直接甲醇燃料电池阳极催化剂及载体的研究现状及展望
Research Progress and Prospect of Anodic Catalysts for Direct Methanol Fuel Cells
DOI: 10.12677/HJCET.2021.115038, PDF,   
作者: 李贵贤, 王首登, 李艳茹, 祁建军：兰州理工大学，石油化工学院，甘肃 兰州；李红伟*：兰州理工大学，石油化工学院，甘肃 兰州；甘肃省低碳能源化工重点实验室，甘肃 兰州
关键词: 直接甲醇燃料电池；阳极催化剂；载体；Direct Methanol Fuel Cell； Anode Catalyst； Carrier
摘要: 我国十四五规划中将清洁能源摆在重要位置，其中甲醇由于其良好的贮氢能力、价格低廉、来源丰富而被誉为“液态阳光”。在燃料电池领域可以作为氢气的良好替代品，因此被认为是最有应用前景的燃料电池技术之一。直接甲醇燃料电池还具有体积小、质量轻、结构简单、安全性高等特点，非常适用于便携式移动电源，也被认为是最有可能替代锂离子电池的电池。本文综述了直接甲醇燃料电池阳极催化剂的催化机理、催化剂和载体的研究进展，并结合当前研究进展阐述了直接甲醇燃料电池未来的发展趋势。
Abstract: In China’s 14th Five-Year Plan, clean energy is placed in an important position, among which methanol is known as “liquid sunshine” because of its good hydrogen storage capacity, low price and abundant sources. It can be used as a good substitute for hydrogen in the field of fuel cell, so it is considered as one of the most promising fuel cell technologies. Direct methanol fuel cell also has the characteristics of small size, light weight, simple structure and high safety, which is very suitable for portable mobile power supply, and is also considered as the most likely alternative to lithium ion battery. In this paper, the reaction mechanism, catalyst and support research progress of direct methanol fuel cell are reviewed, and the future development trend of direct methanol fuel cell is described based on the current research progress.
文章引用：李贵贤, 王首登, 李艳茹, 祁建军, 李红伟. 直接甲醇燃料电池阳极催化剂及载体的研究现状及展望[J]. 化学工程与技术, 2021, 11(5): 283-293. https://doi.org/10.12677/HJCET.2021.115038

参考文献

[1] Dongmulati, N. and Maimaitiyiming, X. (2020) Low-Cost Polyaniline Coated Carbonized Materials as Support for Pt-Based Electrocatalysts for Direct Methanol Fuel Cells (DMFC). Materials Express, 10, 1892-1899. [Google Scholar] [CrossRef] 
[2] Pieta, I.S., Rathi, A., Pieta, P., Nowakowski, R., Hołdynski, M., Pisa-rek, M., Kaminska, A., Gawande, M.B. and Zboril, R. (2019) Electrocatalytic Methanol Oxidation over Cu, Ni and Bi-metallic Cu-Ni Nanoparticles Supported on Graphitic Carbon Nitride. Applied Catalysis B, 244, 272-283. [Google Scholar] [CrossRef] 
[3] Reddy, A., Gowda, S.R., Shaijumon, M.M., et al. (2012) Hybrid Nanostructures for Energy Storage Applications. Advanced Materials, 24, 5045-5064. [Google Scholar] [CrossRef] [PubMed]
[4] Sahoo, N.G., Pan, Y., Li, L., et al. (2012) Graphene-Based Materials for Energy Conversion. Advanced Materials, 24, 4203-4210. [Google Scholar] [CrossRef] [PubMed]
[5] Steinlechner, C. and Junge, H. (2018) Nachhaltige Produktion von Methan aus CO2 mithilfe von Sonnenlicht. Angewandte Chemie, 130, 44-46. [Google Scholar] [CrossRef] 
[6] 郭扬, 吕一铮, 严坤, 田金平, 陈吕军. 中国工业园区低碳发展路径研究[J]. 中国环境管理, 2021, 13(1): 49-58.
[7] Cui, R.Y., Hultman, N., Cui, D., et al. (2021) A Plant-by-Plant Strategy for High-Ambition Coal Power Phaseout in China. Nature Communications, 12, Article No. 1468. [Google Scholar] [CrossRef] [PubMed]
[8] 吕海波. 二氧化碳制甲醇——碳减排的新方向[J]. 气体分离, 2011(5): 12-13.
