains, each four-coordinated Zn(Ⅱ) of 1 is located in the geometric center of the distorted tetrahedron, but the Cu(Ⅱ) metal center of 2 is five-coordinated and holds a triangular bipyramidal geometry. The zigzag 1D chain of complex 3 was obtained by changing the solvent in the synthesis, and the four-coordinated Cu(Ⅱ) ion is in the centre of the square planar. Results indicate that the geometries of metal centers and synthetic solvents have important effects on the structures of complexes. Abundant intermolecular hydrogen bonding plays an important role in the stability of their 3D supramolecular structures. Thermogravimetric analyses revealed that the complexes have good thermal stabilities. Solid fluorescence analyses showed that complex 1 had excellent fluorescence, but the fluorescence intensities of complexes 2 and 3 were much lower than those of ligands.
Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands
Maitri Bhattacharjee, Rekha Boruah Smriti, R. N. Dutta Purkayastha, Waldemar Maniukiewicz, Shubhamoy Chowdhury, Debasish Maiti, Tamanna Akhtar
2024, 40(7): 1409-1422  doi: 10.11862/CJIC.20240007
[摘要]  (14) [HTML全文] (14) [PDF 10357KB] (0)
摘要:
Three new copper(Ⅱ) complexes 1-3 of Schiff base ligands HL1 (2-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone), HL2 (4-hydroxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) and L3 (2-methoxybenzaldehyde2-(2-oxo-1, 2-diphenylethylidene)hydrazone) were synthesized from methanolic medium. The complexes were characterized by elemental analyses, spectroscopic methods, magnetic susceptibility measurements, and density functional theory (DFT) studies. The synthesized ligands were characterized structurally by single-crystal X-ray diffraction studies. The optimized structure of the complexes was ascertained by DFT studies. The DNA binding ability of the complexes with calf thymus DNA (CT-DNA) was studied by UV-Vis absorption and fluorescence emission spectral studies. Absorption spectral studies revealed a hyperchromic effect and suggested the possible mode of interaction with CT-DNA. The competitive binding studies using ethidium bromide (EB) show that the complexes can replace DNA from DNA-EB adduct and suggests that the complexes probably bind to CT-DNA in intercalative mode. In vitro antibacterial activity of the complexes against Gram-negative bacteria Klebsiella pneumoniae (K. pneumoniae), Escherichia coli(E. coli), and Shigella boydii (S. boydii), and gram-positive bacteria Staphylococcus aureus (S. aureus) exhibited an appreciable antibacterial activity of complex 2 against K. pneumoniae and S. boydii, but complexes 1 and 3 did not show any significant antibacterial activity.
