焙烧温度和分散剂对Co<sub>0.8</sub>Cu<sub>0.2</sub>/CNC催化氨硼烷水解制氢性能的影响研究

李蓉; 左佑华; 徐立成; 花俊峰; 冯佳佳; 许立信; 叶明富; 万超

doi:10.1016/S1872-5813(24)60462-7

焙烧温度和分散剂对Co_0.8Cu_0.2/CNC催化氨硼烷水解制氢性能的影响研究

doi: 10.1016/S1872-5813(24)60462-7

李蓉^1,,
左佑华^1,,
徐立成^2,,
花俊峰^3,,
冯佳佳^1,,
许立信^1, ,,
叶明富^{1, 4, 5, 6,},
万超^{1, 5, 7, 8, ,}

1.
安徽工业大学化学与化工学院, 安徽马鞍山 243032
2.
青岛科技大学高分子科学与工程学院, 山东青岛 266042
3.
浙江省环境科技有限公司, 浙江杭州 310027
4.
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
5.
南开大学先进能源材料化学教育部重点实验室, 天津 300071
6.
宁德师范学院绿色能源与环境催化福建高校重点实验室, 福建宁德 352100
7.
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
8.
浙江大学化学工程与生物工程学院, 浙江杭州 310058

基金项目: 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)，中国博士后面上项目(2019M662060, PC2022046, 2020T130580)，江苏省绿色催化材料与技术重点实验室(BM2012110)，绿色能源与环境催化福建省高校重点实验室开放课题(FJ-GEEC202204)，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

详细信息

通讯作者:
E-mail: lxxu@hotmail.com

wanchao@zju.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2024-04-30
- 修回日期: 2024-05-13
- 录用日期: 2024-05-14
- 网络出版日期: 2024-06-05

The effects of calcination temperature and dispersants on the catalytic performance of Co_0.8Cu_0.2/CNC for the hydrolysis of ammonia borane to hydrogen were investigated

LI Rong^1
,,
ZUO Youhua^1
,,
XU Licheng^2
,,
HUA Junfeng^3
,,
FENG Jiajia^1
,,
XU Lixin^{1
, ,},
YE Mingfu^{1, 4, 5, 6
,},
WAN Chao^{1, 5, 7, 8
, ,}

1.
School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan 243032, China
2.
College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
3.
Zhejiang Environment Technology Co., Ltd, Hangzhou 310027, China
4.
Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education, Anhui University of Technology, Ma’anshan 243032, China
5.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
6.
Key Laboratory of Green Energy and Environment Catalysis, Ningde Normal University, Ningde 352100, China
7.
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou 213164, China
8.
College of Chemical Engineering and Biological Engineering, Zhejiang University, Hangzhou 310058, China

Funds: The project was supported by the National Natural Science Foundation of China (22108238、U22A20408), Anhui Provincial Natural Science Foundation (1908085QB68), China Postdoctoral Science Foundation (2019M662060, PC2022046, 2020T130580), Open Research Funds of Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110), Open Research Funds of Key Laboratory of Green Energy and Environment Catalysis(FJ-GEEC202204)and 2022、2023 National Undergraduate Innovation and entrepreneurship training program (202210360037、S202310260212), Supported by the Open Project of Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education (BWPU2023KF06).

摘要

摘要: 氨硼烷（NH₃BH₃，AB）被认为是一种便携式制氢的理想储氢材料。本工作在常温下搅拌反应物得到Co_0.8Cu_0.2-ZIF前驱体，并高温焙烧此前驱体制备了一种双金属碳立方体（Co_0.8Cu_0.2/CNC）催化剂。此外，采用多种表征方法对催化剂的微观结构以及组成成分进行了研究。通过单一变量法探究了催化剂的变化规律。结果表明，少量Cu的加入会对Co_0.8Cu_0.2/CNC催化剂的立方体形貌有一定的稳固作用。当分散剂为CTAB且焙烧温度为873 K时，其催化AB水解制氢的活化能（E_a）为50.79 kJ/mol，转化频率（TOF）值高达23.37 min⁻¹。此外，该催化剂经过25次循环后仍然可以催化AB完全水解制氢，表明该催化剂的稳定性能良好。
- 双金属碳立方体 /
- 氨硼烷 /
- 水解制氢
Abstract: Ammonia borane (NH₃BH₃, AB) is considered as an ideal hydrogen storage material for portable hydrogen production. In this paper, Co_0.8Cu_0.2-ZIF precursor was obtained by stirring the reactants at room temperature, and a bimetallic carbon cube (Co_0.8Cu_0.2/CNC) catalyst was prepared by roasting this precursor at high temperature. In addition, the microstructure as well as the composition of the catalyst was investigated using various characterization methods. The change rule of the catalyst was explored by the single-variable method. The results showed that the addition of a small amount of Cu had a stabilizing effect on the cubic morphology of the Co_0.8Cu_0.2/CNC catalyst. When the dispersant was CTAB and the roasting temperature was 873 K, the activation energy (E_a) for catalyzing the hydrolysis of AB to hydrogen was 50.79 kJ/mol, and the transition frequency (TOF) value was as high as 23.37 min⁻¹. In addition, the catalyst could still catalyze the complete hydrolysis of AB to hydrogen after 25 cycles, which indicated that the catalyst had good stability performance.
- Bimetallic carbon cube /
- ammonia borane /
- hydrogen hydrolysis

