Rh/N-GMCs纳米催化剂的制备及其催化氨硼烷水解产氢性能研究

李贵; 梁雨; 郑君宁; 许立信; 叶明富; 万超

doi:10.19906/j.cnki.JFCT.2022069

Rh/N-GMCs纳米催化剂的制备及其催化氨硼烷水解产氢性能研究

doi: 10.19906/j.cnki.JFCT.2022069

李贵^1,,
梁雨¹,
郑君宁¹,
许立信¹,
叶明富^{1, 2, 3, 4},
万超^{1, 5, ,}

1.
安徽工业大学化学与化工学院工程研究院, 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.
安庆师范大学安徽省光电磁性功能材料重点实验室功能配合物安徽省重点实验室, 安徽安庆 246011
4.
九江学院江西省生态化工工程研究中心, 江西九江 332005
5.
浙江大学化学工程与生物工程学院, 浙江杭州 310027

基金项目: 国家自然科学基金青年基金(22108238)，安徽省自然科学基金青年基金(1908085QB68)，安徽省科技重大专项(201903a05020055)，中国博士后面上项目(2019M662060)和特别资助站中项目(2020T130580)，安徽省光电磁性功能材料重点实验室开放研究基金(ZD2021007)和江西省生态化工工程研究中心开放研究基金(STKF2109)资助

详细信息

通讯作者:
E-mail: wanchao@zju.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2022-06-21
- 修回日期: 2022-08-01
- 录用日期: 2022-08-07
- 网络出版日期: 2022-08-17
- 刊出日期: 2023-04-15

Preparation of Rh/N-GMCs nanocatalyst and its catalytic performance for the hydrolytic dehydrogenation of ammonia borane

LI Gui^1
,,
LIANG Yü¹,
ZHENG Jun-ning¹,
XU Li-xin¹,
YE Ming-fu^{1, 2, 3, 4},
WAN Chao^{1, 5
, ,}

1.
College of Chemistry and Chemical Engineering, Institute of Engineering, Anhui University of Technology, Ma'anshan 243000, China
2.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
3.
Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials, Anhui Key Laboratory of Functional Coordination Compounds, Anqing Normal University, Anqing 246011, China
4.
Jiangxi Province Engineering Research Center of Ecological Chemical Industry, Jiujiang University, Jiujiang 332005, China
5.
College of Chemical Engineering and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Funds: The project was supported by the National Natural Science Foundation of China (22108238), Anhui Provincial Natural Science Foundation (1908085QB68), Major Science and Technology Project of Anhui Province (201903a05020055), China Postdoctoral Science Foundation (2019M662060, 2020T130580), Open Research Funds of Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials (ZD2021007) and Open Research Funds of Jiangxi Province Engineering Research Center of Ecological Chemical Industry (STKF2109).

摘要

摘要:
本实验通过高温焙烧三聚氰胺和葡萄糖混合物制备出具有独特层状结构的氮掺杂石墨相炭材料（N-GMCs）。再以N-GMCs为载体采用浸渍-还原法将金属Rh负载到载体表面，最终制得Rh/N-GMCs催化剂。结果表明，Rh与N-GMCs之间存在强的金属-载体相互作用，Rh的负载量为0.4%时，反应转化频率（TOF）值达到峰值，此时0.4%Rh/N-GMCs催化剂的TOF为645.3 min^–1，该催化剂上氨硼烷水解的活化能（E_a）为54.0 kJ/mol，氨硼烷脱氢速率随氨硼烷浓度和催化剂浓度呈现正相关，该催化剂循环10次之后，催化活性未明显下降，表明该催化剂具有较好的循环稳定性。
- 铑催化剂 /
- 氨硼烷 /
- 氮掺杂炭材料 /
- 水解产氢
Abstract:
In this paper, nitrogen-doped graphitic carbon materials (N-GMCs) with unique layered structure were prepared by calcining a mixture of melamine and glucose at high temperature. The Rh/N-GMCs catalyst was finally prepared by impregnation-reduction method using N-GMCs as the carrier to support the metal Rh on the surface of the carrier. The results showed that there was a strong metal-support interaction between Rh and N-GMCs, and the reaction transition frequency (TOF) value reached a peak when the loading amount of Rh was 0.4%. At this time, the TOF value of AB dehydrogenation reaction catalyzed by 0.4%Rh/N-GMCs catalyst was 645.3 min^–1, and the activation energy (E_a) of ammonia borane hydrolysis on this catalyst was 54.0 kJ/mol. The rate was positively correlated with the ammonia borane concentration and the catalyst concentration. After 10 cycles of the catalyst, the catalytic activity did not decrease significantly, indicating that the catalyst had excellent cyclic stability.
- Rh catalyst /
- ammonia borane /
- nitrogen-doped carbon material /
- hydrolytic dehydrogenation

HTML全文

FIG. 2212. FIG. 2212.