论文
基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用
罗秋洋, 唐晓宁, 夏澍, 刘珺楠, 杨兴富, 雷杰
2024, 40(7): 1243-1253  doi: 10.11862/CJIC.20240110
[摘要]  (18) [HTML全文] (18) [PDF 31979KB] (0)
摘要:
通过在N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过1 700 h(1 mA·cm-2)和1 330 h(3 mA·cm-2)的循环寿命。采用商用MnO2与之匹配得到的Cu@Zn||MnO2全电池不仅在1 A·g-1下具有168.5 mAh·g-1的可逆比容量,还可稳定循环2 000次以上
Cu掺杂对Au11(dppf)4Cl2纳米团簇结构和光学性质的影响
周鹏, 蔡潇, 马清祥, 刘旭
2024, 40(7): 1254-1260  doi: 10.11862/CJIC.20240047
[摘要]  (14) [HTML全文] (14) [PDF 10437KB] (0)
摘要:
通过一锅还原法成功制备了合金纳米团簇Au11-xCux(dppf)4Cl2(x=1、2;dppf=1,1'-双(二苯基膦)二茂铁)。晶体结构解析表明,合金团簇具有与Au11(dppf)4Cl2类似的几何结构,如含有缺陷二十面体金属内核,不同之处在于Cu原子取代了与Cl配位的Au原子。因此,Au11-xCux(dppf)4Cl2可视为Cu对Au11(dppf)4Cl2模板团簇的掺杂。Cu原子的引入并未改变模板团簇Au11(dppf)4Cl2的框架结构,但有效调控了电子结构,进而使其光吸收发生红移。
分级中空结构BiOBr-Pt催化剂用于光催化CO2还原
王坤, 刘文蕊, 江鹏, 宋宇航, 陈丽华, 邓兆
2024, 40(7): 1270-1278  doi: 10.11862/CJIC.20240037
[摘要]  (14) [HTML全文] (14) [PDF 17190KB] (0)
摘要:
以乙二醇为溶剂,聚乙烯吡咯烷酮为表面活性剂,通过一步溶剂热法合成了分级中空结构的BiOBr-Pt催化剂。合成的分级中空结构BiOBr-2h催化剂的比表面积为28 m2·g-1,是对比样品BiOBr-1h的2倍,这种结构为催化反应提供更多的反应活性位点。此外,在催化剂中引入Pt增强了BiOBr的载流子传导速率,而且Pt可以作为电子陷阱捕获周围大量电子,有效抑制光生载流子的复合,从而提高CO2还原的催化活性。光催化CO2还原实验结果表明,BiOBr-Pt的主要产物为CO,产物选择性为99%,其CO产率达到了20.8 μmol·h-1·g-1,为原始BiOBr的2.1倍。这一结果说明,这种Pt负载且具有分级中空结构的催化剂可以有效地将CO2转化为增值化学品。
高硅ZSM-5沸石孔道和酸性的协同调控及其催化甲醇制丙烯反应性能
李兴扬, 刘田菊, 高阳, 张丹丹, 周勇, 潘梦
2024, 40(7): 1279-1289  doi: 10.11862/CJIC.20240026
[摘要]  (10) [HTML全文] (10) [PDF 28560KB] (0)
摘要:
通过碱处理结合铬改性策略实现了对高硅ZSM-5沸石孔道和酸性的协同调控,制备出了一种具有适宜酸性的高硅多级孔沸石催化剂。在碱处理的过程中,通过精细调节合成凝胶组成,在沸石晶体中引入的丰富共生界面,诱导了介孔的形成,从而打破了沸石硅铝比对常规碱处理法的限制。在铬改性的过程中,独特的多级孔结构促进了铬在催化剂中的分散,从而实现了对酸性的深度改性。在甲醇制丙烯催化反应中,制备的催化剂表现出了极佳的催化稳定性以及很高的丙烯和总低碳烯烃选择性。
I2界面修饰对全无机CsPbBr3钙钛矿太阳能电池性能的影响
王则远, 郑松志, 李浩, 翁敬菠, 王威, 汪杨, 孙伟海
2024, 40(7): 1290-1300  doi: 10.11862/CJIC.20240021
[摘要]  (19) [HTML全文] (19) [PDF 24605KB] (0)
摘要:
通过在CsPbBr3薄膜上旋涂一次I2的异丙醇溶液以修饰CsPbBr3吸光层,钝化CsPbBr3层表面缺陷,改善CsPbBr3薄膜形貌。同时通过利用环境友好的绿色溶剂水溶解CsBr,显著提高了其溶解度,减少了旋涂次数,简化了电池制备流程。实验结果表明,在CsPbBr3钙钛矿太阳能电池(perovskite solar cells,PSCs)中,使用5 mg·mL-1 I2的异丙醇溶液界面修饰的器件具有最佳光伏性能,其最高开路电压(open-circuit voltage,VOC)为1.55 V,短路电流密度(short circuit current density,JSC)为7.45 mA·cm-2,填充因子(fill factor,FF)为85.54%,光电转换效率(photoelectric conversion efficiency,PCE)达到了9.88%。