HTML全文

图 1 Co_0.8Cu_0.2/CNC催化剂合成示意图

Figure 1 The synthetic schematic illustration of Co_0.8Cu_0.2/CNC

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图 2 （a）−（f）Co-ZIF、Co_0.8Cu_0.2-ZIF和Cu-ZIF的SEM图像；（g）−（i）Co/CNC、Co_0.8Cu_0.2/CNC和Cu/C催化剂的SEM图像

Figure 2 (a)−(f) SEM images of Co-ZIF, Co_0.8Cu_0.2-ZIF and Cu-ZIF; (g)−(i) SEM images of Co/CNC, Co_0.8Cu_0.2/CNC and Cu/C

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图 3 （a）−（c）Co_0.8Cu_0.2/CNC不同放大倍率的TEM图像；（d）晶格条纹计算；（e）粒径分布；（f）Co_0.8Cu_0.2/CNC中Cu、C和Co的相应元素映射

Figure 3 (a)−(c) TEM image of Co_0.8Cu_0.2/CNC with different magnification; (d) calculation image of lattice fringe; (e) particle size distribution of Co_0.8Cu_0.2/CNC; (f) the corresponding elemental mapping of Cu, C and Co

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图 4 （a）Cu-ZIF、Co_0.8Cu_0.2-ZIF和Co-ZIF；（b）Cu/C、Co_0.8Cu_0.2/CNC和Co/CNC催化剂的XRD谱图

Figure 4 (a) XRD images of Cu-ZIF、Co_0.8Cu_0.2-ZIF and Co-ZIF; (b) XRD images of Cu/C、Co_0.8Cu_0.2/CNC and Co/CNC

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图 5 （a）采用不同分散剂制备的催化剂催化AB水解制氢的速率；（b）对应的TOF值

Figure 5 (a) Hydrolysis rate curves of AB catalyzed by catalysts prepared with different dispersants;(b) the corresponding TOF values

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图 6 （a）不同的焙烧温度对Co_0.8Cu_0.2/CNC催化AB水解制氢的影响；（b）对应的TOF值

Figure 6 (a) Effect of calcination temperature on Co_0.8Cu_0.2/CNC catalyzed hydrolysis of AB; (b) the corresponding TOF values

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图 7 （a）不同反应温度对Co_0.8Cu_0.4/CNC催化AB水解制氢速率；（b）ln k-1/T的Arrhenius图

Figure 7 (a) Rate profiles of hydrogen production from Co_0.8Cu_0.2/CNC-catalyzed AB hydrolysis with different reaction temperatures; (b) Arrhenius diagram for ln k-1/T

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图 8 Co_0.8Cu_0.2/CNC催化AB水解制氢循环性能

Figure 8 Cyclic performance diagram of Co_0.8Cu_0.2/CNC catalyzed AB hydrolysis for hydrogen production

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表 1 Co/CNC、Co_0.8Cu_0.2/CNC和Cu/C催化剂的ICP-AES测试

Table 1 ICP-AES results of Co/CNC、Co_0.8Cu_0.2/CNC and Cu/C catalysts

Catalyst	Co w/%	Cu w/%	Co-Cu initaial composition (molor ratio)	Cu-Co final composition (molor ratio)	Final metals/catalyst (mmol·100 mg⁻¹)
Co/CNC	20.90	—	—	—	0.354
Co_0.8Cu_0.2/CNC	18.50	4.36	80∶20	82∶18	0.382
Cu/C	49.73	—	—	—	0.782

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