电催化甲烷转化为增值化学品研究进展
Research Progress in Electrocatalytic Oxidation of Methane into Value-Added Chemicals
DOI: 10.12677/MS.2023.134033, PDF,    国家自然科学基金支持
作者: 王 瑞, 郑露莹, 江佳怡, 于小晴, 张 航*：沈阳师范大学化学化工学院，辽宁 沈阳
关键词: 甲烷；电催化；含氧化合物； Methane； Electrocatalytic； Oxygenated Compounds
摘要: 甲烷(CH4)是天然气的主要成分，已被用作燃料和储氢器。CH4的部分氧化生成液体燃料方向是一个巨大的挑战，因为含氧产物比CH4更容易氧化。因此，对载流子和自由基的控制是阻止过度反应的关键。电催化是清洁、可持续的CH4转化技术，本文主要讨论了如何设计催化剂来克服CH4电催化部分氧化过程中的瓶颈，重点讨论了界面电荷转移过程、催化剂表面工程策略、影响反应机理和速率决定步骤的关键因素以及提高催化性能的反应条件。最后，本文总结了催化剂的制备，有效地产生电荷载体和中间体与温和的氧化行为，以防止不必要的反应路径。
Abstract: Methane (CH4) is considered as the main component of natural gas and has been used as fuel and hydrogen storage tank. Partial oxidation of CH4 in the direction of liquid fuel generation is a huge challenge, because oxy-gen-containing products are more easily oxidized than CH4. Therefore, the control of carriers and free radicals is the key to prevent harmful reactions. This paper mainly discusses how to design catalysts to overcome the bottleneck in the process of partial oxidation of CH4 electrocatalysis, fo-cusing on the interface charge transfer process, the catalyst surface engineering strategy, the key factors affecting the reaction mechanism and rate-determining steps, and the reaction conditions to improve the catalytic performance. Finally, this paper can guide the preparation of catalysts, effec-tively generate charge carriers and intermediates and mild oxidation behavior to prevent unnec-essary reaction paths.
文章引用：王瑞, 郑露莹, 江佳怡, 于小晴, 张航. 电催化甲烷转化为增值化学品研究进展[J]. 材料科学, 2023, 13(4): 282-296. https://doi.org/10.12677/MS.2023.134033

参考文献

[1] Liu, C.-J., Xue, B., Eliasson, B., et al. (2001) Methane Conversion to Higher Hydrocarbons in the Presence of Carbon Dioxide Using Dielectric-Barrier Discharge Plasmas. Plasma Chemistry and Plasma Processing, 21, 301-310. [Google Scholar] [CrossRef] 
[2] Zhang, Y.-P., Li, Y., Wang, Y., Liu, C.-J. and Eliasson, B. (2003) Plasma Methane Conversion in the Presence of Carbon Dioxide Using Dielectric-Barrier Discharges. Fuel Processing Technology, 83, 101-109. [Google Scholar] [CrossRef] 
[3] Dissanayake, D., Rosynek, M.P., Kharas, K.C.C. and Luns-ford, J.H. (1991) Partial Oxidation of Methane to Carbon Monoxide and Hydrogen over a Ni/Al2O3 Catalyst. Journal of Catalysis, 132, 117-127. [Google Scholar] [CrossRef] 
[4] Horn, R. and Schlögl, R. (2015) Methane Activation by Het-erogeneous Catalysis. Catalysis Letters, 145, 23-39. [Google Scholar] [CrossRef] 
[5] Voge, H.H. (1936) Relation of the States of the Carbon Atom to Its Valence in Methane. The Journal of Chemical Physics, 4, 581-591. [Google Scholar] [CrossRef] 
[6] Wang, M., Tan, X., Motuzas, J., Li, J. and Liu, S. (2021) Hydrogen Pro-duction by Methane Steam Reforming Using Metallic Nickel Hollow Fiber Membranes. Journal of Membrane Science, 620, Article ID: 118909. [Google Scholar] [CrossRef] 
[7] Angeli, S.D., Monteleone, G., Giaconia, A. and Lemonidou, A.A. (2014) State-of-the-Art Catalysts for CH4 Steam Reforming at Low Temperature. International Journal of Hydro-gen Energy, 39, 1979-1997. [Google Scholar] [CrossRef] 
[8] Brown, M.J. and Parkyns, N.D. (1991) Progress in the Partial Oxidation of Methane to Methanol and Formaldehyde. Catalysis Today, 8, 305-335. [Google Scholar] [CrossRef] 
[9] O’Reilly, M.E., Kim, R.S., Oh, S., et al. (2017) Electrochemi-cal Reoxidation Enables Continuous Methane-to-Methanol Catalysis with Aqueous Pt Salts. ACS Central Science, 3, 1174-1179.