两个丁二肟有机锡配合物的合成、结构及抗癌活性
卿菁菁, 何帆, 刘智辉, 侯帅鹏, 刘娅, 蒋一凡, 谭梦婷, 何丽芳, 张复兴, 朱小明
2024, 40(7): 1301-1308  doi: 10.11862/CJIC.20240003
[摘要]  (11) [HTML全文] (11) [PDF 4393KB] (0)
摘要:
合成了2个丁二酮肟有机锡化合物:双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征,对其结构进行量子化学从头计算,并进行了体外抗癌活性研究。结果显示:配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子,锡原子均为四配位的畸变四面体构型;配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构,锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
Cu2O/Cu-垂直石墨烯微电极的制备及尿酸/脑电的检测
白浩, 冀伟志, 陈瑾妍, 李红姬, 李明吉
2024, 40(7): 1309-1319  doi: 10.11862/CJIC.20240001
[摘要]  (14) [HTML全文] (14) [PDF 29658KB] (0)
摘要:
结合Cu(Ⅱ)离子浸渍吸附方法及直流电弧等离子体喷射化学气相沉积技术制备了一种电化学/电生理双模Cu2O/Cu-垂直石墨烯微电极,并研究了电化学方法检测尿酸以及记录脑电信号的双响应性能。使用扫描电子显微镜、透射电子显微镜、X射线衍射仪表征了形貌、微结构及晶体成分,并测试了电化学及脑电记录能力。结果表明,该微电极直径仅为200 μm,大量镶嵌Cu2O/Cu纳米粒子的石墨烯纳米片垂直生长在基片上,排列成了一种三维的多孔结构,使其具有了高的电化学催化活性、短程离子扩散路径、以及长程导电网络。由此,以10 μL的饱和NaCl溶液为介质记录脑电信号时,该微电极的皮肤接触电阻低至约7.05 kΩ,生理电采集性能接近涂导电膏的商用湿电极。此外,该微电极还灵敏响应尿酸的氧化电流,检测浓度范围在0.5~500μmol·L-1,检测限低至0.024 μmol·L-1,且具有良好的抗干扰能力及长期稳定性。
Y(PO3)3双包覆改性对Li[Ni0.8Co0.15Al0.05]O2电化学性能的影响
李泓漪, 吴爱民, 赵刘洋, 刘新朋, 陈凤琴, 李爱魁, 黄昊
2024, 40(7): 1320-1328  doi: 10.11862/CJIC.20230480
[摘要]  (14) [HTML全文] (14) [PDF 31881KB] (0)
摘要:
在镍钴铝酸锂正极材料Li[Ni0.8Co0.15Al0.05]O2(NCA)制备过程中表面遗留的碱性物质会严重影响其循环稳定性能,针对这一难题,提出使用Y(PO3)3对其进行表面包覆改性,利用Y(PO3)3与表面残留的LiOH反应消除表面残碱,并探讨包覆改性对NCA整体性能的影响机制。测试分析结果表明,在低温煅烧过程中前驱体表面会形成均匀致密的Y(PO3)3和LiPO3包覆层,LiPO3有较高的离子电导率,双包覆层能够防止活性物质在电化学循环过程中与电解液相互接触时发生有害副反应,提高电极材料的循环稳定性。其中Y(PO3)3包覆量(质量分数)为1%的样品在0.1C下的首次库仑效率从未改性样品的78.65%提高到88.50%,在1C下循环150圈后容量保持率从59.38%提高到85.33%,相比于未改性样品具有更高的首次库仑效率和更优异的循环性能。
氧化石墨烯浓度对还原氧化石墨烯/ZnS电化学性能的影响
徐志环, 康晴, 龙玉珍, 袁倩, 刘次东, 李信, 唐耿怀, 廖雨清
2024, 40(7): 1329-1336  doi: 10.11862/CJIC.20230447
[摘要]  (14) [HTML全文] (14) [PDF 17783KB] (0)
摘要:
以氧化石墨烯(GO)、乙酸锌(Zn(CH3COO)2)和硫脲为原料,采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料,并将该材料用作锂离子电池负极。高导电性的rGO可以为锂离子和电子的传输提供有效的路径,ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL-1时制备的rGO/ZnS复合材料的倍率性能最好,循环稳定性最佳。
孔内富氨基的高稳定性铟基金属有机骨架高灵敏电化学传感多巴胺
苏婧, 李冰融, 白乙艳, 籍文娟, 杨海英, 范哲锋
2024, 40(7): 1337-1346  doi: 10.11862/CJIC.20230414
[摘要]  (13) [HTML全文] (13) [PDF 11913KB] (0)
摘要:
