C2N负载的过渡金属三聚体催化剂用于CO2电催化还原制CH4：第一性原理研究
Transition Metals Trimers on C2N as Electrochemical Catalysts for CO2 Reduction to CH4: A First-Principles Study
DOI: 10.12677/NAT.2022.124033, PDF,    国家自然科学基金支持
作者: 佟立凯, 张 钰, 张 博*：北京邮电大学集成电路学院，信息光子学与光通信国家重点实验室，北京
关键词: C2N；三原子催化剂；二氧化碳还原反应；CH4；第一性原理；C2N； Triple-Atom Catalyst； Carbon Dioxide Reduction； CH4； First-Principles
摘要: 三原子催化剂(TACs)在二氧化碳还原反应(CO2RR)中展现了巨大潜力，设计新型三原子催化剂具有重要意义。本工作利用第一性原理，建立了单层多孔氮化石墨烯(C2N)负载的过渡金属三聚体(3TM-C2N, TM = Mn, Mo, Ru, Ti)催化剂用于将二氧化碳(CO2)还原为甲烷(CH4)。计算结果表明，3TM-C2N催化剂结构稳定，不但能有效吸附和活化CO2，而且对析氢反应(HER)有良好的抑制性。吉布斯自由能分布图显示，CO2RR在3TM-C2N上会以不同的反应路径生成CH4。极限电势(UL)分析显示，3Mn-C2N表现出了最好的催化性能，对应的UL为−0.44 V。这些发现不仅为实验上调控C2N基催化剂提供了理论依据，还对开发其他高效的CO2RR电催化剂有一定的指导意义。
Abstract: Triple-Atom Catalysts (TACs) have shown great potential in carbon dioxide reduction reactions (CO2RR). It is of great significance to design new Triple-Atom Catalysts. In this work, a monolayer porous nitrogen-doped graphene (C2N) supported transition metal trimers (3TM-C2N, TM = Mn, Mo, Ru, Ti) catalyst models were established to catalyze the reduction of carbon dioxide (CO2) to me-thane (CH4) using first-principles. The results show that the structure of the 3TM-C2N catalyst is stable, not only can effectively adsorb and activate CO2, but also has good inhibition of Hydrogen Evolution Reaction (HER). The Gibbs free energy profiles show that the CO2RR produces CH4 products in different reaction paths on 3TM-C2N. The limiting potential (UL) analysis showed that 3Mn-C2N ex-hibited the best catalytic performance, UL of −0.44 V. These findings not only provide a theoretical basis for the experimental regulation of C2N-based catalysts, but also provide guidance for the development of other efficient CO2RR electrocatalysts.
文章引用：佟立凯, 张钰, 张博. C2N负载的过渡金属三聚体催化剂用于CO2电催化还原制CH4：第一性原理研究[J]. 纳米技术, 2022, 12(4): 330-339. https://doi.org/10.12677/NAT.2022.124033

参考文献

[1] Barnhart, C.J., Dale, M., Brandt, A.R. and Benson, S.M. (2013) The Energetic Implications of Curtailing versus Storing Solar- and Wind-Generated Electricity. Energy & Environmental Science, 6, 2804-2810. [Google Scholar] [CrossRef] 
[2] Mohd Adli, N., et al. (2021) Engineering Atomically Dispersed FeN4 Ac-tive Sites for CO2 Electroreduction. Angewandte Chemie International Edition, 60, 1022-1032. [Google Scholar] [CrossRef] [PubMed]
[3] Ananthaneni, S., Smith, Z. and Rankin, R.B. (2019) Graphene Sup-ported Tungsten Carbide as Catalyst for Electrochemical Reduction of CO2. Catalysts, 9, Article No. 604. [Google Scholar] [CrossRef] 
[4] Fernandes, D.M., Peixoto, A.F. and Freire, C. (2019) Nitrogen-Doped Metal-Free Carbon Catalysts for (Electro)Chemical CO2 Conversion and Valorisation. Dalton Transactions, 48, 13508-13528. [Google Scholar] [CrossRef] 
[5] Kortlever, R., Shen, J., Schouten, K.J.P., Calle-Vallejo, F. and Koper, M.T.M. (2015) Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide. The Journal of Physical Chemistry Letters, 6, 4073-4082. [Google Scholar] [CrossRef] [PubMed]
