Preparation of Co0.5Cu0.5/CNR catalyst and its performance in hydrogen production by hydrolysis of ammonia borane
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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(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。
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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
Abstract: Solution A was prepared with cobalt nitrate and copper nitrate, and solution B was prepared with phenyldicarboxylic acid(PTA) and N,N-dimethylformamide(DMF), and the two solutions were used to prepare Co/Cu Lavashield skeleton series materials(Co/Cu-MIL precursors) by solvothermal method, and the further direct carbonization of the precursor system prepared the MOFs derivatives, i.e., bimetallic carbon nanorods(CoxCu1−x/CNR) catalyst. The morphology and composition were explored by SEM, TEM, XRD, XPS and other characterization means. The results showed that CoxCu1−x/CNR was successfully obtained after Co/Cu-MIL was roasted at high temperature, and the catalytic activity of the catalyst obtained was optimal when x=0.5, the solvent heat temperature was 120°C, and the roasting temperature was 650 ℃. The TOF value of the Co0.5Cu0.5/CNR catalyst catalyzed the hydrolysis of ammonia borane (AB) for the production of hydrogen was 2718.21 h−1, and the reaction The activation energy was 51.64 kJ/mol, and the catalyst had good cycling stability, and the catalytic activity decreased after 10 cycles, but still maintained 100% conversion of AB. -
表 1 钴铜催化剂催化氨硼烷水解制氢的催化活性
Table 1 The reported catalytic activity of cobalt-copper bimetallic catalysts for the hydrolysis of ammonia borane to produce hydrogen
Catalyst Temp./
℃TOF/
h−1Ea/
(kJ·mol−1)Ref. Co0.5Cu0.5/CNR 25 2718.21 51.64 this work Cu0.4Co0.6/BN nanofibers 25 505.2 21.8 [39] CuCo(O)@CN 25 744 33.8 [40] Cu@Co/rGO 25 522 51.3 [41] CuCo2O4 25 2640 23.6 [42] Cu2O-CoO 25 2046 34.1 [43] Cu0.3@Cu0.7CoOx@GO 25 2676 35.4 [44] Co40Cu60@ S16LC-20 25 984 38.1 [45] CuO-Co3O4 25 2004 39.6 [46] -
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