V2CO2 MXene负载过渡金属单原子催化剂氧还原和氢氧化活性的DFT研究

doi:10.1016/S1872-2067(21)63823-8

催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1659-1666.DOI: 10.1016/S1872-2067(21)63823-8

V₂CO₂ MXene负载过渡金属单原子催化剂氧还原和氢氧化活性的DFT研究

邓忠晶, 郑星群, 邓明明, 李莉(), 李静, 魏子栋

重庆大学化学化工学院, 重庆市理论与计算化学重点实验室, 洁净能源与资源化工过程重庆市重点实验室, 输配电装备及系统安全与新技术国家重点实验室, 重庆400044

收稿日期:2021-01-29 接受日期:2021-03-26 出版日期:2021-10-18 发布日期:2021-06-20
通讯作者: 李莉
作者简介:*电话:(023)65678928; 电子信箱:liliracial@cqu.edu.cn
第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金重点项目(21822803);国家自然科学基金重点项目(91834301);国家自然科学基金重点项目(21576032)

Catalytic activity of V₂CO₂MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions: A density functional theory calculation study

Zhongjing Deng, Xingqun Zheng, Mingming Deng, Li Li(), Li Jing, Zidong Wei

The State Key Laboratory of Power Transmission Equipment & System Security and New Technology, Chongqing Key Laboratory of Chemical Process for Clean Energy and Resource Utilization, Chongqing Key Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China

Received:2021-01-29 Accepted:2021-03-26 Online:2021-10-18 Published:2021-06-20
Contact: Li Li
About author:Li obtained her MSc and PhD degree in 2004 and 2010 from Chongqing University. In 2010, she joined the faculty of College of Chemistry and Chemical Engineering, Chongqing University. Her main interests are in the fundamental studies of electrochemical and electrocatalytic processes through the theoretical investigations. Her research focuses on development novel electrocatalysts with high activity and stability, exploring the relationship between the catalytic activity and the electronic structure of the catalysts, and understanding the underlying mechanisms. She has coauthored about more than 100 peer-reviewed papers. Her main academic achievements include: 1. Proposing the “triple effect: charge, spin density and ligand effect” to explain the enhancement mechanism of doped graphene for ORR. 2. Exploring the theoretical foundation for tuning the catalytic activity and stability of carbon supported Pt-based catalysts. 3. Manifesting a general oxygen-vacancies based regulation mechanism for enhancing ORR activity of metal oxides. 4. Proposing a “chimney effect” for enhancing HER activity on the interface between the metal oxide/metal catalysts. She joined the editorial board of Chin. J. Catal. in 2020.First author contact:
^†Contributed to this work equally.
Supported by:
National Natural Science Foundation of China(21822803);National Natural Science Foundation of China(91834301);National Natural Science Foundation of China(21576032)