[6] Li, X., et al. (2020) Opportunity of Atomically Thin Two-Dimensional Catalysts for Promoting CO2 Electroreduction. Accounts of Chemical Research, 53, 2964-2974. [Google Scholar] [CrossRef] [PubMed]
[7] Chen, H., et al. (2019) Catalytic Effect on CO2 Electroreduction by Hydroxyl-Terminated Two-Dimensional Mxenes. ACS Applied Materials & Interfaces, 11, 36571-36579. [Google Scholar] [CrossRef] [PubMed]
[8] Li, T., Yang, C., Luo, J.-L. and Zheng, G. (2019) Electrolyte Driven Highly Selective CO2 Electroreduction at Low Overpotentials. ACS Catalysis, 9, 10440-10447. [Google Scholar] [CrossRef] 
[9] Sun, Y., Gao, S., Lei, F. and Xie, Y. (2015) Atomically-Thin Two-Dimensional Sheets for Understanding Active Sites in Catalysis. Chemical Society Reviews, 44, 623-636. [Google Scholar] [CrossRef] 
[10] Kibria, M.G., et al. (2019) Electrochemical CO2 Reduction into Chemi-cal Feedstocks: From Mechanistic Electrocatalysis Models to System Design. Advanced Materials, 31, e1807166. [Google Scholar] [CrossRef] [PubMed]
[11] Lu, B., Liu, Q. and Chen, S. (2020) Electrocatalysis of Single-Atom Sites: Impacts of Atomic Coordination. ACS Catalysis, 10, 7584-7618. [Google Scholar] [CrossRef] 
[12] Li, H., Zhao, Z., Cai, Q., Yin, L. and Zhao, J. (2020) Nitrogen Elec-troreduction Performance of Transition Metal Dimers Embedded into N-Doped Graphene: A Theoretical Prediction. Journal of Materials Chemistry A, 8, 4533-4543. [Google Scholar] [CrossRef] 
[13] Ouyang, Y., Shi, L., Bai, X., Li, Q. and Wang, J. (2020) Breaking Scaling Relations for Efficient CO2 Electrochemical Reduction through Dual-Atom Catalysts. Chemical Science, 11, 1807-1813. [Google Scholar] [CrossRef] 
[14] Cui, X., et al. (2018) C2N-Graphene Supported Sin-gle-Atom Catalysts for CO2 Electrochemical Reduction Reaction: Mechanistic Insight and Catalyst Screening. Nanoscale, 10, 15262-15272. [Google Scholar] [CrossRef] 
[15] Wang, X., et al. (2018) Regulation of Coordination Number over Single Co Sites: Triggering the Efficient Electroreduction of CO2. Angewandte Chemie International Edi-tion, 57, 1944-1948. [Google Scholar] [CrossRef] [PubMed]
[16] Jiang, K., et al. (2017) Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis. Chem, 3, 950-960. [Google Scholar] [CrossRef] 
[17] Yang, F., et al. (2018) Highly Efficient CO2 Electroreduction on ZnN4-Based Single-Atom Catalyst. Angewandte Chemie International Edition, 57, 12303-12307. [Google Scholar] [CrossRef] [PubMed]
[18] Zha, W., et al. (2021) Efficient Electrochemical CO2 Reduction on C2N Monolayer Supported Transition Metals Trimer Catalysts: A Daft Study. Applied Surface Science, 564, Article ID: 150331. [Google Scholar] [CrossRef] 
[19] Zhou, S., et al. (2021) Triple-Atom Catalysts 3TM-GYs (TM = Cu, Fe, and Co; Gy = Graphyne) for High-Performance CO2 Reduction Reaction to C1 Products. Applied Materials To-day, 25, Article ID: 101245. [Google Scholar] [CrossRef] 
