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

doi:10.1016/S1872-2067(23)64458-4

催化学报 ›› 2023, Vol. 50: 334-342.DOI: 10.1016/S1872-2067(23)64458-4

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

耿仕鹏, 陈利明, 陈海鑫, 王毅, 丁朝斌^*(), 蔡丹丹^*(), 宋树芹^*()

中山大学材料科学与工程学院, 化学工程与技术学院, 广东省低碳化学与过程节能重点实验室, 聚合物复合材料及功能材料教育部重点实验室, 广东广州 510275

收稿日期:2023-03-09 接受日期:2023-05-17 出版日期:2023-07-18 发布日期:2023-07-25
通讯作者: *电子信箱: stsssq@mail.sysu.edu.cn (宋树芹), caidandan86@163.com (蔡丹丹), dingzhb@mail.sysu.edu.cn (丁朝斌).
基金资助:
国家自然科学基金重大研究计划培养项目(90261124);国家自然科学基金项目(21975292);国家自然科学基金项目(21978331);国家自然科学基金项目(22068008);国家自然科学基金项目(52101186);广东省基础与应用基础研究基金项目(2021A1515010167);广东省基础与应用基础研究基金项目(2022A1515011196);广州市基础与应用基础研究计划项目(202201011449);广东省燃料电池技术重点实验室研究基金项目(FC202220);广东省燃料电池技术重点实验室研究基金项目(FC202216)

Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering

Shipeng Geng, Liming Chen, Haixin Chen, Yi Wang, Zhao-Bin Ding^*(), Dandan Cai^*(), Shuqin Song^*()

The Key Lab of Low-carbon Chemistry & Energy Conservation of Guangdong Province, PCFM Laboratory, School of Materials Science and Engineering, School of Chemical Engineering and Technology, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2023-03-09 Accepted:2023-05-17 Online:2023-07-18 Published:2023-07-25
Contact: *E-mail: stsssq@mail.sysu.edu.cn (S. Song), caidandan86@163.com (D. Cai), dingzhb@mail.sysu.edu.cn (Z. Ding).
Supported by:
Training Program of the Major Research Plan of the National Natural Science Foundation of China(90261124);National Natural Science Foundation of China(21975292);National Natural Science Foundation of China(21978331);National Natural Science Foundation of China(22068008);National Natural Science Foundation of China(52101186);Guangdong Basic and Applied Basic Research Foundation(2021A1515010167);Guangdong Basic and Applied Basic Research Foundation(2022A1515011196);Guangzhou Basic and Applied Basic Research Project(202201011449);Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202220);Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202216)

摘要/Abstract

摘要：

电解水制氢具有效率高、操作简单、易于耦合可再生能源等优点, 被认为是大规模产氢最有希望的技术之一. 通常贵金属基材料Pt和Ir(Ru)O₂分别用作阴极析氢反应(HER)和阳极析氧反应(OER)催化剂, 进而提高水裂解效率. 然而, 它们的稀缺性、成本高和稳定性差等缺点严重限制了在电解水中的大规模应用. 因此, 急需开发廉价且高效的水裂解电催化剂. 钼酸钴(CoMoO₄)由于成本低、储量丰富、氧化还原活性位点多和稳定性高等优点, 被认为是替代贵金属基催化剂的理想候选者. 但由于CoMoO₄复杂的单斜晶体结构, 从原子层面揭示其HER和OER电催化机理仍然是一个极大挑战, 而在原子水平探索电催化剂不同晶面的催化活性对理解电催化机制和识别活性位点起着推动作用.

本文采用密度泛函理论(DFT)从层状晶态CoMoO₄的晶面选择到活性位点设计系统研究了其水裂解电催化机制. CoMoO₄沿[110]晶格方向呈现层状排列晶体特征, 通过表面能计算并基于Wulff原则构造了CoMoO₄的热力学稳定晶体结构, 结果表明, 具有较低表面能的(110)A(62 mJ m^‒2)和(001)A(179 mJ m^‒2)面均为理论热力学稳定晶体结构的主导晶面, 分别占据了64.25%和23.53%. 因此以(110)A和(001)A晶面为研究对象, 重点研究了其碱性水裂解的电催化活性及其深入的催化机制. 结果发现, 在CoMoO₄的(110)A面上的O3位点吸附的H可以与两个氧原子(O3和O_adj)相互作用, 理论计算得到的氢吸附吉布斯自由能(ΔG_H*)仅为0.22 eV, 对应了最高的类似Pt的交换电流密度i₀, 所以其表现出最优异的HER活性; 另外, (110)A面水解离(Volmer反应)能垒约为1.6 eV, 远低于(001)A的4.6 eV, 说明(110)A面拥有比(001)A面更好的H₂O解离能力, 更有利于碱性溶液中的HER. 过渡态计算结果表明, (110)A上的H*更倾向于与另一个来自吸附水的H结合, Heyrovsky步骤的能垒为1.63 eV, 低于两个H*结合形成H₂的Tafel步骤能垒(2.04 eV). 因此, CoMoO₄催化剂上的HER是沿着Volmer-Heyrovsky步骤进行的. 此外, 根据吉布斯自由能计算, (110)A面上OER过电位仅为0.74 V, 优于(001)A面(0.84 V), 这是因为(110)A面的Co和O间的结合力更强, 中间体*O的吸附状态更稳定, 使得决速步(*OH → *O)能垒降低. 综上, 本文对CoMoO₄及其同构物质如Mn(Ni, Fe)MoO₄纳米催化剂的选择性合成和电催化机理研究具有借鉴意义.

