为研究络合剂对纳米铜粉体的制备及其催化性能的影响,分别以柠檬酸、葡萄糖为络合剂,采用溶胶-凝胶法制备纳米铜.考察了两种络合剂对制备过程以及产物结构的影响,通过催化苯氧化合成苯酚的反应考察制得的纳米铜粉的催化性能.研究表明:葡萄糖为络合剂制得的纳米铜(G-Cu)平均粒径较小(30 nm),比表面积为5.203 m2/g,在催化苯制苯酚反应时,具有较高的苯转化率(50.30%),但对苯酚的选择性较差;而柠檬酸为络合剂制得的纳米铜(C-Cu)平均粒径为55 nm,比表面积19.517 m2/g,催化苯转化率为21.95%,选择性为38.46%.此外,通过对溶胶凝胶法制备机理分析可知,在形成的胶体结构中,柠檬酸和葡萄糖中的羧基和羟基分别与铜离子进行配位.
To study the influence of complexing agents on the preparation and catalytic performance of nano?copper in sol?gel method, the preparation of nano?copper powders was carried out by sol?gel method using citric acid and glucose as complexing agents, respectively. The influence of complexing agents on the process and product structure was studied. In addition, the catalytic performance of nano?copper powders obtained using the two complexing agents were also investigated for the oxidation reaction of benzene to phenol. Results showed that the nano?copper powder prepared with glucose( G-Cu) possessed smaller mean grain size of 30 nm and smaller specific surface area of 5.203 m2/g than that of citric acid(C-Cu) (55 nm and 19.517 m2/g, respectively). For oxidation reaction, G-Cu displayed higher benzene conversion(50.30%), but bad selectivity of phenol. While C-Cu showed lower benzene conversion(21.95%) and higher selectivity of phenol(38.46%). Furthermore, it was found that copper ions were coordinated with carboxyl and hydroxyl for citric acid and glucose respectively.
参考文献
[1] | Gil Hwan Hong;Sang Wook Kang .Synthesis of Monodisperse Copper Nanoparticles by Utilizing 1-Butyl-3-methylimidazolium Nitrate and Its Role as Counteranion in Ionic Liquid in the Formation of Nanoparticles[J].Industrial & Engineering Chemistry Research,2013(2):794-797. |
[2] | Chunli Zhang;Shengmao Zhang;Laigui Yu;Zhijun Zhang;Zhishen Wu;Pingyu Zhang.Preparation and tribological properties of water-soluble copper/silica nanocomposite as a water-based lubricant additive[J].Applied Surface Science: A Journal Devoted to the Properties of Interfaces in Relation to the Synthesis and Behaviour of Materials,2012:824-830. |
[3] | Zhang Bao-Sen;Xu Bin-Shi;Xu Yi;Gao Fei;Shi Pei-Jing;Wu Yi-Xiong .CU nanoparticles effect on the tribological properties of hydrosilicate powders as lubricant additive for steel-steel contacts[J].Tribology International,2011(7/8):878-886. |
[4] | Ching S. Chen;Jia H. Wu;Tzu W. Lai .Carbon Dioxide Hydrogenation on Cu Nanoparticles[J].The journal of physical chemistry, C. Nanomaterials and interfaces,2010(35):15021-15028. |
[5] | 高旭瑞,王顺兴.纳米铜的制备与表征[J].热加工工艺,2011(24):73-75. |
[6] | ZHANG Qiu-li,YANG Zhi-mao,DING Bing-jun,LAN Xin-zhe,GUO Ying-juan.Preparation of copper nanoparticles by chemical reduction method using potassium borohydride[J].中国有色金属学报(英文版),2010(z1):240-244. |
[7] | Bruce Dunn;Jeffrey I.Zink .Sol-Gel Chemistry and Materials[J].Accounts of Chemical Research,2007(9):729-0. |
[8] | 李双明,张丽,许灿,李文秀,于三三.溶胶-凝胶自蔓延法制备球形纳米铜粉[J].中国粉体技术,2012(04):21-23,26. |
[9] | Markus Niederberger;Georg Garnweitner .Organic Reaction Pathways in the Nonaqueous Synthesis of Metal Oxide Nanoparticles[J].Chemistry: A European journal,2006(28):7282-7302. |
[10] | MARKUS NIEDERBERGER .Nonaqueous Sol-Gel Routes to Metal Oxide Nanoparticles[J].Accounts of Chemical Research,2007(9):793-800. |
[11] | Lucky M. Sikhwivhilu;Sreejarani K. Pillai;Thembela K. Hillie .Influence of Citric Acid on SnO_2 Nanoparticles Synthesized by Wet Chemical Processes[J].Journal of nanoscience and nanotechnology,2011(6):4988-4994. |
[12] | Fatemeh Davar;Asadollah Hassankhani;Mohammad Reza Loghman-Estarki .Controllable synthesis of metastable tetragonal zirconia nanocrystals using citric acid assisted sol-gel method[J].CERAMICS INTERNATIONAL,2013(3):2933-2941. |
[13] | JIANG Y W;YANG SH G;Hua ZH H.Sol-Gel autocombustion synthesis of metals and metal alloys[J].Angew Chem Int Ed,2009:48,1-4. |
[14] | Yang W.;Qi YL.;Ma YJ.;Li X.;Guo XJ.;Gao JZ.;Chen M. .Synthesis of Nd2O3 nanopowders by sol-gel auto-combustion and their catalytic esterification activity[J].Materials Chemistry and Physics,2004(1):52-57. |
[15] | Bela Gyurcsik;Laszol Nagy .Carbohydrates as ligands: coordination equilibria and structure of the metal complexes[J].Coordination chemistry reviews,2000(0):81-149. |
[16] | 赵瑶兴;孙祥玉.有机分子结构光谱鉴定[M].北京:科学出版社,2010 |
[17] | CRISTINA ILEANA COVALIU;OVIDIU OPREA;OANA ADRIANA JINGA .Antioxidant Activity of a Ni (II)-2-deoxy-D-glucose Complex Compound[J].Revista de Chimie,2011(12):1137-1140. |
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