[20] Chen, Z.W., Chen, L.X., Yang, C.C. and Jiang, Q. (2019) Atomic (Single, Double, and Triple Atoms) Catalysis: Frontiers, Opportunities, and Challenges. Journal of Materials Chemistry A, 7, 3492-3515. [Google Scholar] [CrossRef] 
[21] Siahrostami, S., et al. (2020) A Review on Challenges and Successes in Atomic-Scale Design of Catalysts for Electrochemical Synthesis of Hydrogen Peroxide. ACS Catalysis, 10, 7495-7511. [Google Scholar] [CrossRef] 
[22] Mahmood, J., et al. (2015) Nitrogenated Holey Two-Dimensional Structures. Nature Communications, 6, Article No. 6486. [Google Scholar] [CrossRef] [PubMed]
[23] Ma, D.W., et al. (2016) 3d Transition Metal Embedded C2N Monolayers as Promising Single-Atom Catalysts: A First-Principles Study. Carbon, 105, 463-473. [Google Scholar] [CrossRef] 
[24] Hafner, J. (2008) Ab-Initio Simu-lations of Materials Using Vasp: Density-Functional Theory and Beyond. Journal of Computational Chemistry, 29, 2044-2078. [Google Scholar] [CrossRef] [PubMed]
[25] Kresse, G.G. and Furthmüller, J.J. (1996) Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Physical Review B, Condensed Matter, 54, Article No. 11169. [Google Scholar] [CrossRef] 
[26] Marsman, M. and Kresse, G. (2006) Relaxed Core Projec-tor-Augmented-Wave Method. Journal of Chemical Physics, 125, Article No. 17953. [Google Scholar] [CrossRef] [PubMed]
[27] John, et al. (1996) Generalized Gradient Approximation Made Simple. Physical Review Letters, 77, 3865-3868. [Google Scholar] [CrossRef] 
[28] Gong, L., Chen, J.J. and Mu, Y. (2017) Catalytic CO2 Reduc-tion to Valuable Chemicals Using Nife-Based Nanoclusters: A First-Principles Theoretical Evaluation. Physical Chemis-try Chemical Physics, 19, 28344-28353. [Google Scholar] [CrossRef] 
[29] Zhang, B., Fu, X.L., Song, L. and Wu, X.J. (2020) Computational Screening toward Hydrogen Evolution Reaction by the Introduction of Point Defects at the Edges of Group IVA Mono-chalcogenides: A First-Principles Study. Journal of Physical Chemistry Letters, 11, 7664-7671. [Google Scholar] [CrossRef] [PubMed]
[30] Zhang, R., Li, B. and Yang, J. (2015) Effects of Stacking Order, Layer Number and External Electric Field on Electronic Structures of Few-Layer C2N-h2d. Nanoscale, 7, 14062-14070. [Google Scholar] [CrossRef] 
[31] Zhou, S., et al. (2020) Carbon Phosphides: Promising Electric Field Controllable Nanoporous Materials for CO2 Capture and Separation. Journal of Materials Chemistry A, 8, 9970-9980. [Google Scholar] [CrossRef] 
[32] Hu, W., Wu, X., Li, Z. and Yang, J. (2013) Porous Silicene as a Hy-drogen Purification Membrane. Physical Chemistry Chemical Physics, 15, 5753-5757. [Google Scholar] [CrossRef] [PubMed]
[33] Zhang, B., Fu, X., Song, L. and Wu, X. (2021) Improving Hydrogen Evolution Reaction Performance by Combining Ditungsten Carbide and Nitrogen-Doped Graphene: A First-Principles Study. Carbon, 172, 122-131. [Google Scholar] [CrossRef] 

为你推荐