School of Chemistry and Chemical Engineering, Anhui University of Technology
Zhejiang Environment Technology Co., Ltd
Engineering Research Center of Biofilm Water Purification and Utilization Technology, Ministry of Education, Anhui University of Technology
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University
College of Chemical Engineering and Biological Engineering, Zhejiang University

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（CoxCu1−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CoxCu1−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，Co0.5Cu0.5/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,N-dimethylformamide 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 (CoxCu1−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 CoxCu1−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 Co0.5Cu0.5/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.

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)和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

左佑华, 李蓉, 花俊峰, 郝思雨, 谢婧, 许立信, 叶明富, 万超. Co0.5Cu0.5/CNR催化剂制备及其氨硼烷水解制氢性能研究[J]. 燃料化学学报（中英文）, 2024, 52(9): 1307-1317.

ZUO Youhua, LI Rong, HUA Junfeng, HAO Siyu, XIE Jing, XU Lixin, YE Mingfu, WAN Chao. Preparation of Co0.5Cu0.5/CNR catalyst and its performance in hydrogen production by hydrolysis of ammonia borane[J]. Journal of Fuel Chemistry and Technology, 2024, 52(9): 1307-1317.