为设计高稳定性且高灵敏度的纯金属有机骨架(MOF)电化学传感器以检测多巴胺(DA),我们选用铟基MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O(RSMOF-1,RSMOF=resistance switchable metal-organic framework,2-NH2-H2BDC=2-氨基对苯二甲酸)修饰玻碳电极(RSMOF-1/GCE)。制备的电极RSMOF-1/GCE的DPV测试结果显示其线性范围为0.990~663 μmol·L-1、检出限为0.770 μmol·L-1。在多种干扰物质如尿酸、尿素、葡萄糖和对乙酰氨基酚存在的条件下,RSMOF-1/GCE对DA仍具有高的选择性。理论模拟结果显示,在RSMOF-1孔道内壁的—NH2可通过氢键增强与DA分子的相互作用,使RSMOF-1/GCE具有灵敏的电化学传感DA的性能。
一例由多齿席夫碱构筑的Tb2配合物的结构、荧光性质及生物活性
马鑫, 孙娅, 孙楠, 康倩, 张佳佳, 朱瑞涛, 高晓丽
2024, 40(7): 1347-1356  doi: 10.11862/CJIC.20230357
[摘要]  (11) [HTML全文] (11) [PDF 7878KB] (0)
摘要:
使用多齿希夫碱配体H4L(H4L=N',N″-((1E,1'E)-(1,10-菲咯啉-2,9-二酰基)双(亚甲基)双(2-羟基苯甲酰肼))与Tb(acac)3·2H2O反应(acac-=乙酰丙酮根),通过溶剂热法,设计并合成了一例结构新颖的双核铽配合物[Tb2(L)(H2L)]·2CH3OH·CH3CN (1),并研究了该配合物的结构、荧光性质及生物活性。单晶X射线衍射分析表明该配合物主要含有2个Tb离子和2个失去不同质子的配体离子(L4-和H2L2-)。中心Tb1和Tb2离子都是九配位的,其几何构型呈现扭曲的呼啦圈形。固体荧光实验测试结果表明:该配合物在室温下表现出Tb离子的荧光特征发射峰。生物活性研究表明,与配体H4L和稀土离子相比较,配合物具有更强的抗菌活性。采用紫外可见光谱法、循环伏安法、凝胶电泳法和荧光光谱法研究了该配合物与小牛胸腺DNA之间的相互作用,结果表明配合物主要以插入作用的方式与小牛胸腺DNA结合。
PtRu/氮掺杂碳电催化甲醇氧化及电解水析氢性能
陈凯, 吴锋顺, 肖顺, 张进宝, 朱丽华
2024, 40(7): 1357-1367  doi: 10.11862/CJIC.20230350
[摘要]  (16) [HTML全文] (16) [PDF 28210KB] (0)
摘要:
将三聚氰胺、RuCl3及炭黑以一定的比例分散于乙醇中,采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂,并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明,合成的催化剂中Pt1Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能,质量活性达4.96 A·mgPtRu-1,且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时,当电流密度为100mA·cm-2时,Pt1Ru/NC在HER中表现出最低的过电位(103 mV)和最小的Tafel斜率(15.29 mV·dec-1)。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂,其具有优异催化性能的原因如下:(1) PtRu双金属纳米颗粒高度分散于NC上;(2) Pt以纳米团簇或单原子形式负载于Ru上,后负载于NC,形成了Pt-Ru相分离结构;(3) Pt、Ru与N之间存在协同效应。

  

综述
杂多铌氧簇聚物的研究进展
杨宗斐, 赵晓森, 李靖, 庄文昌
2024, 40(3): 465-480  doi: 10.11862/CJIC.20230306
[摘要]  (19) [HTML全文] (19) [PDF 37301KB] (19)
摘要:
多铌氧簇聚物是多金属氧簇聚物的重要组成部分,具有丰富多样的结构类型,在碱催化、光催化产氢等方面具有广泛的应用前景,吸引了越来越多化学工作者的关注。本文系统地综述了主族元素(ⅢA/ⅣA/ⅤA/ⅥA族)为杂原子的杂多铌氧簇聚物和过渡元素(V/Fe/Cu)为杂原子的杂多铌氧聚合物的研究进展,主要包括化合物的合成策略、结构调控、性质及应用的探索。此外,对当前杂多铌氧簇聚物的发展所面临的挑战进行了总结,并对其后续的发展进行了展望。
论文
直接Z型MIL-100(Fe)/BiOBr异质结的构建及光芬顿降解磺胺甲恶唑的性能
李雨佳, 王天予, 王茀学, 王崇臣
2024, 40(3): 481-495  doi: 10.11862/CJIC.20230314
[摘要]  (12) [HTML全文] (12) [PDF 23947KB] (12)
摘要:
通过原位共沉淀法可控制备了系列直接Z型MIL-100(Fe)/BiOBr异质结。使用粉末X射线衍射(PXRD)、傅里叶红外变换(FTIR)光谱、紫外可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)、高倍透射电镜(HRTEM)以及X射线光电子能谱(XPS)对MIL-100(Fe)/BiOBr异质结晶体结构、微观形貌、光学性能、化学组成进行表征。以低功率发光二级管可见光为光源,探究了MIL-100(Fe)/BiOBr异质结光芬顿降解磺胺甲恶唑(SMX)性能。最佳反应体系MB-7/Vis/H2O2(MB-7是MIL-100(Fe)质量为BiOBr质量的70%时制备的样品)在光源照射70 min后可降解99.8% SMX(5 mg·L-1)。同时,还考察了H2O2浓度、催化剂投加量、pH值以及无机阴离子对MB-7/Vis/H2O2降解SMX影响。MB-7/Vis/H2O2能够在经过5轮循环降解实验后保持95%以上的SMX降解效率,表明其具有较好的循环稳定性。通过光致发光(PL)光谱、光电化学测试、活性物质捕获实验以及电子自旋共振(ESR)技术对光芬顿降解SMX机理进行了揭示。增强的光芬顿活性的机制主要来自于异质结的构建加速了光生载流子的分离,进而促进了活性物质产生以及Fe3+/Fe2+的循环。