[10] Gunsalus, N.J., Koppaka, A., Park, S.H., et al. (2017) Homogeneous Functionalization of Methane. Chemical Reviews, 117, 8521-8573. [Google Scholar] [CrossRef] [PubMed]
[11] Cavaliere, V.N. and Mindi-ola, D.J. (2012) Methane: A New Frontier in Organometallic Chemistry. Chemical Science, 3, 3356-3365. [Google Scholar] [CrossRef] 
[12] Duan, Z. and Mao, S. (2006) A Thermodynamic Model for Calculating Methane Solubility, Density and Gas Phase Composition of Methane-Bearing Aqueous Fluids from 273 to 523 K and from 1 to 2000 Bar. Geochimica et Cosmochimica Acta, 70, 3369-3386. [Google Scholar] [CrossRef] 
[13] Liang, Z., Li, T., Kim, M., Asthagiri, A. and Weaver, J.F. (2017) Low-Temperature Activation of Methane on the IrO2 (110) Surface. Science, 356, 299-303. [Google Scholar] [CrossRef] [PubMed]
[14] Moon, G.-H., Kim, S., Cho, Y.-J., et al. (2017) Synergistic Combi-nation of Bandgap-Modified Carbon Nitride and WO3 for Visible Light-Induced Oxidation of Arsenite Accelerated by In-Situ Fenton Reaction. Applied Catalysis B: Environmental, 218, 819-824. [Google Scholar] [CrossRef] 
[15] Hou, Y., Wang, F., Qin, C., et al. (2022) A Self-Healing Elec-trocatalytic System via Electrohydrodynamics Induced Evolution in Liquid Metal. Nature Communications, 13, Article No. 7625. [Google Scholar] [CrossRef] [PubMed]
[16] Liu, L.-Y., Xie, G.-J., Xing, D.-F., et al. (2020) Biological Conversion of Methane to Polyhydroxyalkanoates: Current Advances, Challenges, and Perspectives. Environmental Sci-ence and Ecotechnology, 2, Article ID: 100029. [Google Scholar] [CrossRef] [PubMed]
[17] Henares, M., Ferrero, P., San-Valero, P., Martínez-Soria, V. and Izquierdo, M. (2018) Performance of a Polypropylene Membrane Contactor for the Recovery of Dissolved Methane from Anaerobic Effluents: Mass Transfer Evaluation, Long-Term Operation and Cleaning Strategies. Journal of Membrane Science, 563, 926-937. [Google Scholar] [CrossRef] 
[18] Fornaciari, J.C., Primc, D., Kawashima, K., et al. (2020) A Perspective on the Electrochemical Oxidation of Methane to Methanol in Membrane Electrode Assemblies. ACS Energy Letters, 5, 2954-2963. [Google Scholar] [CrossRef] 
[19] Liu, K., Smith, W.A. and Burdyny, T. (2019) Introductory Guide to Assembling and Operating Gas Diffusion Electrodes for Electrochemical CO2 Reduction. ACS Energy Letters, 4, 639-643. [Google Scholar] [CrossRef] [PubMed]
[20] Yuan, S., Li, Y., Peng, J., et al. (2020) Conversion of Methane into Liquid Fuels—Bridging Thermal Catalysis with Electrocatalysis. Advanced Energy Materials, 10, Article ID: 2002154. [Google Scholar] [CrossRef] 
[21] Promoppatum, P. and Viswanathan, V. (2016) Identifying Material and Device Targets for a Flare Gas Recovery System Utilizing Electrochemical Conversion of Methane to Methanol. ACS Sustainable Chemistry & Engineering, 4, 1736-1745. [Google Scholar] [CrossRef] 