[9] Gao, Y., Liu, J.L. and Bashir, S. (2020) Electrocatalysts for Direct Methanol Fuel Cells to Demon-strate China’s Renewable Energy Renewable Portfolio Standards within the Framework of the 13th Five-Year Plan. Ca-talysis Today, 374, 135-153.
[10] Duan, C., Kee, R., Zhu, H., et al. (2019) Highly Efficient Reversible Protonic Ceramic Electrochemical Cells for Power Generation and Fuel Production. Nature Energy, 4, 230-240. [Google Scholar] [CrossRef] 
[11] Mari, E., Tsai, P.C., Eswaran, M., et al. (2020) Efficient Elec-tro-Catalytic Oxidation of Ethylene Glycol Using Flower-Like Graphitic Carbon Nitride/Iron Oxide/Palladium Nano-composite for Fuel Cell Application. Fuel, 280, Article ID: 118646. [Google Scholar] [CrossRef] 
[12] Arakishvili, N., Tkeshelashvili, T., Dumbadze, N., et al. (2020) Synthesis and Characterization of Sulfonated Poly(phenylene sulfone) Based Phase-Separated Multiblock Copolymers for PEMFC Application. Bayreuth Polymer Symposium 2019, Bayreuth.
[13] 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.
[14] Bhunia, P., et al. (2020) Electrochemistry, Reaction Mechanisms, and Reaction Kinetics in Direct Methanol Fuel Cells. In: Direct Methanol Fuel Cell Technology, Elsevier, Amsterdam, 443-494.
[15] 李冰, 马新建, 乔锦丽, 等. 基于非铂催化剂的质子交换膜燃料电池研究[M]. 上海: 同济大学出版社, 2017: 47-91.
[16] Liang, H., Zhang, X., Wang, Q., et al. (2018) Shape-Control of Pt-Ru Nanocrystals: Tuning Surface Structure for Enhanced Elec-trocatalytic Methanol Oxidation. Journal of the American Chemical Society, 140, 1142-1147. [Google Scholar] [CrossRef] [PubMed]
[17] Huang, W., Wang, H., Zhou, J., et al. (2015) Highly Active and Durable Methanol Oxidation Electrocatalyst Based on the Synergy of Platinum-Nickel Hydroxide-Graphene. Nature Communica-tions, 6, Article No. 10035. [Google Scholar] [CrossRef] [PubMed]
[18] Ren, G., Zhang, Z., Liu, Y., et al. (2020) Facile Synthesis of Composi-tion-Controllable PtPdAuTe Nanowires as Superior Electrocatalysts for Direct Methanol Fuel Cells. Chemistry—An Asian Journal, 15, 98-105. [Google Scholar] [CrossRef] [PubMed]
[19] Guo, W.H., Yao, X.Z., Peng, L.Y., et al. (2020) Platinum Monolayers Stabilized on Dealloyed AuCu Core-Shell Nanoparticles for Improved Activity and Stability on Methanol Oxidation Re-action. Chinese Chemical Letters, 31, 836-840. [Google Scholar] [CrossRef] 
[20] Li, H., Lu, S., Sun, J., et al. (2018) Phase-Controlled Synthesis of Nickel Phosphide Nanocrystals and Their Electrocatalytic Performance for the Hydrogen Evolution Reaction. Chemistry—A European Journal, 24, 11748-11754. [Google Scholar] [CrossRef] [PubMed]
[21] Kim, H.J., Ahn, Y.-D., Kim, J., et al. (2020) Surface Elemental Dis-tribution Effect of Pt-Pb Hexagonal Nanoplates for Electrocatalytic Methanol Oxidation Reaction. Chinese Journal of Catalysis, 41, 813-819.
[22] Coutanceau, C., Urchaga, P. and Baranton, S. (2012) Diffusion of Adsorbed CO on Plati-num (100) and (111) Oriented Nanosurfaces. Electrochemistry Communications, 22, 109-112. [Google Scholar] [CrossRef] 
[23] Huang, L., Jadoon, S., Wang, Z., et al. (2021) Synthesis and Application of Platinum-Based Hollow Nanoframes for Direct Alcohol Fuel Cells. Acta Physico-Chimica Sinica, 37, Ar-ticle ID: 2009035.
