功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应

doi:10.15541/jim20210311

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 547-553.DOI: 10.15541/jim20210311

功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应

王虹力¹(), 王男¹, 王丽莹¹, 宋二红²(), 赵占奎¹()

1. 长春工业大学材料科学与工程学院, 先进结构材料教育部重点实验室, 长春 130012
2. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050

收稿日期:2021-05-17 修回日期:2021-07-12 出版日期:2022-05-20 网络出版日期:2021-07-12
通讯作者: 宋二红, 副研究员. E-mail: ehsong@mail.sic.ac.cn;赵占奎, 教授. E-mail: zhaozk@ccut.edu.cn
作者简介:王虹力(1989-), 女, 副教授. E-mail: wanghongli@ccut.edu.cn
基金资助:
国家自然科学基金(51601018);国家自然科学基金(51671035);上海市自然科学基金面上项目(21ZR1472900);吉林省教育厅“十三五”科学技术项目(JJKH20200660KJ)

Hydrogen Generation from Formic Acid Boosted by Functionalized Graphene Supported AuPd Nanocatalysts

WANG Hongli¹(), WANG Nan¹, WANG Liying¹, SONG Erhong²(), ZHAO Zhankui¹()

1. Key Laboratory of Advanced Structural Materials, Ministry of Education, School of Materials Science and Engineering, Changchun University of Technology, Changchun 130012, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-05-17 Revised:2021-07-12 Published:2022-05-20 Online:2021-07-12
Contact: SONG Erhong, associate professor. E-mail: ehsong@mail.sic.ac.cn;ZHAO Zhankui, professor. E-mail: zhaozk@ccut.edu.cn
About author:WANG Hongli (1989-), female, associate professor. E-mail:wanghongli@ccut.edu.cn
Supported by:
National Natural Science Foundation of China(51601018);National Natural Science Foundation of China(51671035);Shanghai Natural Science Foundation of China(21ZR1472900);Science and Technology Research Project of the Education Department of Jilin Province(JJKH20200660KJ)

摘要/Abstract

摘要：

甲酸(FA)因具有储氢量高、易加注等优点而成为极具应用前景的新型储氢材料, 寻求高效率催化剂对于解决甲酸制氢反应动力学缓慢的问题尤为重要。本工作以聚乙烯亚胺修饰石墨烯(PEI-rGO)作为催化剂衬底, 通过湿化学法制备PEI-rGO担载型AuPd纳米复合材料(Au_0.3Pd_0.7/PEI-rGO)。Au_0.3Pd_0.7/PEI-rGO催化剂在催化FA制氢的反应中表现出极其优异的活性, 在无添加剂辅助下的转化频率(TOF)为2357.5 mol_H2∙ mol_catalyst ^-1∙h ^-1, 高于大多数相同反应条件下的异相催化剂。这归因于PEI-rGO衬底与AuPd纳米颗粒之间的强相互作用对金属活性组分的尺寸、分散度和电子结构的调控。此外, 循环测试结果表明该催化剂的稳定性良好。

关键词: 功能化石墨烯, 纳米金属催化剂, 甲酸, 制氢反应

Abstract:

Formic acid (FA) is considered as a new type of hydrogen storage material with great application prospect due to its high hydrogen content and easy recharging as a liquid. Seeking high efficiency catalysts to solve the problem of slow reaction kinetics of hydrogen evolution from FA is vital. In this work, polyethyleneimine modified graphene (PEI-rGO) was used as the catalyst substrate, and PEI-rGO supported AuPd nanocomposite material (Au_0.3Pd_0.7/PEI-rGO) was prepared by wet chemical method. The Au_0.3Pd_0.7/PEI-rGO catalyst exhibits remarkable activity for the hydrogen generation from FA, affording an unprecedented turnover frequency (TOF) of 2357.5 mol_H2∙ mol_catalyst ^-1∙h ^-1 without any additives, which is superior to most heterogeneous catalysts under similar reaction conditions. Its excellent catalytic performance is attributed to the strong interaction between PEI-rGO substrate and AuPd nanoparticles, which regulates the size, dispersion and electronic structure of metal active components. Furthermore, the recycle test result shows that the catalyst has good stability.

Key words: functionalized graphene, nano metal catalyst, formic acid, hydrogen generation reaction

中图分类号:

TQ174

王虹力, 王男, 王丽莹, 宋二红, 赵占奎. 功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应[J]. 无机材料学报, 2022, 37(5): 547-553.