关键词: 密度泛函理论, 水裂解, 层状晶体CoMoO₄, 晶面选择, 活性位点设计

Abstract:

Deciphering the atomic-level properties and mechanism of electrocatalysts for water splitting is vital for the development of highly active non-noble-metal catalysts. Herein, we conduct a detailed study of layered crystalline CoMoO₄ using density functional theory (DFT) calculations. The layered arrangement of CoMoO₄ along the [110] lattice direction is observed, and the two thermodynamically stable and most exposed (110)A and (001)A crystal facets are selected among all low-index facets by surface energy calculations and Wulff construction to study the electrocatalytic activity for alkaline water splitting and corresponding mechanism. CoMoO₄ with an exposed (110)A facet (i.e., CMO (110)A) exhibited a high hydrogen evolution reaction (HER) activity, with a ΔG_H* of 0.22 eV, which is similar to that of Pt because the adsorbed H is allowed to interact with two oxygen atoms (O3 and O_adj). The (110)A facet also possesses better H₂O adsorption and dissociation abilities than the (001)A facet, benefiting the HER performance in alkaline solutions. Moreover, the overpotential of the (110)A facet for the electrocatalytic oxygen evolution reaction (OER) is only 0.74 V according to the Gibbs free-energy calculation, this overpotential is lower than that of the (001)A facet (0.84 V) owing to the stronger binding and more stable adsorption states between Co and O for the intermediate *O. By allowing us to identify highly active facets and sites, this approach guided the selective synthesis of CoMoO₄ and its isostructural substances, such as Mn(Ni, Fe)MoO₄ nanocatalysts, for alkaline water splitting.

Key words: Density functional theory, Water splitting, Layered crystalline CoMoO₄, Facet selecting, Active-site engineering

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: 334-342.

Shipeng Geng, Liming Chen, Haixin Chen, Yi Wang, Zhao-Bin Ding, Dandan Cai, Shuqin Song. Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering[J]. Chinese Journal of Catalysis, 2023, 50: 334-342.

×
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(23)64458-4

https://www.cjcatal.com/CN/Y2023/V50/I7/334

图/表 6

Fig. 1. (a) Optimized unit cell of bulk monoclinic CoMoO4 (CMO) and top view along the C axis. Surface energies (b) and corresponding surface models (c) for different low-index facets of CMO. (d) Thermodynamic equilibrium shape of CMO obtained by the Wulff construction and area percentage of the different facets.

Fig. 2. Different H adsorption sites and corresponding ΔGH* for (110)A facet (a) and (001)A facet (b). (c) Volcano plot of exchange current as a function of ΔGH* for (110)A and (001)A facets of CMO. (d) Optimized structure having the best ΔGH* in the (110)A facet.

Fig. 3. Partial DOS of different O sites in the (110)A (a) and (001)A (b) facets. The Bader charge analysis and the charge-density difference of the top layer for the H adsorption structure possesses the optimal ΔGH* for the (110)A (c) and (001)A (d) facets. The colors cyan and yellow are associated with the depletion and accumulation of the total valence electrons, respectively. The isosurface value is 0.005 e bohr?3.

Fig. 4. H2O adsorption energies and corresponding charge-density differences for (110)A (a) and (001)A (b) facets. The colors yellow and cyan correspond to the accumulation and depletion of total valence electrons, respectively. The isosurface value is 0.01 e bohr?3. (c) H2O dissociation barrier for the reaction pathway of the (110)A facet. The insets show the structure of the corresponding initial state (IS), transition state (TS), and final state (FS). (d) Calculated free-energy diagrams of HER pathways for (110)A and (001)A facets.

