Abstract
Platinum-based catalysts are widely used in oxygen reduction reactions, but platinum’s high cost and low reserves have restricted their sustainable development. With continuous in-depth research, it has been found that metal-free catalysts also have better catalytic activity in oxygen reduction reactions and have great potential for development due to the low cost and abundant reserves of metal-free catalysts, which has become a hot research direction. This paper reviews the application of metal-free catalysts in oxygen reduction reactions, including heteroatom-doped carbon-based catalysts, polymeric nitrogen catalysts, and emerging carbon catalysts. This work provides insights into developing non-platinum catalysts for oxygen reduction reactions by comparing the catalytic activity, selectivity, and prolonged stability.
References
Wang Q, Hisatomi T, Jia Q, Tokudome H, Zhong M, Wang C, et al. Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nat Mater. 2016; 15: 611-5. https://doi.org/10.1038/nmat4589
Zhao P, Xu W, Hua X, Luo W, Chen S, Cheng G. Facile synthesis of a N-doped Fe C@CNT/Porous carbon hybrid for an advanced oxygen reduction and water oxidation electrocatalyst. J Phys Chem. C 2016; 120: 11006-13. https://doi.org/10.1021/acs.jpcc.6b03070
Melchionna M, Fornasiero P, Prato M. The rise of hydrogen peroxide as the main product by metal‐free catalysis in oxygen reductions. Adv Mater. 2019; 31: 1802920. https://doi.org/10.1002/adma.201802920
Yi S, Jiang H, Bao X, Zou S, Liao J, Zhang Z. Recent progress of Pt-based catalysts for oxygen reduction reaction in preparation strategies and catalytic mechanism. J Electroanal Chem. 2019; 848: 113279. https://doi.org/10.1016/j.jelechem.2019.113279
Zhou W, Meng X, Gao J, Alshawabkeh AN. Hydrogen peroxide generation from O2 electroreduction for environmental remediation: A state-of-the-art review. Chemosphere 2019; 225: 588-607. https://doi.org/10.1016/j.chemosphere.2019.03.042
Xue L, Li Y, Liu X, Liu Q, Shang J, Duan H, et al. Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Nat Commun. 2018; 9: 3819. https://doi.org/10.1038/s41467-018-06279-x
Dai L. Functionalization of graphene for efficient energy conversion and storage. Acc Chem Res. 2013; 46: 31-42. https://doi.org/10.1021/ar300122m
Paraknowitsch JP, Thomas A. Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications. Energy Environ Sci. 2013; 6: 2839-55. https://doi.org/10.1039/c3ee41444b
Wang H, Shao Y, Mei S, Lu Y, Zhang M, Sun J, et al. Polymer-derived heteroatom-doped porous carbon materials. Chem Rev. 2020; 120: 9363-419. https://doi.org/10.1021/acs.chemrev.0c00080
Li Y, Tong Y, Peng F. Metal-free carbocatalysis for electrochemical oxygen reduction reaction: Activity origin and mechanism. J Energy Chem. 2020; 48: 308-21. https://doi.org/10.1016/j.jechem.2020.02.027
Chen S, Bi J, Zhao Y, Yang L, Zhang C, Ma Y, et al. Nitrogen-doped carbon nanocages as efficient metal-free electrocatalysts for oxygen reduction reaction. Adv Mater. 2012; 24: 5593-7. https://doi.org/10.1002/adma.201202424
Feng L, Wang T, Sun H, Jiang M, Chen Y. Carbon nitride anchored on a nitrogen-doped carbon nanotube surface for enhanced oxygen reduction reaction. ACS Appl Mater Interfaces. 2020; 3: 986-91.