[22] Petrik, N.G. and Kimmel, G.A. (2011) Electron- and Hole-Mediated Reactions in UV-Irradiated O2 Adsorbed on Reduced Rutile TiO2 (110). The Journal of Physical Chem-istry C, 115, 152-164. [Google Scholar] [CrossRef] 
[23] Wu, S., Žurauskas, J., Domański, M., et al. (2021) Hole-Mediated Photoredox Catalysis: Tris(p-Substituted) Biarylaminium Radical Cations as Tunable, Precomplexing and Potent Photooxidants. Organic Chemistry Frontiers, 8, 1132-1142. [Google Scholar] [CrossRef] 
[24] Di Valentin, C. (2016) A Mechanism for the Hole-Mediated Water Photooxidation on TiO2 (101) Surfaces. Journal of Physics: Condensed Matter, 28, Article ID: 074002. [Google Scholar] [CrossRef] [PubMed]
[25] Qiao, M. and Titirici, M.M. (2018) Engineering the Interface of Carbon Electrocatalysts at the Triple Point for Enhanced Oxygen Reduction Reaction. Chemistry—A European Journal, 24, 18374-18384. [Google Scholar] [CrossRef] [PubMed]
[26] Wagner, A., Sahm, C.D. and Reisner, E. (2020) Towards Molecular Understanding of Local Chemical Environment Effects in Electro- and Photocatalytic CO2 Reduction. Nature Catalysis, 3, 775-786. [Google Scholar] [CrossRef] 
[27] Moon, G.-H., Yu, M., Chan, C.K. and Tüysüz, H. (2019) High-ly Active Cobalt-Based Electrocatalysts with Facile Incorporation of Dopants for the Oxygen Evolution Reaction. An-gewandte Chemie, 131, 3529-3533. [Google Scholar] [CrossRef] 
[28] Yu, M., Moon, G., Bill, E. and Tüysüz, H. (2019) Optimizing Ni-Fe Electrocatalysts for Oxygen Evolution Reaction by Using Hard Templating as a Toolbox. ACS Applied Energy Materials, 2, 1199-1209. [Google Scholar] [CrossRef] 
[29] Moon, G.-H., Wang, Y., Kim, S., Budiyanto, E. and Tüysüz, H. (2022) Preparation of Practical High-Performance Electrodes for Acidic and Alkaline Media Water Electrolysis. ChemSusChem, 15, e202102114. [Google Scholar] [CrossRef] [PubMed]
[30] Rocha, R.S., Reis, R.M., Lanza, M.R.V. and Bertazzoli, R. (2013) Electrosynthesis of Methanol from Methane: The Role of V2O5 in the Reaction Selectivity for Methanol of a TiO2/RuO2/V2O5 Gas Diffusion Electrode. Electrochimica Acta, 87, 606-610. [Google Scholar] [CrossRef] 
[31] Kim, R.S. and Surendranath, Y. (2019) Electrochemical Reoxi-dation Enables Continuous Methane-to-Methanol Catalysis with Aqueous Pt Salts. ACS Central Science, 5, 1179-1186. [Google Scholar] [CrossRef] [PubMed]
[32] Ma, J., Mao, K., Low, J., et al. (2021) Efficient Photoelectrochem-ical Conversion of Methane into Ethylene Glycol by WO3 Nanobar Arrays. Angewandte Chemie, 133, 9443-9447. [Google Scholar] [CrossRef] 
[33] Jang, J., Shen, K. and Morales-Guio, C.G. (2019) Electrochemical Direct Partial Oxidation of Methane to Methanol. Joule, 3, 2589-2593. [Google Scholar] [CrossRef] 
[34] Wang, Q., Kan, M., Han, Q. and Zheng, G. (2021) Electrochemical Methane Conversion. Small Structures, 2, Article ID: 2100037. [Google Scholar] [CrossRef] 