[24] Huang, T.H., Halothia, D.B., Lin, S., et al. (2020) The Ethanol Oxidation Reaction Performance of Carbon-Supported PtRuRh Nanorods. Applied Sciences, 10, 3923. [Google Scholar] [CrossRef] 
[25] Nb, A., Sr, A., Wz, A., et al. (2020) Highly Efficient Methanol Oxida-tion on Durable PtxIr/MWCNT Catalysts for Direct Methanol Fuel Cell Applications. International Journal of Hydrogen Energy, 45, 6447-6460. [Google Scholar] [CrossRef] 
[26] Shi, L. (2019) Preparation of Pt-Pd/PANI/Graphene Nanosheets Composites as Electrocatalysts for Direct Methanol Fuel Cell. International Journal of Electrochemical Sci-ence, 14, 7104-7115. [Google Scholar] [CrossRef] 
[27] Burhan, H., Ay, H., Kuyuldar, E., et al. (2020) Monodisperse Pt-Co/GO Anodes with Varying Pt:Co Ratios as Highly Active and Stable Electrocatalysts for Methanol Electrooxidation Reaction. Scientific Reports, 10, Article No. 6114. [Google Scholar] [CrossRef] [PubMed]
[28] Zhao, F., Ye, J.Y., Yuan, Q., et al. (2020) Realizing a CO-Free Pathway and Enhanced Durability in Highly Dispersed Cu-Doped PtBi Nanoalloys towards Methanol Full Electrooxida-tion. Journal of Materials Chemistry A, 8, 11564-11572. [Google Scholar] [CrossRef] 
[29] Kianfar, S., Golikand, A.N. and Zarenezhad, B. (2020) Bimetal-lic-Metal Oxide Nanoparticles of Pt-M (M: W, Mo, and V) Supported on Reduced Graphene Oxide (rGO): Radiolytic Synthesis and Methanol Oxidation Electrocatalysis. Journal of Nanostructure in Chemistry, 11, 287. [Google Scholar] [CrossRef] 
[30] Aramesh, N., Hoseini, S.J., Shahsavari, H.R., et al. (2020) PtSn Nanoalloy Thin Films as Anode Catalysts in Methanol Fuel Cells. Inorganic Chemistry, 59, 10688-10698. [Google Scholar] [CrossRef] [PubMed]
[31] Yin, S.W., Chen, P., Jin, P.J. and Chen, Y. (2020) Porous Pd-PdO Nanotubes for Methanol Electrooxidation. Advanced Functional Materials, 30, Article ID: 2000534. [Google Scholar] [CrossRef] 
[32] Yin, S., Wang, Z., Liu, S., et al. (2021) Flexible Synthesis of Au@Pd Core-Shell Mesoporous Nanoflowers for Efficient Methanol Oxidation. Nanoscale, 13, 3208-3213. [Google Scholar] [CrossRef] 
[33] Dobrovetska, O., Saldan, I., Orovčik, L., et al. (2019) Electrocatalytic Activity of Pd-Au Nanoalloys during Methanol Oxidation Reaction. International Journal of Hydrogen Energy, 45, 4444-4456. [Google Scholar] [CrossRef] 
[34] Li, Z.R., Shen, T., Hu, Y.Z., Chen, K., Lu, Y., Wang, D.L., et al. (2021) Progress on Ordered Intermetallic Electrocatalysts for Fuel Cells Application. Acta Physico-Chimica Sinica, 37, Article ID: 2010029. [Google Scholar] [CrossRef] 
[35] Ma, J., Ai, D., Xie, X., et al. (2011) Novel Metha-nol-Tolerant Ir-S/C Chalcogenide Electrocatalysts for Oxygen Reduction in DMFC Fuel Cell. Particuology, 9, 155-160. [Google Scholar] [CrossRef] 
[36] Xiong, L., Sun, Z., Zhang, X., et al. (2019) Octahedral Gold-Silver Nanoframes with Rich Crystalline Defects for Efficient Methanol Oxidation Manifesting a CO-Promoting Effect. Nature Communications, 10, Article No. 3782. [Google Scholar] [CrossRef] [PubMed]
[37] Sunitha, M., Durgadevi, N., Sathish, A., et al. (2018) Perfor-mance Evaluation of Nickel as Anode Catalyst for DMFC in Acidic and Alkaline Medium. Journal of Fuel Chemistry and Technology, 46, 592-599. [Google Scholar] [CrossRef] 
[38] Yang, P., Stamenkovic, V., Somorjai, G.A., et al. (2015) Nanoframes with Three-Dimensional Electrocatalytic Surfaces.
