介孔炭负载铂纳米粒子的高效氧还原催化剂的可控设计

doi:10.19894/j.issn.1000-0518.210113

摘要/Abstract

摘要： 研制高效的氧还原催化剂对推动燃料电池的发展具有十分重要的意义,本研究利用水热法处理得到的富含缺陷的介孔炭材料为前驱体制备了介孔炭负载铂纳米粒子的高效氧还原催化剂Pt/BP_a(a表示酸处理),并对其进行成分和形貌结构表征。在酸性电解质中,该催化剂表现出良好的电催化氧还原反应(ORR)活性(半波电势为0.829 V)和稳定性(10000圈CV测试后其半波电势仅下降9 mV),优于商业Pt/C催化剂的催化效果和稳定性。通过对反应机理的解析发现,Pt/BP_a催化ORR的电子转移数为3.98,H₂O₂产率均低于5%,此类介孔碳负载铂纳米粒子的催化剂在未来燃料电池领域有着很大的应用前景。

关键词: 介孔碳材料, 缺陷, 铂基催化剂, 氧还原反应, 燃料电池, 高活性

Abstract: A carbon black-supported cost-effective carrier, the mesoporous carbon precursors with a lot of defects, were prepared by the hydrothermal method. After adding chloroplatinic acid and calcining at high temperature, the oxygen reduction catalyst of mesoporous carbon materials loaded with platinum nanoparticles was obtained. The composition and morphology of the prepared catalyst were characterized by a series of test methods. Combined with the activity and stability of the catalyst in the electrocatalytic oxygen reduction reaction (ORR) in acidic electrolyte, the potential law of oxygen defect on carbon materials and the electrochemical properties of the material itself was explored. The half-wave potential of Pt/BP_a (a stands for acid treatment) catalyst prepared under acidic condition is 0.829 V. After 10000 circles of the CV test, the half-wave potential decreases by 0.009 V, showing that the catalytic effect and stability are better than that of commercial Pt/C catalyst in the voltage range of 0.3~0.8 V. The electron transfer number of ORR with Pt/BP_a catalyst is approximately 3.98 and the intermediate product yields of H₂O₂ are all lower than 5%. It is further proved that the Pt/BP_a catalyst is in an effective four-electron process during the oxygen reduction reaction, is expected to be a commercial alternative to Pt/C, and also has great application prospect in the future fuel cell field.

Key words: Mesoporous carbon, Defects, Platinum, Oxygen reduction reaction, Fuel cell, Highly active

中图分类号:

O643

李宫, 金龙一, 姚鹏飞, 刘聪, 徐维林. 介孔炭负载铂纳米粒子的高效氧还原催化剂的可控设计[J]. 应用化学, 2021, 38(12): 1639-1646.

LI Gong, JIN Long-Yi, YAO Peng-Fei, LIU Cong, XU Wei-Lin. Controllability Design of High Performance Oxygen Reduction Catalysts Supported by Platinum Nanoparticles Loaded on Mesoporous Carbon[J]. Chinese Journal of Applied Chemistry, 2021, 38(12): 1639-1646.