[35] Xie, S., Lin, S., Zhang, Q., Tian, Z. and Wang, Y. (2018) Selective Electrocatalytic Conversion of Methane to Fuels and Chemicals. Journal of Energy Chemistry, 27, 1629-1636. [Google Scholar] [CrossRef] 
[36] Sher, M.S.A., Oh, C., Park, H., et al. (2020) Catalytic Oxidation of Methane to Oxygenated Products: Recent Advancements and Prospects for Electrocatalytic and Photocatalytic Conversion at Low Temperatures. Advanced Science, 7, Article ID: 2001946. [Google Scholar] [CrossRef] [PubMed]
[37] Baltrusaitis, J., Jansen, I. and Schuttlefield Christus, J.D. (2014) Renewable Energy Based Catalytic CH4 Conversion to Fuels. Catalysis Science & Technology, 4, 2397-2411. [Google Scholar] [CrossRef] 
[38] Shi, T., Sridhar, D., Zeng, L. and Chen, A. (2022) Recent Advances in Catalyst Design for the Electrochemical and Photoelectrochemical Conversion of Methane to Value-Added Products. Electrochemistry Communications, 135, Article ID: 107220. [Google Scholar] [CrossRef] 
[39] Zhang, Y., Li, J. and Kornienko, N. (2021) Towards Atomic Precision in HMF and Methane Oxidation Electrocatalysts. Chemical Communications, 57, 4230-4238. [Google Scholar] [CrossRef] 
[40] Yin, H., Dou, Y., Chen, S., et al. (2020) 2D Electrocatalysts for Con-verting Earth-Abundant Simple Molecules into Value-Added Commodity Chemicals: Recent Progress and Perspectives. Advanced Materials, 32, Article ID: 1904870. [Google Scholar] [CrossRef] [PubMed]
[41] de Souza, R.F.B., Florio, D.Z., Antolini, E., Antolini, E. and Neto, A.O. (2022) Partial Methane Oxidation in Fuel Cell-Type Reactors for Co-Generation of Energy and Chemicals: A Short Review. Catalysts, 12, Article No. 217. [Google Scholar] [CrossRef] 
[42] Richard, D., Huang, Y.-C. and Morales-Guio, C.G. (2021) Recent Ad-vances in the Electrochemical Production of Chemicals from Methane. Current Opinion in Electrochemistry, 30, Article ID: 100793. [Google Scholar] [CrossRef] 
[43] Abdelkader Mohamed, A.G., Zahra Naqviab, S.A. and Wang, Y. (2021) Advances and Fundamental Understanding of Electrocatalytic Methane Oxidation. ChemCatChem, 13, 787-805. [Google Scholar] [CrossRef] 
[44] Luo, J.H., Hong, Z.S., Chao, T.H. and Cheng, M.J. (2019) Quantum Mechanical Screening of Metal-N4-Functionalized Graphenes for Electrochemical Anodic Oxidation of Light Alkanes to Oxygenates. The Journal of Physical Chemistry C, 123, 19033-19044. [Google Scholar] [CrossRef] 
[45] Tomita, A., Nakajima, J. and Hibino, T. (2008) Direct Oxidation of Methane to Methanol at Low Temperature and Pressure in an Electrochemical Fuel Cell. Angewandte Chemie Interna-tional Edition, 46, 1462-1464. [Google Scholar] [CrossRef] [PubMed]
[46] Van Vleck, J.H. (1933) On the Theory of the Structure of CH4 and Related Molecules. Part I. The Journal of Chemical Physics, 1, 177-182. [Google Scholar] [CrossRef] 
