氧还原是许多能量转换装置中的关键反应。在简要阐述氧还原反应机理的同时,结合笔者自身团队研究成果重点介绍了近年来新兴的多孔材料(金属有机框架MOF、共轭微孔聚合物CMP等)在电催化中的应用。针对目前电催化剂存在的问题,指出未来的研究思路,包括利用先进的技术手段原位表征催化剂的活性位点,由高活性位逆向推算催化剂的最优结构,优化材料的制备条件。由理论指导实践,在深入认识氧还原反应机理的前提下开发高效稳定、经济环保的新型电催化剂。
Oxygen reduction reaction (ORR) is central to many devices of energy storage and conversion.Along with a succinct introduction of the mechanism of ORR,basing on current research findings of authors' group,focuses on reviewing the status of novel porous materials (i.e.,MOF,CMP,etc.) in electrocatalyst.However,some obstacles such as low activity complex structures of functional carbon materials hindering the commercialization of these catalysts.In terms of the issues,the trend of further development for ORR catalysts was put forward.Great efforts were supposed to be made including the use of advanced technique to identify the active site in suit,predicted the optimal structure for ORR from the high-active site,and optimized the preparation of materials.In addition,theory was combined with practice.Only fully understanding the mechanism of ORR,a new class of electrocatalyst with high efficiency,stability,economy and environment friendly will be developed.
[1] Debe M K.Electrocatalyst approaches and challenges for automotive fuel cells[J].Nature,2012,486(7401):43-51.
[2] 吕旭初,韩俊,贺山山,等.绿色能源电催化电极用氮化碳基纳米材料的设计[J].现代化工,2018,38(1):30-34.
[3] 刘云梅.氮硫共掺杂碳纳米管的制备及其催化性能研究[J].化工新型材料,2018,46(7):127-130.
[4] Jia Q,Liu E,Jiao L,et al.X-ray absorption spectroscopy characterizations on PGM-free electrocatalysts:justification,advantages,and limitations[J].Advanced Materials,2019,31(31):1805157.
[5] Cheng W,Zhao X,Su H,et al.Lattice-strained metal-organic-framework arrays for bifunctional oxygen electrocatalysis[J].Nature Energy,2019,4(2):115-122.
[6] Chen S,Niu Z,Xie C,et al.Effects of catalyst processing on the activity and stability of Pt-Ni nanoframe electrocatalysts[J].ACS Nano,2018,12(8):8697-8705.
[7] Sial M,Lin H,Zulfiqar M,et al.Trimetallic PtCoFe alloy monolayer superlattices as bifunctional oxygen-reduction and ethanol-oxidation electrocatalysts[J].Small,2017,13(24):1700250.
[8] Kang Y,Ye X,Chen J,et al.Design of Pt-Pd binary superlattices exploiting shape effects and synergistic effects for oxygen reduction reactions[J].Journal of the American Chemical Society,2013,135(1):42-45.
[9] Yuan K,Zhuang X,Fu H,et al.Two-dimensional core-shelled porous hybrids as highly efficient catalysts for the oxygen reduction reaction[J].Angewandte Chemie International Edition,2016,55(24):6858-6863.
[10] Roy S,Bandyopadhyay A,Das M,et al.Redox-active and semi-conducting donor-acceptor conjugated microporous polymers as metal-free ORR catalysts[J].Journal of Materials Chemistry A,2018,6(14):5587-5591.
[11] Sarapuu A,Kibena-Põldsepp E,Borghei M,et al.Electrocatalysis of oxygen reduction on heteroatom-doped nanocarbons and transition metal-nitrogen-carbon catalysts for alkaline membrane fuel cells[J].Journal of Materials Chemistry A,2018,6(3):776-804.
[12] Majidi L,Yasaei P,Warburton R E,et al.New class of electrocatalysts based on 2D transition metal dichalcogenides in ionic liquid[J].Advanced Materials,2019,31(4):1804453.
[13] Gong K,Du F,Xia Z,et al.Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J].Science,2009,323(5915):760.
[14] 王启晨,王璟,雷永鹏,等.碳纳米管基非贵金属催化剂在电催化氧化还原中的应用研究进展[J].无机化学学报,2018,34(5):807-822.
[15] 赵卫芳,郭梦薇,朱振涛,等.一步热解合成氮掺杂石墨烯载钴纳米粒子及其对氧还原反应的电催化性能[J].化工新型材料,2017,45(5):84-86.
[16] Nørskov J K,Rossmeisl J,Logadottir A,et al.Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J].The Journal of Physical Chemistry B,2004,108(46):17886-17892.