Fig. 5. OER free-energy diagrams for the (110)A (a) and (001)A (b) facets, and structural diagrams of the optimized intermediates *, *OH, *O, and *OOH for the (110)A (c) and (001)A (d) facets.

Fig. 6. Bader charge analysis of Co for the slab model *; optimized local structures of *OH, *O, and *OOH; and corresponding bond lengths in the (110)A facet (a) and (001)A facet (b).

参考文献

[1]	Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Chem. Soc. Rev., 2015, 44, 2060-2086.
[2]	V. R. Stamenkovic, D. Strmcnik, P. P. Lopes, N. M. Markovic, Nat. Mater. 2017, 16, 57-69.
[3]	D. Voiry, H. S. Shin, K. P. Loh, M. Chhowalla, Nat. Rev. Chem. 2018, 2, 0105.
[4]	P. Wang, Z. Pu, W. Li, J. Zhu, C. Zhang, Y. Zhao, S. Mu, J. Catal. 2019, 377, 600-608.
[5]	M. A. Abbas, J. H. Bang, Chem. Mater. 2015, 27, 7218-7235.
[6]	Y. Lee, J. Suntivich, K. J. May, E.E. Perry, Y. Shao-Horn, J. Phys. Chem. Lett. 2012, 3, 399-404.
[7]	X. Yan, L. Tian, K. Li, S. Atkins, H. Zhao, J. Murowchick, L. Liu, X. Chen, Adv. Mater. Interfaces, 2016, 3, 1600368.
[8]	H. Xu, R. Q. Zhang, A. M. C. Ng, A. B. Djurisic, H. T. Chan, W. K. Chan, S. Y. Tong, J. Phys. Chem. C, 2011, 115, 19710-19715.
[9]	Y. Zhao, C. Chang, F. Teng, Y. Zhao, G. Chen, R. Shi, G. I. N. Waterhouse, W. Huang, T. Zhang, Adv. Energy Mater. 2017, 7, 1700005.
[10]	J. Zhang, S. Geng, R. Li, X. Zhang, Y. Zhou, T. Yu, Y. Wang, S. Song, Z. Shao, Chem. Eng. J. 2021, 420, 130492.
[11]	Z. Liu, C. Yuan, F. Teng, J. Alloys Compd. 2019, 781, 460-466.
[12]	K. Chi, X. Tian, Q. Wang, Z. Zhang, X. Zhang, Y. Zhang, F. Jing, Q. Lv, W. Yao, F. Xiao, S. Wang, J. Catal. 2020, 381, 44-52.
[13]	Z. Wang, J. Chen, E. Song, N. Wang, J. Dong, X. Zhang, P. M. Ajayan, W. Yao, C. Wang, J. Liu, J. Shen, M. Ye, Nat. Commun. 2021, 12, 5960.
[14]	W. Xie, J. Huang, L. Huang, S. Geng, S. Song, P. Tsiakaras, Y. Wang, Appl. Catal. B, 2022, 303, 120871.
[15]	C. Xiao, B.-A. Lu, P. Xue, N. Tian, Z.-Y. Zhou, X. Lin, W.-F. Lin, S.-G. Sun, Joule, 2020, 4, 2562-2598.
[16]	C. L. Bentley, M. Kang, P. R. Unwin, J. Am. Chem. Soc. 2019, 141, 2179-2193.
[17]	Z. Liu, H. M. A. Amin, Y. Peng, M. Corva, R. Pentcheva, K. Tschulik, Adv. Funct. Mater. 2023, 33, 2210945.
[18]	S. Yang, X. Yang, Q. Wang, X. Cui, H. Zou, X. Tong, N. Yang, Chem. Eng. J. 2022, 449, 137790.
[19]	T. Jiang, W. Xie, S. Geng, R. Li, S. Song, Y. Wang, Chin. J. Catal. 2022, 43, 2434-2442.
[20]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[21]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[22]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865-3868.
[23]	G. Hautier, S. P. Ong, A. Jain, C. J. Moore, G. Ceder, Phys. Rev. B, 2012, 85, 155208.
[24]	J. K. Nørskov, T. Bligaard, A. Logadottir, J. R. Kitchin, J. G. Chen, S. Pandelov, U. Stimming, J. Electrochem. Soc. 2005, 152, J23.
[25]	G. Henkelman, B. P. Uberuaga, H. Jonsson, J. Chem. Phys. 2000, 113, 9901-9904.
[26]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jonsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[27]	S. Liu, Y. Yin, D. Ni, K. S. Hui, K. N. Hui, S. Lee, C.-Y. Ouyang, S. C. Jun, Energy Storage Mater. 2019, 19, 186-196.
[28]	H. Chen, X. Ai, W. Liu, Z. Xie, W. Feng, W. Chen, X. Zou, Angew. Chem. Int. Ed. 2019, 58, 11409-11413.
[29]	G. Wulff, Z. Kristallogr.-Cryst. Mater. 1901, 34, 449-530.
[30]	Z. Zeng, X. Chen, K. Weng, Y. Wu, P. Zhang, J. Jiang, N. Li, Npj Comput. Mater. 2021, 7, 80.
[31]	X. Mao, L. Wang, Y. Xu, P. Wang, Y. Li, J. Zhao, Npj Comput. Mater. 2021, 7, 46.
[32]	J. K. Norskov, T. Bligaard, J. Rossmeisl, C. H. Christensen, Nat. Chem. 2009, 1, 37-46.
[33]	S. Xu, Y. Wang, Y. Li, Phys. Chem. Chem. Phys. 2022, 24, 9930-9935.
[34]	C. Yang, W. Zhong, K. Shen, Q. Zhang, R. Zhao, H. Xiang, J. Wu, X. Li, N. Yang, Adv. Energy Matter. 2022, 12, 2200077.
[35]	A. Zagalskaya, V. Alexandrov, ACS Catal. 2020, 10, 3650-3657.
[36]	X. Cao, Y. Tan, H. Zheng, J. Hu, X. Chen, Z. Chen, Phys. Chem. Chem. Phys. 2022, 24, 4644-4652.

