层状多孔碳片负载钌催化剂的制备及其催化氨硼烷水解制氢性能研究

左佑华; 吴慧; 花俊峰; 郑君宁; 许立信; 叶明富; 万超

doi:10.1016/S1872-5813(23)60385-8

层状多孔碳片负载钌催化剂的制备及其催化氨硼烷水解制氢性能研究

doi: 10.1016/S1872-5813(23)60385-8

左佑华^1,,
吴慧^1,,
花俊峰²,
郑君宁^1,,
许立信^1, ,,
叶明富^{1, 3, 4, 5,},
万超^{1, 2, ,}

1.
安徽工业大学, 化学与化工学院, 安徽马鞍山 243000
2.
南开大学, 先进能源材料化学教育部重点实验室, 天津 300071
3.
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
4.
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
5.
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项目(22108238)和联合项目(U22A20408)、安徽省自然科学基金青年基金项目(1908085QB68)、中国博士后面上项目(2019M662060)、派出项目(PC2022046)和特别资助站中项目(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年国家级大学生创新创业训练计划项目(202210360037)

详细信息

通讯作者:
E-mail: lxxu@hotmail.com

wanchao@zju.edu.cn

中图分类号: O643.36
计量
- 文章访问数: 19
- HTML全文浏览量: 19
- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2023-07-28
- 修回日期: 2023-09-18
- 录用日期: 2023-09-20
- 网络出版日期: 2023-10-12

Preparation of layered porous carbon supported ruthenium catalyst and its catalytic performance for hydrolyzing amborane to hydrogen

ZUO Youhua^1
,,
WU Hui^1
,,
HUA Junfeng²,
ZHENG Junning^1
,,
XU Lixin^{1
, ,},
YE Mingfu^{1, 3, 4, 5
,},
WAN Chao^{1, 2
, ,}

1.
School of Chemistry and Chemical Engineering, Anhui University of Technology, Anhui Ma’anshan 243000, China
2.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
3.
Key Laboratory of Green Energy and Environment Catalysis, Ningde Normal University, Ningde, Fujian, 352100, China
4.
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou 213164, China
5.
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 National Undergraduate Innovation and entrepreneurship training program (202210360037).

摘要

摘要: 本文以煤沥青为碳材料，氯化钠为模板剂，碳酸钾为活化剂，在氩气气氛下高温煅烧得到载体层状多孔碳片(LPCS)，之后通过浸渍法向其中加入RuCl₃金属溶液，将活性组分Ru负载到LPCS载体上合成Ru/LPCS催化剂，并对其催化氨硼烷水解制氢的性能进行了研究。探究结果表明，Ru/LPCS催化剂中，当煅烧温度为1123 K时，Ru的负载量为2%时，催化剂的反应转化频率(TOF)值最大，此时有光下催化剂的TOF为334.8 min⁻¹，是无光照时TOF的1.38倍。在光照下，催化剂的活化能(E_a)从90.60 kJ/mol下降到70.33 kJ/mol。氨硼烷水解制氢速率相对于其浓度的级数为0.75，而相对于催化剂的用量满足于一级动力学关系。
- 钌基催化剂 /
- 氨硼烷 /
- 水解制氢 /
- 层状多孔碳片
Abstract: In this paper, coal pitch was used as carbon material, sodium chloride as template agent, potassium carbonate as activator, and the carrier layered porous carbon sheet (LPCS) was obtained by high temperature calcination under argon atmosphere, and then RuCl₃ metal solution was added to it by impregnation method, and the active component Ru was loaded onto the LPCS carrier to synthesize Ru/LPCS catalyst, and its catalytic hydrogen production by hydrolysis of ammonia borane was studied. The results of the investigation showed that the maximum value of the reaction transition frequency (TOF) of the Ru/LPCS catalysts was obtained at a calcination temperature of 1123 K and a loading of 2% of Ru, when the TOF of the catalysts in the presence of light was 334.8 min^-1, which is 1.38 times higher than that of the TOF in the absence of light. The activation energy (E_a) of the catalyst decreased from 90.60 kJ/mol to 70.33 kJ/mol in the presence of light. The rate of hydrogen production from hydrolysis of aminoborane with respect to its concentration was of the order of 0.75, whereas with respect to the amount of the catalyst the first-order kinetic relationship was fulfilled.
- ruthenium catalyst /
- ammoniaborane /
- hydrogen production by hydrolysis /
- layered porous carbon sheet