[47] Prajapati, A., Collins, B.A., Goodpaster, J.D. and Singh, M.R. (2021) Fundamental Insight into Electrochemical Oxidation of Methane towards Methanol on transition Metal Oxides. Proceed-ings of the National Academy of Sciences of the United States of America, 118, e2023233118. [Google Scholar] [CrossRef] [PubMed]
[48] Kang, Y., Li, Z., Lv, X., et al. (2021) Active Oxygen Promoted Electrochemical Conversion of Methane on Two-Dimensional Carbide (MXenes): From Stability, Reactivity and Selec-tivity. Journal of Catalysis, 393, 20-29. [Google Scholar] [CrossRef] 
[49] Boyd, M.J., Latimer, A.A., Dickens, C.F., et al. (2019) Elec-tro-Oxidation of Methane on Platinum under Ambient Conditions. ACS Catalysis, 9, 7578-7587. [Google Scholar] [CrossRef] 
[50] Lee, B. and Hibino, T. (2011) Efficient and Selective Formation of Methanol from Methane in a Fuel Cell-Type Reactor. Journal of Catalysis, 279, 233-240. [Google Scholar] [CrossRef] 
[51] Song, Y., Zhao, Y., Nan, G., et al. (2020) Electrocatalytic Oxidation of Methane to Ethanol via NiO/Ni Interface. Applied Catalysis B: Environmental, 270, Article ID: 118888. [Google Scholar] [CrossRef] 
[52] Oh, C., Kim, J., Hwang, Y.J., Ma, M. and Park, J.H. (2021) Electrocatalytic methane oxidation on Co3O4-incorporated ZrO2 nanotube powder. Applied Catalysis B: Environmental, 283, Article ID: 119653. [Google Scholar] [CrossRef] 
[53] Xie, Z., Chen, M., Chen, Y., et al. (2021) Electrocatalytic Me-thane Oxidation to Ethanol via Rh/ZnO Nanosheets. The Journal of Physical Chemistry C, 125, 13324-13330. [Google Scholar] [CrossRef] 
[54] Ma, M., Oh, C., Kim, J., Moon, J.H. and Park, J.H. (2019) Electro-chemical CH4 Oxidation into Acids and Ketones on ZrO2: NiCo2O4 Quasi-Solid Solution Nanowire Catalyst. Applied Catalysis B: Environmental, 259, Article ID: 118095. [Google Scholar] [CrossRef] 
[55] Hahn, F. and Melendres, C .A. (2001) Anodic Oxidation of Methane at Noble Metal Electrodes: an “in Situ” Surface Enhanced Infrared Spectroelectrochemical Study. Electrochimica Acta, 46, 3525-3534. [Google Scholar] [CrossRef] 
[56] Nandenha, J., Fontes, E.H., Piasentin, R.M., Fonseca, F.C. and Neto, A.O. (2018) Direct Oxidation of Methane at Low Temperature Using Pt/C, Pd/C, Pt/C-ATO and Pd/C-ATO Electrocatalysts Prepared by Sodium Borohydride Reduction Process. Journal of Fuel Chemistry and Technology, 46, 1137-1145. [Google Scholar] [CrossRef] 
[57] Ren, X., Wang, Y., Liu, A., et al. (2020) Current Progress and Performance Improvement of Pt/C Catalysts for Fuel Cells. Journal of Materials Chemistry A, 8, 24284-24306. [Google Scholar] [CrossRef] 
[58] Nandenha, J., Piasentin, R.M., Silva, L.M.G., et al. (2019) Partial Oxi-dation of Methane and Generation of Electricity Using a PEMFC. Ionics, 25, 5077-5082. [Google Scholar] [CrossRef] 
[59] Wang, Q., Li, T., Yang, C., et al. (2021) Electrocatalytic Methane Oxidation Greatly Promoted by Chlorine Intermediates. Angewandte Chemie International Edition, 60, 17398-17403. [Google Scholar] [CrossRef] [PubMed]