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

Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	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.
[2]	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.
[3]	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.
[4]	王元男, 王立娜, 张可新, 徐靖尧, 武倩楠, 谢周兵, 安伟, 梁宵, 邹晓新. 钙钛矿氧化物在水裂解反应中的电催化研究[J]. 催化学报, 2023, 50(7): 109-125.
[5]	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.
[6]	黄正清, 贺姝玥, 班涛, 高新, 许云华, 常春然. Pt-Cu合金催化剂上甲烷无氧偶联的机理与微观动力学研究: 从单原子位点到单团簇位点[J]. 催化学报, 2023, 48(5): 90-100.
[7]	井会娟, 龙军, 李欢, 傅笑言, 肖建平. 电催化硝酸盐还原合成氨电势相关性的计算见解[J]. 催化学报, 2023, 48(5): 205-213.
[8]	赵志月, 蒋志伟, 黄一哲, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, 罗惠霞, 严凯. 富空穴CoSi合金无溶剂无碱醇氧化[J]. 催化学报, 2023, 48(5): 175-184.
[9]	Sue-Faye Ng, 陈星竹, Joel Jie Foo, 熊墨, Wee-Jun Ong. 2D氮化碳: 通过调节非金属硼掺杂C₃N₅阐明宽酸性及碱性pH范围的光催化析氢的反应机理[J]. 催化学报, 2023, 47(4): 150-160.
[10]	陈成成, 刘芳庭, 张巧钰, 张正国, 刘琼, 方晓明. 理论设计和实验研究吡啶掺杂聚合氮化碳提升光催化CO₂还原性能[J]. 催化学报, 2023, 46(3): 91-102.
[11]	蒋婷婷, 谢伟伟, 耿仕鹏, 李如春, 宋树芹, 王毅. 构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应[J]. 催化学报, 2022, 43(9): 2434-2442.
[12]	孟翔宇, 李睿, 杨峻懿, 许世明, 张辰晨, 尤可嘉, 马宝春, 管红霞, 丁勇. 六核环状钴配合物用于光催化CO₂到CO转化[J]. 催化学报, 2022, 43(9): 2414-2424.
[13]	李楠, 王传义, 章柯, 吕海钦, 苑明哲, Detlef W. Bahnemann. 光催化转化低浓度NO的进展与展望[J]. 催化学报, 2022, 43(9): 2363-2387.
[14]	崔彤, 翟雪君, 郭莉莉, 迟京起, 张昱, 朱家伟, 孙雪梅, 王磊. 自组装百合花状超低Ru, Ni掺杂的Fe₂O₃用于大电流碱性海水电解双功能电催化[J]. 催化学报, 2022, 43(8): 2202-2211.
[15]	高怡静, 张世杰, 孙翔, 赵伟, 卓涵, 庄桂林, 王式彬, 姚子豪, 邓声威, 钟兴, 魏中哲, 王建国. 氧官能团MXenes用于电催化合成氨的理论筛选[J]. 催化学报, 2022, 43(7): 1860-1869.