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. -
图 1 （a）−（c）Co-MIL、Co0.5Cu0.5-MIL和Cu-MIL的SEM图像；（d）−（i）Co/CNR、Co0.5Cu0.5/CNR和Cu/CN催化剂的SEM图像
Figure 1 (a)−(c) SEM images of Co-MIL、Co0.5Cu0.5-MIL and Cu-MIL, (d)−(i) SEM images of Co/CNR、Co0.5Cu0.5/CNR and Cu/CN
图 2 （a）−（c）Co0.5Cu0.5/CNR不同放大倍率的TEM图；（d）晶格条纹计算图像；（e）Co0.5Cu0.5/CNR中Co、Cu和C的相应元素映射
Figure 2 (a)−(c) TEM image of Co0.5Cu0.5/CNR with different magnification, (d) calculation image of lattice fringe,(e) the corresponding elemental mapping of Co、Cu、and C
图 3 （a）不同金属摩尔比的CoxCu1−x-MIL对应的XRD谱图；（b）不同金属摩尔比的CoxCu1−x/CNR对应的XRD谱图
Figure 3 (a) XRD patterns of CoxCu1−x-MIL with different molar ratios of metals, (b) XRD patterns of CoxCu1−x/CNR with different molar ratios of metals
图 4 （a）Co/CNR、Co0.5Cu0.5/CNR和Cu/CN的全谱图以及相对应的精细谱图（b）C 1s，（c）Co 2p，（d）Cu 2p
Figure 4 (a) Full spectrum of Co/CNR, Co0.5Cu0.5/CNR and Cu/CN and fine spectrum of corresponding (b) C 1s, (c) Co 2p and (d) Cu 2p
图 5 （a）不同CoCu摩尔比例催化剂催化AB水解制氢的速率曲线以及（b）与之对应的TOF值
Figure 5 (a) Hydrolysis rate curves of AB catalyzed with different CoCu molar ratios and (b) the corresponding TOF values
图 6 （a）不同溶剂热温度所制备的催化剂催化AB水解制氢的速率曲线以及（b）与之对应的TOF值
Figure 6 (a) Hydrolysis rate curves of AB catalyzed with different solvothermal temperatures (b) the corresponding TOF values
图 7 （a）焙烧温度对Co0.5Cu0.5/CNR催化AB水解制氢的影响以及（b）与之对应的TOF值
Figure 7 (a) Effect of calcination temperature on Co0.5Cu0.5/CNR catalyzed hydrolysis of AB and (b) the corresponding TOF values
图 8 （a）不同用量的Co0.5Cu0.5/CNR催化AB水解制氢的速率曲线；（b）ln[k]-ln[cat.]拟合曲线
Figure 8 (a) The rate curves of hydrolysis of AB catalyzed by different dosage of Co0.5Cu0.5/CNR, (b) the fitting curve of ln[k]-ln[cat.]
图 9 （a）Co0.5Cu0.5/CNR催化AB水解制氢速率随自身浓度变化；（b）ln[k]-ln[AB]的拟合曲线
Figure 9 (a) The hydrolytic rate of AB catalyzed by Co0.5Cu0.5/CNR varies with its own concentration, (b) the fitting curve of ln[k]-ln[AB]
图 10 反应温度对催化剂Co/CNR、Co0.5Cu0.5/CNR和Cu/CN催化AB水解制氢的影响以及ln[k]-1/T的Arrhenius图
Figure 10 Effect of reaction temperature on hydrolysis of AB over Co/CNR、Co0.5Cu0.5/CNR and Cu/CN catalysts and Arrhenius diagram of ln[k]-1/T
图 11 Co0.5Cu0.5/CNR催化AB水解制氢循环性能图
Figure 11 Cycle stability test of Co0.5Cu0.5/CNR for hydrogen generation from AB
图 12 Co0.5Cu0.5/CNR循环测试反应后的不同倍率SEM图
Figure 12 SEM images of different magnifications after Co0.5Cu0.5/CNR cycling test reaction
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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