[39] Wkj, A., Smb, C., Del, D., et al. (2020) Cobalt- and Iron-Coordinated Graphitic Carbon Nitride on Reduced Graphene Oxide: A Nonprecious Bimetallic M-N-C Analogue Electrocatalyst for Efficient Oxygen Reduction Reaction in Acidic Media. Applied Surface Science, 531, Article ID: 147367.
[40] 孙世刚, 陈胜利, 等. 电催化[M]. 北京: 化学工业出版社, 2020: 242-253.
[41] Hao, L., Kang, D., Hui, W., et al. (2011) Carbon-Supported Pt-RuCo Nanoparticles with Low-Noble-Metal Content and Superior Catalysis for Ethanol Oxidization. International Journal of Electrochemical Science, 6, 1058-1065.
[42] Maiyalagan, T., Alaje, T.O. and Scott, K. (2012) Highly Stable Pt-Ru Nanoparticles Supported on Three-Dimensional Cubic Ordered Mesopo-rous Carbon (Pt-Ru/CMK-8) as Promising Electrocatalysts for Methanol Oxidation. Journal of Physical Chemistry C, 116, 2630-2638. [Google Scholar] [CrossRef] 
[43] Panagiotis, T., et al. (2017) Pt/CN-Doped Electrocatalysts: Superior Electrocatalytic Activity for Methanol Oxidation Reaction and Mechanistic Insight into Interfacial Enhancement. Applied Catalysis, B. Environmental: An International Journal Devoted to Catalytic Science and Its Applications, 203, 541-548. [Google Scholar] [CrossRef] 
[44] Hoseini, S.J., Bahrami, M. and Dehghani, M. (2014) Formation of Snowman-Like Pt/Pd Thin Film and Pt/Pd/Reduced- Graphene Oxide Thin Film at Liquid-Liquid Interface by Use of Organometallic Complexes, Suitable for Methanol Fuel Cells. Rsc Advances, 4, 13796-13804. [Google Scholar] [CrossRef] 
[45] Zhong, G., et al. (2016) Composition-Tunable PtCu Alloy Nanowires and Electrocatalytic Synergy for Methanol Oxidation Reaction. The Journal of Physical Chemistry, C. Nanomaterials and Interfaces, 120, 10476-10484.
[46] Qiu, H.J., et al. (2015) Aligned Nanoporous Pt-Cu Bimetallic Microwires with High Catalytic Activity toward Methanol Electrooxidation. Acs Catalysis, 5, 3779-3785. [Google Scholar] [CrossRef] 
[47] Dadelen, Z., Yldz, Y., Eri, S., et al. (2017) Enhanced Electrocatalytic Activity and Durability of Pt Nanoparticles Decorated on GO-PVP Hybride Material for Methanol Oxidation Reaction. Applied Catalysis B: Environmental, 219, 511-516. [Google Scholar] [CrossRef] 
[48] Lazaro, M.J., Calvillo, L., Celorrio, V., et al. (2011) Study and Application of Carbon Black Vulcan XC-72R in Polymeric Electrolyte Fuel Cells.
[49] Hff, A., Mka, B., Fpa, B., et al. (2020) Application of N-Doped Carbon Nanotube-Supported Pt-Ru as Electrocatalyst Layer in Passive Direct Methanol Fuel Cell. International Journal of Hydrogen Energy, 45, 25307-25316. [Google Scholar] [CrossRef] 
[50] Wei, Q., Liu, T., et al. (2019) Three-Dimensional N-Doped Graphene Aerogel-Supported Pd Nanoparticles as Efficient Catalysts for Solvent-Free Oxidation of Benzyl Alcohol. Rsc Advances, 9, 9620-9628. [Google Scholar] [CrossRef] 
[51] Liu, J.W., et al. (2018) Recent Progress in Graphene-Based No-ble-Metal Nanocomposites for Electrocatalytic Applications. Advanced Materials, 31, Article ID: 1800696.
