Co_(0.5)Cu_(0.5)/CNR催化剂制备及其氨硼烷水解制氢性能研究  

Preparation of Co_(0.5)Cu_(0.5)/CNR catalyst and its performance in hydrogen production by hydrolysis of ammonia borane

作　　者：左佑华 李蓉 花俊峰 郝思雨 谢婧 许立信[1] 叶明富[1,3,4] 万超[1,4,5,6] ZUO Youhua;LI Rong;HUA Junfeng;HAO Siyu;XIE Jing;XU Lixin;YE Mingfu;WAN Chao(School of Chemistry and Chemical Engineering,Anhui University of Technology,Ma’anshan 243032,China;Zhejiang Environment Technology Co.,Ltd,Hangzhou 310027,China;Engineering Research Center of Biofilm Water Purification and Utilization Technology,Ministry of Education,Anhui University of Technology,Ma’anshan 243032,China;Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University,Tianjin 300071,China;Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology,Changzhou University,Changzhou 213164,China;College of Chemical Engineering and Biological Engineering,Zhejiang University,Hangzhou 310058,China)

机构地区：[1]安徽工业大学化学与化工学院,安徽马鞍山243032 [2]浙江省环境科技有限公司,浙江杭州310027 [3]安徽工业大学生物膜法水质净化及利用技术教育部工程研究中心,安徽马鞍山243032 [4]南开大学先进能源材料化学教育部重点实验室,天津300071 [5]常州大学江苏省绿色催化材料与技术重点实验室,江苏常州213164 [6]浙江大学化学工程与生物工程学院,浙江杭州310058

出　　处：《燃料化学学报（中英文）》2024年第9期1307-1317,共11页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金青年基金(22108238,U22A20408);安徽省自然科学基金青年基金(1908085QB68);中国博士后项目(2019M662060,PC2022046,2020T130580);江苏省绿色催化材料与技术重点实验室(BM2012110);2022、2023年国家级大学生创新创业训练计划项目(202210360037,S202310260212);生物膜法水质净化及利用技术教育部工程研究中心开放基金(BWPU2023KF06)资助。

摘　　要：以硝酸钴和硝酸铜制备溶液A,苯二甲酸(PTA)和N,N-二甲基甲酰胺(DMF)制备溶液B,两种溶液通过溶剂热法制备Co/Cu拉瓦希尔骨架系列材料(Co/Cu-MIL前驱体),进一步直接碳化前驱体制备出MOFs衍生物,即双金属碳纳米棒(CoxCu_(1-x)/CNR)催化剂。通过SEM、TEM、XRD、XPS等表征手段探究其形貌和组成。结果表明,Co/Cu-MIL经过高温焙烧后成功得到CoxCu_(1-x)/CNR,当x=0.5、溶剂热温度为120℃、焙烧温度为650℃时得到的催化剂催化活性最优,Co_(0.5)Cu_(0.5)/CNR催化剂催化氨硼烷(AB)水解制氢的TOF值为2718.21 h^(-1),反应的活化能为51.64 kJ/mol,且催化剂的循环稳定性较好,在循环10次后催化活性虽然有所下降,但对AB仍然保持100%的转化率。Cobalt nitrate and copper nitrate was mixed to prepare solution A.Phenyldicarboxylic acid and N,Ndimethylformamide was mixed to prepare solution B.Co/Cu Lavashield skeleton series materials(Co/Cu-MIL precursors)was then synthesized by mixing the above two solution via solvothermal method.The precursor was further carbonized to produce the MOFs derivatives,i.e.bimetallic carbon nanorods(Co_(x)Cu_(1−x)/CNR)catalysts.The morphology and composition of the catalysts were explored by SEM,TEM,XRD,XPS and other characterization means.The results showed that Co_(x)Cu_(1−x)/CNR was successfully obtained after calcination of Co/Cu-MIL at high temperature.The activity of the catalyst was optimal when x=0.5,the solvothermal temperature of 120℃and the calcination temperature of 650℃.The TOF value of the Co_(0.5)Cu_(0.5)/CNR catalyst for the hydrolysis of ammonia borane for the production of hydrogen was 2718.21 h−1 with activation energy of 51.64 kJ/mol.The catalyst had good cyclic stability.Although the activity decreased,the conversion of AB still maintained 100% after 10 cycles.

关 键 词：拉瓦希尔骨架系列材料 MOFs衍生物 双金属碳纳米棒催化剂 氨硼烷 水解制氢 

分 类 号：O643.36[理学—物理化学]