Wang T, Chen Z-X, Chen Y-G, Yang L-J, Yang X-D, Ye J-Y, et al. Identifying the active site of N-doped graphene for oxygen reduction by selective chemical modification. ACS Energy Lett. 2018; 3: 986-91. https://doi.org/10.1021/acsenergylett.8b00258
Han H, Noh Y, Kim Y, Jung WS, Park S, Kim WB. An N-doped porous carbon network with a multidirectional structure as a highly efficient metal-free catalyst for the oxygen reduction reaction. Nanoscale 2019; 11: 2423-33. https://doi.org/10.1039/C8NR10242B
Ren G, Chen S, Zhang J, Zhang N, Jiao C, Qiu H, et al. N-doped porous carbon spheres as metal-free electrocatalyst for oxygen reduction reaction. J Mater Chem A Mater. 2021; 9: 5751-8. https://doi.org/10.1039/D0TA11493F
Jang A-R, Lee Y-W, Lee S-S, Hong J, Beak S-H, Pak S, et al. Electrochemical and electrocatalytic reaction characteristics of boron-incorporated graphene via a simple spin-on dopant process. J Mater Chem A Mater. 2018; 6: 7351-6. https://doi.org/10.1039/C7TA09517A
Yang L, Jiang S, Zhao Y, Zhu L, Chen S, Wang X, et al. Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem Int Ed. 2011; 50: 7132-5. https://doi.org/10.1002/anie.201101287
Radovic LR, Salgado-Casanova AJA, Mora-Vilches CV. On the active sites for the oxygen reduction reaction catalyzed by graphene-based materials. Carbon 2020; 156: 389-98. https://doi.org/10.1016/j.carbon.2019.09.059
Bakhtavar S, Mehrpooya M, Manoochehri M, Karimkhani M. Proposal of a facile method to fabricate a multi-dope multiwall carbon nanotube as a metal-free electrocatalyst for the oxygen reduction reaction. Sustainability 2022; 14: 965. https://doi.org/10.3390/su14020965
Yang Z, Yao Z, Li G, Fang G, Nie H, Liu Z, et al. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano. 2012; 6: 205-11. https://doi.org/10.1021/nn203393d
Puziy AM, Poddubnaya OI, Gawdzik B, Tascón JMD. Phosphorus-containing carbons: Preparation, properties and utilization. Carbon 2020; 157: 796-846. https://doi.org/10.1016/j.carbon.2019.10.018
Yang D-S, Bhattacharjya D, Inamdar S, Park J, Yu J-S. Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. J Am Chem Soc. 2012; 134: 16127-30. https://doi.org/10.1021/ja306376s
Durajski AP, Gruszka KM, Niegodajew P. The influence of heteroatom doping on local properties of phosphorene monolayer. Sci Rep. 2021; 11: 18494. https://doi.org/10.1038/s41598-021-98014-8
Quílez-Bermejo J, Ghisolfi A, Grau-Marín D, San-Fabián E, Morallón E, Cazorla-Amorós D. Post-synthetic efficient functionalization of polyaniline with phosphorus-containing groups. Effect of phosphorus on electrochemical properties. Eur Polym J. 2019; 119: 272-80. https://doi.org/10.1016/j.eurpolymj.2019.07.048
Lei W, Deng Y-P, Li G, Cano ZP, Wang X, Luo D, et al. Two-dimensional phosphorus-doped carbon nanosheets with tunable porosity for oxygen reactions in zinc-air batteries. ACS Catal. 2018; 8: 2464-72. https://doi.org/10.1021/acscatal.7b02739
Zhao Y, Yang L, Chen S, Wang X, Ma Y, Wu Q, et al. Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes? J Am Chem Soc. 2013; 135: 1201-4. https://doi.org/10.1021/ja310566z