参考文献

[1] STEELE B C H, HEINZEL A. Materials for fuel-cell technologies in materials for sustainable energy[M]. UK: Macmillan Publishers Ltd, 2010: 224-231.
[2] TANG T, WEN J J, SHUAI N, et al. Metastable rock salt oxide-mediated synthesis of high-density dual-protected M@NC for long-life rechargeable zinc-air batteries with record power density[J]. J Am Chem Soc, 2020, 142(15): 7116-7127.
[3] HE D, ZENG C, XU C, et al. Polyaniline-functionalized carbon nanotube supported platinum catalysts[J]. Langmuir, 2011, 27(9): 5582-5588.
[4] TAN J L, DE JESUS A M, CHUA S L, et al. Preparation and characterization of palladium-nickel on graphene oxide support as anode catalyst for alkaline direct ethanol fuel cell[J]. Appl Catal A, 2017, 531: 29-35.
[5] HUANG X X, SHEN T, Z T, et al. Efficient oxygen reduction catalysts of porous carbon nanostructures decorated with transition metal species[J]. Adv Energy Mater, 2020, 10(11): 1900375.
[6] SHAO M, CHANG Q, DODELET J P, et al. Recent advances inelectrocatalysts for oxygen reduction reaction[J]. Chem Rev, 2016, 116(6): 3594-3657.
[7] HE D, KOU Z, XIONG Y, et al. Simultaneous sulfonation and reduction of graphene oxide as highly efficient supports for metal nanocatalysts[J]. Carbon, 2014, 66: 312-319.
[8] YOU B, KANG F, YIN P, et al. Hydrogel-derived heteroatom-doped porous carbon networks for supercapacitor and electrocatalytic oxygen reduction[J]. Carbon, 2016, 103: 9-15.
[9] WANG J, HUANG Z, LIU W, et al. Design of N-coordinated dual-metal sites: a stable and active Pt-free catalyst for acidic oxygen reduction reaction[J]. J Am Chem Soc, 2017, 139(48): 17281-17284.
[10] WANG J, LIU W, LUO G, et al. Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction[J]. Energy Environ Sci, 2018, 11(12): 3375-3379.
[11] WU X, TANG C J, CHENG Y, et al. Bifunctional catalysts for reversible oxygen evolution reaction and oxygen reduction reaction[J]. Chem Eur J, 2020, 26(18): 3906-3929.
[12] PANCHENKO A, KOPER M T M, SHUBINA T E , et al. Ab initio calculations of intermediates of oxygen reduction on low-index platinum surfaces[J]. J Electrochem Soc, 2004, 151: A2016-A2027.
[13] VASIC D, PASTI I, GAVRILOV N, et al. DFT study of interaction of O, O₂, and OH with unreconstructed Pt(hkl) (h, k, l=0, 1) surfaces-similarities, differences, and universalities[J]. Russ J Phys Chem A, 2013, 87: 2214-2218.
[14] NORSKOV J K, ROSSMEISL J, LOGADOTTIR A, et al. Origin of theoverpotential for oxygen reduction at a fuel-cell cathode[J]. J Phys Chem B, 2004, 108: 17886-17892.
[15] LITSTER S, MCLEAN G. PEM fuel cell electrodes[J]. J Power Sources , 2004, 130: 61-76.
[16] JUNG N, CHUNG D Y, RYU J, et al. Pt-basednanoarchitecture and catalyst design for fuel cell applications[J]. Nano Today, 2014, 9: 433-456.
[17] ANTOLINI E. Carbon supports for low-temperature fuel cell catalysts[J]. Appl Catal, B, 2009, 88: 1-24.
[18] ROY S C, HARDING A W, RUSSELL A E, et al. Spectroelectrochemical study of the role played by carbon functionality in fuel cell electrodes[J]. J Electrochem Soc, 1997, 144: 2323-2328.
[19] SHAO Y, LIU J, WANG Y, et al. Novel catalyst support materials for PEM fuel cells: current status and future prospects[J]. J Mater Chem, 2009, 19(1): 46-59.
[20] SUI S, WANG X, ZHOU X, et al. A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: nanostructure, activity, mechanism and carbon support in PEM fuel cells[J]. J Mater Chem A, 2017, 5(5): 1808-1825.
[21] DEVIVARAPRASAD R, RAMESH R, NARESH N, et al. Oxygen reduction reaction and peroxide generation on shape-controlled and polycrystalline platinum nanoparticles in acidic and alkaline electrolytes[J]. Langmuir, 2014, 30(29): 8995-9006.
[22] SHAO Y, ZHANG S, WANG C, et al. Highly durable graphene nanoplatelets supported Pt nanocatalysts for oxygen reduction[J]. J Power Sources, 2010, 195(15): 4600-4605.
[23] JIANG Y, YANG L, SUN T, et al. Significant contribution of intrinsic carbon defects to oxygen reduction activity[J]. J ACS Catal, 2015, 5: 6707-6712.
[24] AUER E, FREUND A, PIETSCH J, et al. Carbons as supports for industrial precious metal catalysts[J]. Appl Catal A, 1998, 173: 259-271.
[25] TAN Y M, XU C F, CHEN G X, et al. Facile synthesis of manganese-oxide-containing mesoporous nitrogen-doped carbon for efficient oxygen reduction[J]. Adv Funct Mater, 2012, 22: 4584-4591.
[26] WU G, LI D, DAI C, et al. Well-dispersed high-loading Pt nanoparticles supported by shell-core nanostructured carbon for methanol electrooxidation[J]. Langmuir, 2008, 24(7): 3566-3575.
[27] DUAN X, XU J, WEI Z. Metal-free carbon materials for CO₂ electrochemical reduction[J]. Adv Mater, 2017, 29(41): 1701784-1701804.
[28] DU S, LU Y, MALLADI S K, et al. A simple approach for ptni-mwcnt hybrid nanostructures as high performance electrocatalysts for the oxygen reduction reaction[J]. J Mater Chem A, 2014, 2: 692-698.
[29] BO X J, GUO L P. Ordered mesoporous boron-doped carbons as metal-free electrocatalysts for the oxygen reduction reaction in alkaline solution[J] . PCCP, 2013, 15(7): 2459-2465.
[30] LIU J, JIAO M, LU L, et al. High performance platinum single atom electrocatalyst for oxygen reduction reaction[J]. Nat Commun, 2017, 8: 15938.
[31] JACKSON C,SMITH G T, INWOOD D, et al. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum[J]. Nat Commun, 2017, 8: 15802.
[32] YANG L, CHENG D, XU H, et al. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction[J]. Proc Natl Acad Sci, 2018, 115: 6626-6631.