HTML全文

图 1 2%Ru/LPCS₈₅₀催化剂的 (a, b)不同放大倍数下的TEM图像；(c)HAADF图；(d) C, (e) N, (f) O, (g) Ru元素分布图

Figure 1 2% Ru/LPCS₈₅₀ catalyst of (a, b) TEM image at different magnifications ; (c) HAADF plots; (d) elemental distribution of C, (e) N, (f) O, and (g) Ru

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图 2 2%Ru/LPCS₈₅₀催化剂的XRD谱图

Figure 2 The X-ray diffraction patterns of 2%Ru/LPCS₈₅₀ catalysts

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图 3 2%Ru/LPCS₈₅₀催化剂的XPS图谱(a)全谱图; (b) Ru 3p精细谱图;(c)C 1s精细谱图, (d) N 1s精细谱图

Figure 3 (a) XPS pattern of 2.5%Ru/LPCS₈₅₀ catalyst (a) Full spectrum; (b) Ru 3p fine spectrum; (c) C 1s fine spectra, (d) N 1s fine spectra

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图 4 不同煅烧温度下的2.5%Ru/LPCS_x催化AB分解产氢反应中的脱氢速率曲线

Figure 4 Dehydrogenation rate curve in 2.5%Ru/LPCS_x catalyzed AB decomposition hydrogen production reaction at different calcination temperatures

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图 5 (a)不同Ru负载量的Ru/LPCS₈₅₀催化剂在298 K催化AB水解反应中的脱氢速率曲线; (b)为(a)所对应的TOF图

Figure 5 (a) Dehydrogenation rate curve of Ru/LPCS₈₅₀ catalyst with different Ru loading in 298 K catalyzed AB hydrolysis reaction;(b) is the TOF diagram corresponding to (a)

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图 6 (a) 298 K时 AB 脱氢速率随 AB 浓度变化关系曲线； (b)AB脱氢速率与 AB 浓度的对数值关系曲线

Figure 6 (a) Plots of hydrogen evolution rate for the dehydrogenation of AB with different AB concentrations at 298 K; (b) Thelogarithmic plot of hydrogen evolution rate versus AB concentration

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图 7 (a)298 K时，AB脱氢速率随催化剂含量的变化曲线； (b)AB脱氢速率与催化剂质量的对数值关系曲线

Figure 7 (a) Plots of hydrogen evolution rate for the dehydrogenation of AB with different catalyst concentration at 298 K；(b) Plot of hydrogen evolution rate versus catalyst concentration, both in logarithmic scale

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图 8 (a)无光和无光条件下，AB脱氢速率随催化剂含量的变化曲线； (b)为(a)对应的TOF值

Figure 8 (a) Curves of AB dehydrogenation rate as a function of catalyst content under no light and no light conditions; (b) is the TOF value corresponding to (a)

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图 9 (a)有光照、(c)无光照下不同温度下2%Ru/LPCS₈₅₀催化AB脱氢速率曲线； (b)(d)分别是(a)(c)对应的阿伦尼乌斯方程：lnk与 1000/T 关系曲线

Figure 9 (a) catalytic AB dehydrogenation rate curve of 2%Ru/LPCS₈₅₀ at different temperatures without illumination; (b)(d) are the Arrhenius equations corresponding to (a)(c) lnk vs. 1000/T curves

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表 1 催化剂的ICP和BET的测试结果

Table 1 Test results of ICP and BET of catalysts

Catalyst	S_BET (m²·g⁻¹)	Theoretical Ru(mmol)	Reality Ru(mmol)
3%Ru/LPCS₈₅₀	1042.1	0.06	0.041
2.5%Ru/LPCS₈₅₀	−	0.05	0.037
2%Ru/LPCS₈₅₀	980.6	0.04	0.027
1.5%Ru/LPCS₈₅₀	−	0.03	0.021
1%Ru/LPCS₈₅₀	964.5	0.02	0.013
LPCS₈₅₀	990.2	0	0

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