Sun T, Wang J, Qiu C, Ling X, Tian B, Chen W, et al. B, N codoped and defect-rich nano-carbon material as a metal-free bifunctional electrocatalyst for oxygen reduction and evolution reactions. Adv Sci. 2018; 5(7): 1-9. https://doi.org/10.1002/advs.201800036
Li Z, Zhao W, Yin C, Wei L, Wu W, Hu Z, et al. Synergistic effects between doped nitrogen and phosphorus in metal-free cathode for zinc-air battery from covalent organic frameworks coated CNT. ACS Appl Mater Interfaces. 2017; 9: 44519-28. https://doi.org/10.1021/acsami.7b14815
Zhao G, Shi L, Xu J, Yan X, Zhao TS. Role of phosphorus in nitrogen, phosphorus dual-doped ordered mesoporous carbon electrocatalyst for oxygen reduction reaction in alkaline media. Int J Hydrogen Energy. 2018; 43: 1470-8. https://doi.org/10.1016/j.ijhydene.2017.11.165
Zhang J, Zhao Z, Xia Z, Dai L. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol. 2015; 10: 444-52. https://doi.org/10.1038/nnano.2015.48
Yang M, Shu X, Zhang J. A defect‐rich N, P Codoped carbon foam as efficient electrocatalyst toward oxygen reduction reaction. ChemCatChem. 2020; 12: 4105-11. https://doi.org/10.1002/cctc.202000363
Hu C, Dai L. Multifunctional carbon‐based metal‐free electrocatalysts for simultaneous oxygen reduction, oxygen evolution, and hydrogen evolution. Adv Mater. 2017; 29: 1-9. https://doi.org/10.1002/adma.201604942
Kim M-J, Park JE, Kim S, Lim MS, Jin A, Kim O-H, et al. Biomass-derived air cathode materials: Pore-controlled S,N-Co-doped carbon for fuel cells and metal–air batteries. ACS Catal 2019; 9: 3389-98. https://doi.org/10.1021/acscatal.8b03730
Zhou S, Zang J, Gao H, Tian X, Tian P, Song S, et al. Deflagration method synthesizing N, S co-doped oxygen-functionalized carbons as a bifunctional catalyst for oxygen reduction and oxygen evolution reaction. Carbon N Y 2021; 181: 234-45. https://doi.org/10.1016/j.carbon.2021.05.034
Zhang B, Chen R, Yang Z, Chen Y, Zhou L, Yuan Y. Rapeseed meal-based autochthonous N and S-doped non-metallic porous carbon electrode material for oxygen reduction reaction catalysis. Int J Hydrogen Energy. 2021; 46: 508-17. https://doi.org/10.1016/j.ijhydene.2020.09.198
Zhu P, Gao J, Chen X, Liu S. An efficient metal-free bifunctional oxygen electrocatalyst of carbon co-doped with fluorine and nitrogen atoms for rechargeable Zn-air battery. Int J Hydrogen Energy. 2020; 45: 9512-21. https://doi.org/10.1016/j.ijhydene.2020.01.131
Lv Y, Yang L, Cao D. Nitrogen and fluorine-codoped porous carbons as efficient metal-free electrocatalysts for oxygen reduction reaction in fuel cells. ACS Appl Mater Interfaces. 2017; 9: 32859-67. https://doi.org/10.1021/acsami.7b11371
Zhang J, Dai L. Nitrogen, phosphorus, and fluorine tri‐doped graphene as a multifunctional catalyst for self-powered electrochemical water splitting. Angew Chem Int Ed. 2016; 55: 13296-300. https://doi.org/10.1002/anie.201607405
Long Y, Ye F, Shi L, Lin X, Paul R, Liu D, et al. N, P, and S tri-doped holey carbon as an efficient electrocatalyst for oxygen reduction in whole pH range for fuel cell and zinc-air batteries. Carbon. 2021; 179: 365-76. https://doi.org/10.1016/j.carbon.2021.04.039
Liu Z, Wang M, Luo X, Li S, Li S, Zhou Q, et al. N-, P-, and O-doped porous carbon: A trifunctional metal-free electrocatalyst. Appl Surf Sci. 2021; 544: 1-10. https://doi.org/10.1016/j.apsusc.2020.148912