摘要/Abstract

摘要：

开发廉价且高性能的电催化剂对推动燃料电池的商业应用具有重要意义. 二维(2D) MXenes和单原子(SAs)催化剂是催化研究中的两个前沿领域. 2D MXenes材料具有独特的几何和电子结构, 能够有效调节负载SAs的催化性能. 而负载的SAs又会反过来影响2D MXenes材料的本征活性, 使2D MXenes形成更加丰富的活性位, 进而提升其催化性能.
为了拓展2D负载SAs催化剂在燃料电池中的应用, 本文采用密度泛函理论(DFT)计算, 系统地研究了V₂CO₂ MXenes负载过渡金属(TM, 包括一系列3d、部分4d和5d金属) SAs催化剂的稳定结构、电子结构及其催化氧还原(ORR)和氢氧化(HOR)的催化活性, 并筛选出潜在的可替代贵金属铂的ORR/HOR的双功能催化剂. 稳定结构计算结果表明, 3d TM SAs倾向于以锚定的形式负载于V₂CO₂表面与O原子作用, 而4d, 5d TM原子倾向于以掺杂的形式负载于含氧空穴的V₂CO₂表面与V原子作用; 同时, Sc, Ti, V, Rh, Pd, Pt, Ag和Au SAs在V₂CO₂表面因具有较高扩散能垒, 不易团聚, 具有较高的热力学稳定性. 电子结构计算结果表明, 锚定型的TM SAs与O形成共价键, 伴随发生明显的电荷转移, 带较多正电荷; 掺杂型的TM SAs与V形成金属键, 因TM-V和V-O键间电荷转移的协同影响, 导致TM SAs仅带有少量的电荷. TM-V₂CO₂电子结构与ORR/HOR中间物种的吸附关系为, TM位点为ORR中间物种(O, OH和OOH)的吸附位点, 且d电子数为1、5、10的TM比其他TM对ORR物种的吸附更弱; 而TM-V₂CO₂表面的O原子为HOR中间物种(H)的有效吸附位点, 且H的吸附强弱与O位点的电荷有关, 即O位点负电荷越多, 对H的吸附越弱. TM-V₂CO₂催化剂各活性位对ORR和HOR反应物种的选择性吸附结果表明, 催化剂有利于形成丰富多样的活性位, 并具备作为双功能催化剂的内在优势. TM-V₂CO₂催化剂ORR和HOR理论活性筛选发现: 与Pt(111)相比, Sc-、Mn-、Rh-和Pt-V₂CO₂具有较高的ORR活性, 而Sc-、Ti-、V-、Cr-和Mn-V₂CO₂表现出较高的HOR活性. 其中, Sc-V₂CO₂和Mn-V₂CO₂因同时具有较高的ORR和HOR活性和稳定性, 有望成为高效和低成本的燃料电池双功能催化剂. 本文从研究TM-V₂CO₂性质和活性出发, 深入研究了SAs与2D MXenes间相互作用及其对ORR与HOR催化活性的影响机制, 筛选出了高效、低成本的ORR/HOR双功能催化剂, 为合理设计燃料电池双功能催化剂提供了理论指导.

关键词: 单原子催化剂, MXenes材料, 氧还原, 氢氧化, 密度泛函理论, 燃料电池

Abstract:

Two-dimensional (2D) MXene and single-atom (SA) catalysts are two frontier research fields in catalysis. 2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs, which, in turn, affect the intrinsic activity of 2D materials. Density functional theory calculations were used to systematically explore the potential of O-terminated V₂C MXene (V₂CO₂)-supported transition metal (TM) SAs, including a series of 3d, 4d, and 5d metals, as oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) catalysts. The combination of TM SAs and V₂CO₂ changes their electronic structure and enriches the active sites, and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR. Among the investigated TM-V₂CO₂ models, Sc-, Mn-, Rh-, and Pt-V₂CO₂ showed high ORR activity, while Sc-, Ti-, V-, Cr-, and Mn-V₂CO₂ exhibited high HOR activity. Specifically, Mn- and Sc-V₂CO₂ are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability. This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.

Key words: Single atoms catalyst, MXenes, Oxygen reduction reaction, Hydrogen oxidation reaction, Density functional theory, Fuel cells

邓忠晶, 郑星群, 邓明明, 李莉, 李静, 魏子栋. V₂CO₂ MXene负载过渡金属单原子催化剂氧还原和氢氧化活性的DFT研究[J]. 催化学报, 2021, 42(10): 1659-1666.

Zhongjing Deng, Xingqun Zheng, Mingming Deng, Li Li, Li Jing, Zidong Wei. Catalytic activity of V₂CO₂MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions: A density functional theory calculation study[J]. Chinese Journal of Catalysis, 2021, 42(10): 1659-1666.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63823-8

https://www.cjcatal.com/CN/Y2021/V42/I10/1659

图/表 7

Fig. 1. Binding energy and optimized geometries of TM-V2CO2. (The red, light gray, blue, and dark blue colors represent O, C, V, and TM atoms respectively.)

Fig. 2. Migration energy barriers of TM SAs on V2CO2 MXenes. (a) The anchoring; (b) Doping type.

Fig. 3. Bader charge of TM SAs, O, and V near TM on TM-V2CO2 MXenes.

Fig. 4. (a) O, OH, and OOH adsorption energy (?Eads); (b,c) Free energy diagrams of ORR on TM-V2CO2.

Fig. 5. H adsorption energy (?EH*) on TM-V2CO2 and Bader charge of O atom in TM-V2CO2.