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图 1 Rh/N-GMCs合成示意图

Figure 1 Schematic illustration of synthesis of Rh/N-GMCs

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图 2 0.4%Rh/N-GMCs催化剂的XRD谱图

Figure 2 X-ray diffraction patterns for 0.4%Rh/N-GMCs

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图 3 ((a)、(b)、(c)) 0.4%Rh/N-GMCs催化剂不同放大倍数下的TEM照片；(d) 0.4%Rh/N-GMCs催化剂的STEM照片；(e) C, (f) N, (g) Rh三种元素的分布

Figure 3 ((a), (b), (c)) TEM images of 0.4%Rh/N-GMCs with different magnification; (d) HADDF-STEM images and elemental mapping of elements, (e) C, (f) N and (g) Rh of 0.4%Rh/N-GMCs catalysts

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图 4 (a) 0.4%Rh/N-GMCs催化剂的XPS谱图；相对应的精细谱图 (b) Rh 3d, (c) C 1s和(d) N 1s

Figure 4 (a) XPS spectrum of 0.4% Rh/N-GMCs catalyst, corresponding fine spectrum (b) Rh 3d, (c) C 1s and (d) N 1s

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图 5 (a) 0.4%Rh/GMCs催化剂的XPS谱图；相对应的精细谱图 (b) Rh 3d

Figure 5 (a) XPS spectrum of 0.4% Rh/GMCs catalyst, corresponding fine spectrum (b) Rh 3d

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图 6 (a) 不同Rh负载量的Rh/N-GMCs催化剂在283 K催化AB水解反应中的脱氢速率；(b) 脱氢速率与Rh负载量的对数值；(c) AB的转化率随Rh负载量的变化；(d) 不同Rh负载量的Rh/N-GMCs催化剂在283 K脱氢AB所对应的TOF值

Figure 6 (a) Plots of hydrogen evolution rate for the hydrolysis of AB with different rhodium concentration at 283 K; (b) logarithmic plot of hydrogen evolution rate versus Rh loading; (c) conversion rate of AB for the dehydrogenation of AB at different rhodium concentration; (d) turnover frequency (TOF) values for the dehydrogenation of AB at 283 K when Rh/N-GMCs with different rhodium loading

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图 7 (a) 283 K时AB脱氢速率随AB浓度的变化；(b) AB脱氢速率与AB浓度的对数值

Figure 7 (a) Plots of hydrogen evolution rate for the dehydrogenation of AB with different AB concentrations at 283 K; (b) logarithmic plot of hydrogen evolution rate versus AB concentration

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图 8 (a) 283 K时AB脱氢速率随催化剂含量的变化；(b) AB脱氢速率与催化剂质量的对数值

Figure 8 (a) Plots of hydrogen evolution rate for the dehydrogenation of AB with different catalyst concentration at 283 K；(b) Plot of hydrogen evolution rate versus catalyst concentration, both in logarithmic scale

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图 9 0.4%Rh/N-GMCs催化AB水解产氢的循环稳定性

Figure 9 Stability test AB hydrolysis catalyzed by 0.4% Rh/N-GMCs

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图 10 0.4%Rh/N-GMCs催化剂循环10次的透射电镜照片

Figure 10 TEM images of 0.4%Rh/N-GMCs after the tenth cycle tests

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图 11 0.4%Rh/N-GMCs催化剂循环10次的XPS谱图；相对应的精细谱图 (b) Rh 3d, (c) C 1s和(d) N 1s

Figure 11 XPS spectra of 0.4%Rh/N-GMCs after the tenth cycle tests, corresponding fine spectrum (b) Rh 3d, (c) C 1s and (d) N 1s

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图 12 (a) 不同温度下0.4%Rh/N-GMCs催化AB脱氢速率；(b) lnk与1000/T关系

Figure 12 (a) AB dehydrogenation rate curves of 0.4%Rh/N-GMCs at different temperatures; (b) lnk versus 1000/T

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表 1 室温下水溶液中AB水解制氢各种贵金属催化剂的催化活性

Table 1 Catalytic activities of various noble metal catalysts for AB hydrolysis in aqueous solution at room temperature

Catalyst	TOF/min^–1	E_a/(kJ·mol^–1)	Ref.
Rh/N-GMCs	645.3	54	this work
Rh/Ni@CN	351	33.5	[30]
Rh@TiO₂	334	28.3	[31]
Rh⁰/AC	188	39.9	[32]
Rh/C-SC	336	37.1	[33]
Rh⁰/Co₃O₄	1800	61.7	[34]
Rh@S-1-H	699	75.5	[35]
Rh⁰/nanoZrO₂	198	48	[36]
Pt@PC-POP	104.3	56.4	[37]
Rh@UiO-66	219.8	38.4	[38]

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