[17] Seh Z W,Kibsgaard J,Dickens C F,et al.Combining theory and experiment in electrocatalysis:insights into materials design[J].Science,2017,355(6321):eaad4998.
[18] Yan D,Li Y,Huo J,et al.Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions[J].Advanced Materials,2017,29(48):1606459.
[19] Zhu C,Li H,Fu S,et al.Highly efficient nonprecious metal catalysts towards oxygen reduction reaction based on three-dimensional porous carbon nanostructures[J].Chemical Society Reviews,2016,45(3):517-531.
[20] Norskov J K,Bligaard T,Rossmeisl J,et al.Towards the computational design of solid catalysts[J].Nature chemistry,2009,1(1):37-46.
[21] 王昌安,王为.有机多孔催化研究进展[J].化学学报,2015,73(6):498-529.
[22] 任浩,朱广山.有机多孔材料:合成策略与性质研究[J].化学学报,2015,73(6):587-599.
[23] Yang L,Zeng X,Wang W,et al.Recent progress in MOF-derived,heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells[J].Advanced Functional Materials,2018,28(7):1704537.
[24] Furukawa H,Cordova K E,O'Keeffe M,et al.The chemistry and applications of metal-organic frameworks[J].Science,2013,341(6149):1230444.
[25] Zhong R,Wu Y,Liang Z,et al.Fabricating hierarchically porous and Fe3C-embeded nitrogen-rich carbon nanofibers as exceptional electocatalysts for oxygen reduction[J].Carbon,2019,142:115-122.
[26] Zhang C L,Lu B R,Cao F H,et al.Electrospun metal-organic framework nanoparticle fibers and their derived electrocatalysts for oxygen reduction reaction[J].Nano Energy,2019,55:226-233.
[27] Miner E M,Fukushima T,Sheberla D,et al.Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2[J].Nature Communications,2016,7:10942.
[28] Gonen S,Lori O,Cohen-Taguri G,et al.Metal organic frameworks as a catalyst for oxygen reduction:an unexpected outcome of a highly active Mn-MOF-based catalyst incorporated in activated carbon[J].Nanoscale,2018,10(20):9634-9641.
[29] Jiang J X,Wang C,Laybourn A,et al.Metal-organic conjugated microporous polymers[J].Angewandte Chemie International Edition,2011,50(5):1072-1075.
[30] Jiang J X,Su F,Trewin A,et al.Conjugated microporous poly(aryleneethynylene) networks[J].Angewandte Chemie International Edition,2007,119(45):8728-8732.
[31] Li A,Lu R F,Wang Y,et al.Lithium-doped conjugated microporous polymers for reversible hydrogen storage[J].Angewandte Chemie International Edition,2010,49(19):3330-3333.
[32] Li A,Sun H X,Tan D Z,et al.Superhydrophobic conjugated microporous polymers for separation and adsorption[J].Energy & Environmental Science,2011,4(6):2062-2065.
[33] Qian X,Zhu Z Q,Sun H X,et al.Capture and reversible storage of volatile iodine by novel conjugated microporous polymers containing thiophene units[J].ACS Applied Materials & Interfaces,2016,8(32):21063-21069.
[34] Wei H,Wang F,Qian X,et al.Superhydrophobic fluorine-rich conjugated microporous polymers monolithic nanofoam with excellent heat insulation property[J].Chemical Engineering Journal,2018,351:856-866.
[35] Mu P,Zhang Z,Bai W,et al.Superwetting monolithic hollow-carbon-nanotubes aerogels with hierarchically nanoporous structure for efficient solar steam generation[J].Advanced Energy Materials,2019,9:1802158.
[36] Lin D,Hu C,Chen H,et al.Microporous N,P-codoped graphitic nanosheets as an efficient electrocatalyst for oxygen reduction in whole pH range for energy conversion and biosensing dissolved oxygen[J].Chemistry-A European Journal,2018,24(69):18487-18493.
[37] 王秀利,何兴权.氮/硫双掺多孔碳负载Fe9S10纳米粒子的氧还原电催化性能[J].高等学校化学学报,2018,39(7):1524-1531.
[38] Yang W,Chen L,Liu X,et al.A new method for developing defect-rich graphene nanoribbons/onion-like carbon@Co nanoparticles hybrid materials as an excellent catalyst for oxygen reactions[J].Nanoscale,2017,9(4):1738-1744.
[39] Guo J,Lin C Y,Xia Z,et al.A pyrolysis-free covalent organic polymer for oxygen reduction[J].Angewandte Chemie International Edition,2018,57(38):12567-12572.
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