Fig. 6. HOR free energy diagrams on TM-V2CO2 at θH of 1/16 (a), 1/15 (b), 9/16 (c), and 8/15 (d).

Fig. 7. Summary of overpotentials for ORR and HOR (ηORR and ηHOR respectively) and TM migration Ebarriers on TM-V2CO2.

参考文献

[1]	M. K. Debe, Nature, 2012,486, 43-51.
[2]	S. Zhou, J. Qin, X. Zhao, J. Yang, Chin. J. Catal., 2021,42, 571-582.
[3]	X. Zheng, L. Li, M. Deng, J. Li, W. Ding, Y. Nie, Z. Wei, Catal. Sci. Technol., 2020,10, 4743-4751.
[4]	G. Gao, A. P. O’Mullane, A. Du, ACS Catal., 2017,7, 494-500.
[5]	T. Y. Ma, J. L. Cao, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed., 2016,55, 1138-1142.
[6]	X. Xie, S. Chen, W. Ding, Y. Nie, Z. Wei, Chem. Commun., 2013,49, 10112-10114.
[7]	N. Peng, D. Hu, J. Zeng, Y. Li, L. Liang, C. Chang, ACS Sustain. Chem. Eng., 2016,4, 7217-7224.
[8]	M. Naguib, J. Come, B. Dyatkin, V. Presser, P.-L. Taberna, P. Simon, M. W. Barsoum, Y. Gogotsi, Electrochem. Commun., 2012,16, 61-64.
[9]	X. Zhang, Y. Zhang, C. Cheng, Z. Yang, K. Hermansson, Nanoscale, 2020,12, 12497-12507.
[10]	J. Peng, X. Chen, W.-J. Ong, X. Zhao, N. Li, Chem, 2019,5, 18-50.
[11]	H. Lin, L. Chen, X. Lu, H. Yao, Y. Chen, J. Shi, Sci. China Mater., 2019,62, 662-670.
[12]	Y. Zhang, X. Zhang, C. Cheng, Z. Yang, Chin. Chem. Lett., 2020,31, 931-936.
[13]	Z. W. Seh, K. D. Fredrickson, B. Anasori, J. Kibsgaard, A. L. Strickler, M. R. Lukatskaya, Y. Gogotsi, T. F. Jaramillo, A. Vojvodic, ACS Energy Lett., 2016,1, 589-594.
[14]	H. Lin, L. Chen, X. Lu, H. Yao, Y. Chen, J. Shi, Sci. China Mater., 2019,62, 662-670.
[15]	G. Gao, A. P. O’Mullane, A. Du, ACS Catal., 2016,7, 494-500.
[16]	Y. Chen, S. Ji, C. Chen, Q. Peng, D. Wang, Y. Li, Joule, 2018,2, 1242-1264.
[17]	X. Zhang, J. Lei, D. Wu, X. Zhao, Y. Jing, Z. Zhou, J. Mater. Chem. A, 2016,4, 4871-4876.
[18]	P. Li, J. Zhu, A. D. Handoko, R. Zhang, H. Wang, D. Legut, X. Wen, Z. Fu, Z. W. Seh, Q. Zhang, J. Mater. Chem. A, 2018,6, 4271-4278.
[19]	J. Qu, J. Xiao, H. Chen, X. Liu, T. Wang, Q. Zhang, Chin. J. Catal., 2021,42, 288-296.
[20]	J. Zhou, G. Liu, Q. Jiang, W. Zhao, Z. Ao, T. An, Chin. J. Catal., 2020,41, 1633-1644.
[21]	Z. Zhang, H. Li, G. Zou, C. Fernandez, B. Liu, Q. Zhang, J. Hu, Q. Peng, ACS Sustain. Chem. Eng., 2016,4, 6763-6771.
[22]	N. Peng, D. Hu, J. Zeng, Y. Li, L. Liang, C. Chang, ACS Sustain. Chem. Eng., 2016,4, 7217-7224.
[23]	S.-L. Li, H. Yin, X. Kan, L.-Y. Gan, U. Schwingenschlögl, Y. Zhao, Phys. Chem. Chem. Phys., 2017,19, 30069-30077.
[24]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996,54, 11169-11186.
[25]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996,77, 3865-3868.
[26]	P. E. Blöchl, Phys. Rev. B, 1994,50, 17953-17979.
[27]	K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys., 2014,140, 084106.
[28]	G. Henkelman, H. Jonsson, J. Chem. Phys., 2000,113, 9978-9985.
[29]	J. Zheng, W. Sheng, Z. Zhuang, B. Xu, Y. Yan, Sci. Adv., 2016,2, e1501602.
[30]	P. J. Rheinländer, J. Herranz, J. Durst, H. A. Gasteiger, J. Electrochemi. Soc., 2014,161, F1448-F1457.
[31]	K. J. P. Schouten, M. Van Der Niet, M. T. M. Koper, Phys. Chem. Chem. Phys., 2010,12, 15217-15224.
[32]	Y. Cong, B. Yi, Y. Song, Nano Energy, 2018,44, 288-303.
[33]	H.-F. Wang, Z.-P. Liu, J. Am. Chem. Soc., 2008,130, 10996-11004.
[34]	M. Li, L. Zhang, Q. Xu, J. Niu, Z. Xia, J. Catal., 2014,314, 66-72.
[35]	N. Yang, L. Li, J. Li, W. Ding, Z. Wei, Chem. Sci., 2018,9, 5795-5804.
[36]	J. Zhang, Z. Zhao, Z. Xia, L. Dai, Nat. Nanotech., 2015,10, 444-452.
[37]	H. Hajiyani, R. Pentcheva, ACS Catal., 2018,8, 11773-11782.
[38]	C. Ling, L. Shi, Y. Ouyang, Q. Chen, J. Wang, Adv. Sci., 2016,3, 1600180.
[39]	C. P. Huang, M. C. Tsai, X. M. Wang, H. S. Cheng, Y. H. Mao, C. J. Pan, J. N. Lin, L. D. Tsai, T. S. Chan, W. N. Su, B. J. Hwang, Catal. Sci. Technol., 2020,10, 893-903.
[40]	S. Lu, Z. Zhuang, Sci. China Mater., 2016,59, 217-238.