UiO-66-NH2负载铜催化剂的制备及其对醇的催化氧化
段章圭, 裴毅, 郑姗姗, 王召阳, 王勇光, 王骏杰, 胡杨, 吕春欣, 钟伟
2024, 40(3): 496-506  doi: 10.11862/CJIC.20230317
[摘要]  (13) [HTML全文] (13) [PDF 41011KB] (13)
摘要:
通过溶剂热法成功制备了一种基于金属有机骨架(MOF)的复合材料Cu-Cu2O/UiO-66-NH2,采用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)对材料进行全面表征。在空气作氧化剂条件下,以苯甲醇氧化为苯甲醛作为模型反应,系统地考察了溶剂、温度、催化剂各组分用量等因素对催化效果的影响。研究结果表明,该复合催化剂在醇选择性氧化反应中表现出优异的催化性能,60 ℃下反应5 h便可将苯甲醇定量转化为苯甲醛,并对其他苄基醇、烯丙基醇和杂芳基醇等底物也展现出良好活性。此外,循环利用3次后,该催化剂活性几乎不变,表明其具有良好的稳定性和重复使用性。
MFI纳米片沉积层气相转化制备超薄b轴取向沸石膜
陈姣, 李毅, 谢毅, 刁丹丹, 肖强
2024, 40(3): 507-514  doi: 10.11862/CJIC.20230403
[摘要]  (15) [HTML全文] (15) [PDF 7434KB] (15)
摘要:
利用乙二胺-水蒸汽进行气相转化(VPT)制备超薄、取向MFI沸石膜,通过将MFI纳米片沉积层转化为致密的沸石膜,实现了膜厚度的有效控制。扫描电子显微镜和X射线衍射表明,制备的沸石膜膜厚度约为280 nm,具有高度b轴取向的致密结构。丁烷异构体双组分分离测试结果表明,在333 K下,等物质的量的正丁烷/异丁烷混合物的正丁烷渗透速率和分离因子分别为1.5×10-7 mol·m-2·s-1·Pa-1和14.8。Na2SiO3作为低聚硅源在MFI沸石纳米片二次生长过程中能够提供硅源和碱度,通过在胺类蒸汽中实现MFI沸石纳米片间的融合生长,进一步提高了膜的取向度和致密性。
碱金属修饰的萘炔/萘二炔对CO2选择性吸附分离的理论计算
赵杰, 刘森, 殷齐康, 鲁效庆, 王兆杰
2024, 40(3): 515-522  doi: 10.11862/CJIC.20230385
[摘要]  (15) [HTML全文] (15) [PDF 20853KB] (15)
摘要:
采用巨正则蒙特卡洛模拟和密度泛函理论结合的方式探究了不同碱金属(alkali metal,AM,包括Li、Na、K)修饰提升萘炔(naphyne,NY)和萘二炔(naphdiyne,NDY)的CO2吸附分离性能。通过结合能和结构的电子性质分析发现,AM修饰的NY和NDY具有良好的结构稳定性。在298 K、100 kPa的条件下,Li修饰的萘二炔(Li-NDY)表现出高达11.37 mmol·g-1的CO2吸附量和430.85的CO2选择性(优于N2)。同时,利用气体吸附密度分布揭示了不同AM修饰的NY/NDY (AM-NY、AM-NDY)具有高吸附量的原因,以及二者作用效果差异的本质。最后,从吸附热、库仑和范德瓦耳斯相互作用等角度详细说明了AM引入的改性机制。
W18O49/NH2-UiO-66复合催化剂的高效光催化CO2环加成
程若霖, 王浩然, 任静, 马莹莹, 梁华根
2024, 40(3): 523-532  doi: 10.11862/CJIC.20230349
[摘要]  (9) [HTML全文] (9) [PDF 18612KB] (9)
摘要:
以2-氨基对苯二甲酸(H2ATA)为配体,通过溶剂热法合成了Zr基MOF:NH2-UiO-66,继而以氯化钨为前驱体,通过溶剂热法实现了富含氧空位的缺陷氧化钨(W18O49)在NH2-UiO-66上的原位生长,构建了具有典型Ⅱ型异质结的复合光催化剂W18O49/NH2-UiO-66。通过粉末X射线衍射、扫描电子显微镜、X射线光电子能谱和紫外可见漫反射光谱对催化剂的组成与结构进行了表征。在室温常压、模拟太阳光下,以氧化苯乙烯为模型底物,对所有样品的光催化活性进行了考察,W18O49/NH2-UiO-66展现了最高的碳酸苯乙烯酯产率(58 mmol·g-1·h-1)。
石蜡/碱改性硅藻土/膨胀石墨复合相变储热材料的制备及性能
陈丽梅, 赵梦菲, 陈琳, 李丁, 李巍, 韩维野, 王鸿斌
2024, 40(3): 533-543  doi: 10.11862/CJIC.20230312
[摘要]  (14) [HTML全文] (14) [PDF 6560KB] (14)
摘要:
通过碱处理,优化了硅藻土(DIA)的孔隙结构,提高了孔隙率,增加了石蜡(paraffin)负载量。通过直接浸渍法制备了新型性状稳定的石蜡/碱改性DIA/膨胀石墨(EG-alDIAP)复合材料,并研究了其结构与性能的关系。结果表明,复合相变材料的石蜡负载量从47.4%提高到了61.1%,进而提高了复合材料的储热性能;向改性DIA中添加膨胀石墨(EG)提高了复合材料的传热能力,添加质量分数10% EG时导热系数提高了113%(从0.276 W·m-1·K-1提高到了0.589 W·m-1·K-1)。随着EG含量的升高,复合相变材料的相变潜热有所增加,但化学相容性、稳定性等无明显变化。含10% EG的石蜡/碱改性DIA复合材料具有可靠的储能性能、良好的温度调节性能和蓄放热能力。
用于高效去除水中孔雀石绿的三层结构磁性复合材料Fe3O4@聚丙烯酸@ZiF-8的制备
徐鹏, 王莎莎, 陈难难, 王澳, 于冬妹
2024, 40(3): 544-554  doi: 10.11862/CJIC.20230239
[摘要]  (9) [HTML全文] (9) [PDF 6557KB] (9)
摘要:
设计并合成了一种以磁性纳米粒子为核,聚合物为中间层,金属有机骨架材料为外层的三层结构磁性复合材料(Fe3O4@PAA@ZIF-8)。首先利用溶剂热法制备Fe3O4纳米粒子,然后通过蒸馏沉淀聚合法在Fe3O4纳米粒子表面包覆聚丙烯酸(PAA)层,最后通过原位沉积法在PAA外部包覆ZIF-8。在对Fe3O4@PAA@ZIF-8的组成和结构进行表征的基础上,深入研究其对孔雀石绿(MG)的吸附性能。透射电子显微镜(TEM)显示Fe3O4@PAA@ZIF-8具有明显的三层结构,Fe3O4的平均粒径为117 nm,PAA层厚度约为17 nm,ZIF-8层的厚度约为14 nm。Fe3O4@PAA@ZIF-8对MG的吸附量随着pH的升高而增大,吸附过程符合准二阶动力学模型和Langmuir等温吸附模型。此外,Fe3O4@PAA@ZIF-8还表现出良好的重复利用性能,8次循环利用后对MG (500 mg·L-1)的最大吸附量仍可达982 mg·g-1
基于第一性原理的无铅无机钙钛矿Cs3Bi2X9(X=Cl、Br、I)光电性能表面效应研究
彭程, 韦建卫, 陈亚婷, 胡南, 曾晖
2024, 40(3): 555-560  doi: 10.11862/CJIC.20230282
[摘要]  (12) [HTML全文] (12) [PDF 9683KB] (12)
摘要:
用基于第一性原理的密度泛函理论方法,对Cs3Bi2X9(X=Cl、Br、I)的光电特性进行理论计算,并系统阐述这3种晶体的表面效应对光电性能的影响。结果表明,3种材料的光学特性由铋原子和卤素原子最外层p轨道上的价电子主导。在可见光区中,材料的吸收峰会随卤素原子序数的增加呈现红移,其中一维结构的Cs3Bi2Cl9表面结构在光吸收能力上尤为特别且敏感;二维结构的Cs3Bi2Br9光吸收能力会受厚度影响;零维结构的Cs3Bi2I9非常稳定,且几乎不受表面特性和晶体厚度的影响。
La促进水滑石衍生镍基催化剂的原位制备及其CO2甲烷化性能
杨文, 王迪迪, 黄子怡, 周亚平, 冯艳艳
2024, 40(3): 561-570  doi: 10.11862/CJIC.20230276
[摘要]  (13) [HTML全文] (13) [PDF 13271KB] (13)
摘要:
采用原位生长法制备水滑石衍生Ni-La/Al2O3催化剂,并用于CO2甲烷化反应,以研究La掺杂量对所得催化剂形貌结构及催化性能的影响。利用电感耦合等离子体发射光谱、X射线衍射、氢气程序升温还原、低温氮气吸附-脱附、扫描电镜和透射电镜对催化剂的形貌结构进行分析。结果表明,适宜的La掺杂量能够提高活性金属Ni在载体中的分散性,减弱Ni与载体的相互作用,并且改善催化剂的孔隙结构,提高催化剂的比表面积。CO2甲烷化性能表明,当Ni负载量(质量分数)为30%、La掺杂量(质量分数)为10%时,催化剂30Ni-10La/Al2O3具有较优的催化性能;350℃时其CO2转化率及CH4产率分别达到91.9%和91.5%,并且连续测试60 h后催化性能基本保持不变。
微量Mg/F表面梯度渗透改善高电压LiCoO2界面脆弱
王鑫龙, 程真国, 王果, 张晓琨, 向勇, 王欣全
2024, 40(3): 571-580  doi: 10.11862/CJIC.20230259
[摘要]  (18) [HTML全文] (18) [PDF 26426KB] (18)
摘要:
采用高温固相法在1 050℃下烧结,制备了LiCoO2低浓度梯度改性样品,分别为LiF掺杂包覆(LCOLF、LCO@LF)和MgF2掺杂包覆(LCOMF、LCO@MF)。通过光电子能谱、透射电子显微镜和电化学技术等表征方法,对比分析材料形貌及电化学性能。结果表明,体相掺杂复合电极中,LCOLF热重测试显示出最优热稳定性,LCOMF晶体中(003)和(104)晶面间距收缩;45℃下1C倍率循环70圈后,LCOLF和LCOMF比容量分别为141.45和166.98 mAh·g-1,循环性能优于LiCoO2。表面包覆复合电极中,LCO@LF和LCO@MF晶粒表面光洁且晶格氧键价都向更高结合能方向增强;LCO@MF构建了坚实且紧密的包覆层,循环70圈后,放电比容量和容量保持率分别为183 mAh·g-1和91.26%(LCO@LF分别为154.38 mAh·g-1和77.54%),循环性能显著优于体相掺杂。
泡沫镍负载NiMoO4/NiMoS4复合材料的制备及其电化学性能
郑佳红, 申嘉钧, 白昕
2024, 40(3): 581-590  doi: 10.11862/CJIC.20230253
[摘要]  (20) [HTML全文] (20) [PDF 19477KB] (20)