WANG Hongli, WANG Nan, WANG Liying, SONG Erhong, ZHAO Zhankui. Hydrogen Generation from Formic Acid Boosted by Functionalized Graphene Supported AuPd Nanocatalysts[J]. Journal of Inorganic Materials, 2022, 37(5): 547-553.

图/表 5

图2 Au0.3Pd0.7/PEI-rGO的TEM照片、XRD及EDX图谱

Fig. 2 TEM images, XRD pattern and EDX spectrum of Au0.3Pd0.7/PEI-rGO (a-b) TEM images and (c)HRTEM image for Au0.3Pd0.7/PEI-rGO with inset in (b) showing corresponding histogram of particle size distribution, (d) XRD pattern and (e) EDX pattern for Au0.3Pd0.7/PEI-rGO

图3 Au0.3Pd0.7/PEI-rGO与Au0.3Pd0.7/rGO的XPS图谱

Fig. 3 XPS spectra of Au0.3Pd0.7/PEI-rGO and Au0.3Pd0.7/rGO (a) XPS total spectra for (1) Au0.3Pd0.7/rGO and (2) Au0.3Pd0.7/PEI-rGO; (b) High resolution XPS spectra of N1s for Au0.3Pd0.7/PEI-rGO; (c) Au4f, (d) Pd3d XPS spectra for (1) Au0.3Pd0.7/PEI-rGO and (2) Au0.3Pd0.7/rGO

图4 Au0.3Pd0.7/PEI-rGO、Au0.3Pd0.7/rGO与Au0.3Pd0.7催化剂在FA分解制氢反应中的催化性能对比

Fig. 4 Comparison of the catalytic performances for hydrogen evolution from FA dehydrogenation reaction of Au0.3Pd0.7/PEI-rGO, Au0.3Pd0.7/rGO and Au0.3Pd0.7 catalysts (a) Volume of gas versus time for the dehydrogenation of FA (1 mol/L, 5 mL) catalyzed by (1) Au0.3Pd0.7/PEI-rGO, (2) Au0.3Pd0.7/rGO and (3) Au0.3Pd0.7; (b) Corresponding TOF values

表1 不同FA脱氢催化剂的TOF

Table 1 TOF of different catalysts for FA dehydrogenation

Catalyst	Temperature/K	n_catalyst/n_FA	TOF/(mol_H2∙ mol_catalyst^-1∙h^-1)
Pd-NPs@TA-CoP^[22]	328	0.013	233.0^a
Pd@ED/Cr-MIL-101^[23]	328	0.003	583.0^b
Ni_0.4Pd_0.6/NH₂-N-rGO^[10]	298	0.020	954.3^a
Pd_0.7Ag_0.3/CeO_x-NPC^[24]	323	0.008	1101.9^a
Pd@TB-POP^[7]	323	0.100	1344.0^b
Pd/ImIP-2^[25]	323	0.008	1593.0^b
AuPd/n-CNS^[26]	333	0.020	1896.0^a
PdAg-CeO₂^[27]	303	0.033	2272.8^a
Au_0.3Pd_0.7/PEI-rGO	323	0.020	2357.5^a
Pd/MSC-30^[28]	323	0.013	2623.0^a
Pd-Co₂P/NPC^[13]	323	0.026	2980.0^b

图5 (a) Au0.3Pd0.7/PEI-rGO催化剂在不同温度下催化FA脱氢的气体体积与时间的关系曲线, (b) Au0.3Pd0.7/PEI-rGO催化剂的lnTOF与1/T的关系拟合直线, (c) 在323 K下,不同比例金属组分的AuxPd1-x/PEI-rGO(x=0, 0.1, 0.3, 0.7, 0.9, 1.0)催化FA脱氢的气体体积与时间的关系曲线, (d) Au0.3Pd0.7/PEI-rGO催化FA(1.0 mol/L, 5.0 mL)分解制氢的循环稳定性测试

Fig.5 (a) Volume of gas versus time for the dehydrogenation of FA at different temperatures over Au0.3Pd0.7/PEI-rGO catalyst; (b) Arrhenius plot (lnTOF versus 1/T) for Au0.3Pd0.7/PEI-rGO; (c) Volume of gas versus time for the dehydrogenation of FA at different ratios of AuxPd1-x/PEI-rGO (x=0, 0.1, 0.3, 0.7, 0.9, 1.0) at 323 K; (d) Durability tests of Au0.3Pd0.7/PEI-rGO towards the decomposition of FA (1.0 mol/L, 5.0 mL)

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功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应

Hydrogen Generation from Formic Acid Boosted by Functionalized Graphene Supported AuPd Nanocatalysts

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