V₂CO₂ MXene负载过渡金属单原子催化剂氧还原和氢氧化活性的DFT研究

Catalytic activity of V₂CO₂MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions: A density functional theory calculation study

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 7

参考文献

相关文章 15

编辑推荐

Metrics

[1]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[2]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[3]	卢明佳, 梁乐程, 冯彬彬, 常译文, 黄志宏, 宋慧宇, 杜丽, 廖世军, 崔志明. 燃料电池多孔碳载体高石墨化的超快速碳热冲击策略[J]. 催化学报, 2023, 52(9): 228-238.
[4]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[5]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[6]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[7]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[8]	程璐, 陈许宁, 胡培君, 曹宵鸣. 双氧水对于单核铜分子筛催化甲烷直接氧化制甲醇反应性能的利弊[J]. 催化学报, 2023, 51(8): 135-144.
[9]	刘赵春, 宗雪, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. 金属掺杂SnO₂电化学还原CO₂制甲酸的计算研究[J]. 催化学报, 2023, 50(7): 249-259.
[10]	贡立圆, 王颖, 刘杰, 王显, 李阳, 侯帅, 武志坚, 金钊, 刘长鹏, 邢巍, 葛君杰. 重塑位于火山曲线右支的弱吸附金属单原子位点的配位环境及电子结构[J]. 催化学报, 2023, 50(7): 352-360.
[11]	耿仕鹏, 陈利明, 陈海鑫, 王毅, 丁朝斌, 蔡丹丹, 宋树芹. 揭示层状晶态CoMoO₄的水裂解电催化机制: 从晶面选择到活性位点设计的理论研究[J]. 催化学报, 2023, 50(7): 334-342.
[12]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. 用于电化学能量转换反应的非贵金属单原子催化剂[J]. 催化学报, 2023, 50(7): 195-214.
[13]	张光颖, 刘旭, 张欣欣, 梁志坚, 邢耕宇, 蔡斌, 沈迪, 王蕾, 付宏刚. P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池[J]. 催化学报, 2023, 49(6): 141-151.
[14]	姜润, 乔泽龙, 许昊翔, 曹达鹏. 用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程[J]. 催化学报, 2023, 48(5): 224-234.
[15]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.