[52] Demirkan, B., et al. (2019) Composites of Bimetallic Platinum-Cobalt Alloy Nanoparticles and Reduced Graphene Oxide for Electrochemical Determination of Ascorbic Acid, Dopamine, and Uric Acid. Scientific Reports, 9, Article No. 12258. [Google Scholar] [CrossRef] [PubMed]
[53] Gao, H., Yuan, C., He, Z., et al. (2020) En-hanced Electrocatalytic Oxidation of Methanol on Pt-Decorated Bi2WO6/Graphene Nanosheets with Visible Light Assis-tance. Energy Technology, 8, Article ID: 2000210. [Google Scholar] [CrossRef] 
[54] Shi, C. and Maimaitiyiming, X. (2021) FeNi-Functionalized 3D N, P Doped Graphene Foam as a Noble Metal-Free Bifunctional Electrocatalyst for Direct Methanol Fuel Cells. Journal of Al-loys and Compounds, 2021, Article ID: 158732. [Google Scholar] [CrossRef] 
[55] He, C. and Tao, J. (2016) Pt Loaded Two-Dimensional TaC-Nanosheet/Graphene Hybrid as an Efficient and Durable Electrocatalyst for Direct Methanol Fuel Cells. Journal of Power Sources, 324, 317-324. [Google Scholar] [CrossRef] 
[56] Kou, R., Shao, Y., Mei, D., et al. (2011) Stabilization of Electrocatalytic Metal Nanoparticles at Metal-Metal Oxide-Graphene Triple Junction Points. Journal of the American Chemi-cal Society, 133, 2541. [Google Scholar] [CrossRef] [PubMed]
[57] Gil-Castell, O., Santiago, S., Pascual-Jose, B., et al. (2020) Performance of Sulfonated Poly(Vinyl Alcohol)/Graphene Oxide Polyelectrolytes for Direct Methanol Fuel Cells. Energy Technology, 8, Article ID: 2000124. [Google Scholar] [CrossRef] 
[58] Lolak, N., Kuyuldar, E., Burhan, H., et al. (2019) Composites of Pal-ladium-Nickel Alloy Nanoparticles and Graphene Oxide for the Knoevenagel Condensation of Aldehydes with Malono-nitrile. ACS Omega, 4, 6848-6853. [Google Scholar] [CrossRef] [PubMed]
[59] Liu, H., Li, C., Chen, D., et al. (2017) Uniformly Dispersed Platinum-Cobalt Alloy Nanoparticles with Stable Compositions on Carbon Substrates for Methanol Oxidation Reaction. Scientific Reports, 7, Article No. 11421. [Google Scholar] [CrossRef] [PubMed]
[60] Baronia, R., Goel, J., Kaswan, J., et al. (2018) PtCo/rGO Nano-Anode Catalyst: Enhanced Power Density with Reduced Methanol Crossover in Direct Methanol Fuel Cell. Materials for Renewable and Sustainable Energy, 7, 27. [Google Scholar] [CrossRef] 
[61] Baronia, R., Goel, J. and Singhal, S.K. (2019) High Methanol Electro-Oxidation Using PtCo/Reduced Graphene Oxide (rGO) Anode Nanocatalysts in Direct Methanol Fuel Cell. Journal of Nanoscience and Nanotechnology, 19, 4315-4322. [Google Scholar] [CrossRef] [PubMed]
[62] Hy, A., Liang, G.A., Yz, B., et al. (2019) Graphene-Templated Synthesis of Palladium Nanoplates as Novel Electrocatalyst for Direct Methanol Fuel Cell. Applied Surface Science, 466, 385-392. [Google Scholar] [CrossRef] 
[63] Ali, A. and Shen, P.K. (2019) Recent Advances in Graphene-Based Platinum and Palladium Electrocatalysts for the Methanol Oxidation Reaction. Journal of Materials Chemistry A, 7, 22189-22217. [Google Scholar] [CrossRef]