摘要:
以泡沫镍作为基底,采用水热法原位生长出具有片状结构的NiMoO4活性材料,然后通过水热硫化制备出NiMoO4/NiMoS4复合材料,研究了水热时间和硫脲添加量对样品形貌和电化学性能的影响。电化学结果表明,NiMoO4/NiMoS4电极在电流密度为1 A·g-1时,比电容为1 560.7 F·g-1,在电流密度为40 A·g-1时循环2 000次后,比电容仍为初始比电容的76.7%。将NiMoO4/NiMoS4电极材料与活性炭(AC)分别作为正、负极组装的非对称超级电容器(ASC)在400 W·kg-1的功率密度下可提供29.0 Wh·kg-1的能量密度。
钨掺杂BiVO4光阳极降解环丙沙星的表面态行为
路子峥, 苏婉宜, 施钦, 潘鸿辉, 赵传起, 黄承锋, 彭进国
2024, 40(3): 591-600  doi: 10.11862/CJIC.20230225
[摘要]  (9) [HTML全文] (9) [PDF 8580KB] (9)
摘要:
采用简单浸渍的方法对BiVO4光阳极进行表面钨(W)掺杂,以环丙沙星(CIP)为药品和个人护理产品(PPCPs)模型污染物,研究了W掺杂BiVO4光阳极降解CIP的表面态行为。结果表明,低浓度W掺杂对BiVO4光阳极的晶体结构、表面形貌和光吸收性能没有显著影响。但W掺杂取代了BiVO4光阳极表面的V5+,能抑制BiVO4光阳极表面V5+/V4+还原过程,减少复合中心表面态,同时引入更多氧空穴,增加活性位点表面态。CIP的降解反应受表面活性位点控制。表面W掺杂能有效促进CIP降解的电荷转移,提高BiVO4光阳极光电催化降解性能。
Articles
Preparation and photocatalytic performance of AgNi bimetallic modified polyhedral bismuth vanadate
Jun LI, Huipeng LI, Hua ZHAO, Qinlong LIU
2024, 40(3): 601-612  doi: 10.11862/CJIC.20230401
[摘要]  (14) [HTML全文] (14) [PDF 11639KB] (14)
摘要:
Polyhedral bismuth vanadate (BVO) material was prepared using a straightforward hydrothermal method, and then a small-sized AgNi bimetallic co-catalyst was synthesized in situ on the surface of the polyhedral BVO through a chemical reduction method. The photocatalytic performance of the catalyst was studied. The physicochemical properties of the prepared AgNi/BVO material were characterized through various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, and nitrogen adsorption-desorption analysis. The results indicated that AgNi bimetallic co-catalysts were extensively loaded onto the unique morphology of BVO polyhedra, significantly increasing the metal attachment sites. Simultaneously, the AgNi loading also improved the crystallinity of BVO. The silver surface plasmon resonance effect, in conjunction with the nickel's lattice interface effect, enhanced the BVO catalyst's absorption of visible light and improved the separation of photo-generated electrons, thereby increasing the photocatalytic activity. Photocatalytic degradation experiments using MB (methylene blue) as a model pollutant demonstrated that when the ratio was 3:1, AgNi/BVO exhibited the highest catalytic activity, with a reaction rate of 5.4 times higher than that of BVO under visible light irradiation. This photocatalyst retained excellent photocatalytic activity even after four cycles of use.
Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties
Shuwen SUN, Gaofeng WANG
2024, 40(3): 613-620  doi: 10.11862/CJIC.20230368
[摘要]  (13) [HTML全文] (13) [PDF 8730KB] (13)
摘要:
Based on Ⅴ-shaped auxiliary ligands, two novel coordination polymers, {[Cd(bipmo)(NDC)]·1.75H2O}n (1), {[Cd(bppmo)(NDC)(H2O)]·H2O}n (2), where H2NDC=2,6-naphthalenedicarboxylic acid, bipmo=bis(4-(1H-imidazol-1-yl)phenyl)methanone, bppmo=bis(4-(pyridin-4-yl)phenyl)methanone, have been synthesized under solvothermal conditions. They have been characterized by single-crystal X-ray diffraction, bond valence sum calculations, IR spectra, and elemental analyses. Complex 1 shows 2-fold interpenetrating sheets of {63} topology, which interpenetrate in a 2D → 2D parallel manner. Complex 2 reveals a 3-fold interpenetrating {63} network. The results indicate that the Ⅴ-shaped ligands have a great effect on the formation of the final structures. In addition, the luminescent properties of complexes 1 and 2 were investigated in detail.
Syntheses, crystal structures, catalytic and anti-wear properties of nickel(Ⅱ) and zinc(Ⅱ) coordination polymers based on 5-(2-carboxyphenyl)nicotinic acid
Zhenghua ZHAO, Qin ZHANG, Yufeng LIU, Zifa SHI, Jinzhong GU
2024, 40(3): 621-628  doi: 10.11862/CJIC.20230342
[摘要]  (12) [HTML全文] (12) [PDF 9866KB] (12)
摘要:
Two nickel(Ⅱ) and zinc(Ⅱ) coordination polymers, namely {[Ni(μ3-cpna)(μ-dpea)0.5]·H2O}n (1) and {[Zn(μ3-cpna)(μ-dpey)0.5]·H2O}n (2) have been constructed hydrothermally using 5-(2-carboxyphenyl)nicotinic acid (H2cpna), 1, 2-di(4-pyridyl)ethane (dpea), 1, 2-di(4-pyridyl)ethylene (dpey), and nickel and zinc chlorides at 160℃. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the monoclinic or orthorhombic systems, space groups, P21/c or Pbca. Both compounds show 3D metal-organic frameworks. Compound 2 exhibited an effective catalytic activity in the Knoevenagel condensation reaction at room temperature. Meanwhile, compound 2 showed an effective anti-wear performance in poly-α-olefine synthetic lubricant.
Denitration performance of HoCeMn/TiO2 catalysts prepared by co-precipitation and impregnation methods
Lihua HUANG, Jian HUA
2024, 40(3): 629-645  doi: 10.11862/CJIC.20230315
[摘要]  (13) [HTML全文] (13) [PDF 6143KB] (13)
摘要:
Impregnation and co-precipitation methods were used to synthesize HoCeMn/TiO2 catalysts for the reduction of NOx with NH3. Different kinds of characterization methods were used to explore the structures and performances of the catalysts. The results show that the co-precipitation method enhances the interactivity between the active component and carrier, thereby increasing the content of Ce3+, Mn4+, and adsorption oxygen on the surface of HoCeMnTi-C. As a result, it showed excellent low-temperature redox performance. In addition, HoCeMnTi-C prepared by the co-precipitation method possessed more surface acidic sites and stronger surface acidity. The improvement of surface acidity and redox performance is conducive to the adsorption and activation of ammonia, and thereby significantly improved its activity. The increase of acidic sites also restrained the adsorption of H2O and SO2, and therefore sulfur and water resistance of HoCeMnTi-C were significantly promoted. The reaction of selective catalytic reduction (SCR) on catalysts obeys the Eley-Rideal (E-R) mechanism. SO2 poisoning of catalysts was caused by the formation of sulfates, which cover or damage the active sites of the catalysts.
A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol
Huan ZHANG, Jijiang WANG, Guang FAN, Long TANG, Erlin YUE, Chao BAI, Xiao WANG, Yuqi ZHANG
2024, 40(3): 646-654  doi: 10.11862/CJIC.20230291
[摘要]  (12) [HTML全文] (12) [PDF 5155KB] (12)
摘要:
A new metal-organic framework (MOF) {[Cd(L)0.5(4, 4'-bpy)0.5]·H2O}n (1), where H4L=(1, 1': 4', 1″-terphenyl)-2, 2″, 4, 4″-tetracarboxylic acid, 4, 4'-bpy=4, 4'-bipyridine, was synthesized by hydro-solvothermal method. The structure of complex 1 was characterized by single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and infrared spectrum analysis. The analysis of single crystal structure shows that 1 is a 3D structure, belonging to the monoclinic crystal system, C2/c space group. Cd(Ⅱ) connects L4- and 4, 4'-bpy to form a 2D plane structure, and the layers are connected by L4- to form a 3D network structure. The MOF shows good stability and can be used for the detection of tetracycline (TET) and p-nitrophenol (4-NP) by fluorescence quenching. The detection limits of TET and 4-NP were 0.15 and 0.062 μmol·L-1, respectively. In addition, the fluorescence quenching mechanism of 1 was also studied. 1 can be successfully applied to the determination of TET and 4-NP content in Yanhe water samples.