[60] Exner, K.S., Anton, J., Jacob, T. and Over, H. (2014) Controlling Se-lectivity in the Chlorine Evolution Reaction over RuO2-Based Catalysts. Angewandte Chemie, 126, 11212-11215. [Google Scholar] [CrossRef] 
[61] Feng, N., Lin, H., Song, H., et al. (2021) Efficient and Selective Photocatalytic CH4 Conversion to CH3OH with O2 by Controlling Overoxidation on TiO2. Nature Communications, 12, Article No. 4652. [Google Scholar] [CrossRef] [PubMed]
[62] Perry, S.C., de León, C.P. and Walsh, F.C. (2020) The Design, Performance and Continuing Development of Electrochemical Reactors for Clean Electrosynthesis. Journal of the Elec-trochemical Society, 167, Article ID: 155525. [Google Scholar] [CrossRef] 
[63] Xu, Y. and Lin, L. (1999) Recent Advances in Methane Dehy-dro-Aromatization over Transition Metal Ion-Modified Zeolite Catalysts Under Non-Oxidative Conditions. Applied Ca-talysis A: General, 188, 53-67. [Google Scholar] [CrossRef] 
[64] Lin, X.-Y., Li, J.-Y., Qi, M.-Y., Tang, Z.-R. and Xu, Y.-J. (2021) Methane Conversion over Artificial Photocatalysts. Catalysis Communications, 159, Article ID: 106346. [Google Scholar] [CrossRef] 
[65] Spinner, N. and Mustain, W.E. (2013) Electrochemical Methane Activation and Conversion to Oxygenates at Room Temperature. ECS Transactions, 53, 1-20. [Google Scholar] [CrossRef] 
[66] Li, W., He, D., Hu, G., et al. (2018) Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2. ACS Central Science, 4, 631-637. [Google Scholar] [CrossRef] [PubMed]
[67] O’Reilly, M.E., Kim, R.S., Oh, S. and Surendranath, Y. (2017) Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate. ACS Central Science, 3, 1174-1179. [Google Scholar] [CrossRef] [PubMed]
[68] Ma, M., Jin, B.J., Li, P., et al. (2017) Ultrahigh Electrocatalytic Conversion of Methane at Room Temperature. Advanced Science, 4, Article ID: 1700379. [Google Scholar] [CrossRef] [PubMed]
[69] Rocha, R.S., Camargo, L.M., Lanza, M.R.V. and Bertazzoli, R. (2010) A Feasibility Study of the Electro-Recycling of Greenhouse Gases: Design and Characterization of a (TiO2/RuO2)/PTFE Gas Diffusion Electrode for the Electrosynthesis of Methanol from Methane. Electrocatalysis, 1, 224-229. [Google Scholar] [CrossRef] 
[70] Frese Jr., K.W. (1991) Partial Electrochemical Oxidation of Me-thane under Mild Conditions. Langmuir, 7, 13-15. [Google Scholar] [CrossRef] 
[71] Omasta, T.J., Rigdon, W.A., Lewis, C.A., Stanis, R.J., Liu, R., Fan, C.Q. and Mustain, W.E. (2015) Two Pathways for Near Room Temperature Electrochemical Conversion of Methane to Methanol. ECS Transactions, 66, 129-136. [Google Scholar] [CrossRef] 
[72] Morejudo, S.H., Zanón, R., Escolástico, S., et al. (2016) Direct Con-version of Methane to Aromatics in a Catalytic Co-Ionic Membrane Reactor. Science, 353, 563-566. [Google Scholar] [CrossRef] [PubMed]

为你推荐