Xue L, Li Y, Liu X, Liu Q, Shang J, Duan H, et al. Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Nat Commun. 2018; 9: 1-8. https://doi.org/10.1038/s41467-018-06279-x
Dong F, Wu M, Zhang G, Liu X, Rawach D, Tavares AC, et al. Defect engineering of carbon‐based electrocatalysts for rechargeable zinc‐air batteries. Chem Asian J. 2020; 15: 3737-51. https://doi.org/10.1002/asia.202001031
Hu C, Dai L. Doping of carbon materials for metal‐free electrocatalysis. Adv Mater. 2019; 31: 1-17. https://doi.org/10.1002/adma.201804672
Tao L, Wang Q, Dou S, Ma Z, Huo J, Wang S, et al. Edge-rich and dopant-free graphene as a highly efficient metal-free electrocatalyst for the oxygen reduction reaction. Chem Commun. 2016; 52: 2764-7. https://doi.org/10.1039/C5CC09173J
Ma X, Li S, Hessel V, Lin L, Meskers S, Gallucci F. Synthesis of N-doped carbon dots via a microplasma process. Chem Eng Sci. 2020; 220: 1-10. https://doi.org/10.1016/j.ces.2020.115648
Zhu J, Huang Y, Mei W, Zhao C, Zhang C, Zhang J, et al. Effects of intrinsic pentagon defects on electrochemical reactivity of carbon nanomaterials. Angew Chem Int Ed Engl. 2019; 58: 3859-64. https://doi.org/10.1002/anie.201813805
Jia Y, Zhang L, Zhuang L, Liu H, Yan X, Wang X, et al. Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping. Nat Catal. 2019; 2: 688-95. https://doi.org/10.1038/s41929-019-0297-4
Wu Z, Benchafia EM, Iqbal Z, Wang X. N8 (-) polynitrogen stabilized on multi-wall carbon nanotubes for oxygen-reduction reactions at ambient conditions. Angew Chem Int Ed. 2014; 53: 12555-9. https://doi.org/10.1002/anie.201403060
Gao J, Wang Y, Wu H, Liu X, Wang L, Yu Q, et al. Construction of a sp3 /sp2 carbon interface in 3D N‐doped nanocarbons for the oxygen reduction reaction. Angew Chem Int Ed Engl. 2019; 58: 15089-97. https://doi.org/10.1002/anie.201907915
Shi X, Liu B, Liu S, Niu S, Liu S, Liu R, et al. Polymeric nitrogen A7 layers stabilized in the confinement of a multilayer BN matrix at ambient conditions. Sci Rep. 2018; 8: 1-8. https://doi.org/10.1038/s41598-018-31973-7
Niu S, Liu S, Liu B, Shi X, Liu S, Liu R, et al. High energetic polymeric nitrogen sheet confined in a graphene matrix. RSC Adv. 2018; 8: 30912-8. https://doi.org/10.1039/C8RA03453B
Yao Z, Hu M, Iqbal Z, Wang X. N8 - Polynitrogen stabilized on boron-doped graphene as metal-free electrocatalysts for oxygen reduction reaction. ACS Catal. 2020; 10: 160-7. https://doi.org/10.1021/acscatal.9b03610
Yao Z, Fan R, Ji W, Yan T, Hu M. N8− Polynitrogen stabilized on nitrogen-doped carbon nanotubes as an efficient electrocatalyst for oxygen reduction reaction. Catalysts 2020;10: 1-11. https://doi.org/10.3390/catal10080864
Gao J, Wang Y, Wu H, Liu X, Wang L, Yu Q, et al. Construction of a sp3 /sp2 carbon interface in 3D N‐doped nanocarbons for the oxygen reduction reaction. Angew Chem Int Ed. 2019; 58: 15089-97. https://doi.org/10.1002/anie.201907915
Yang Q, Xiao Z, Kong D, Zhang T, Duan X, Zhou S, et al. New insight to the role of edges and heteroatoms in nanocarbons for oxygen reduction reaction. Nano Energy. 2019; 66: 1-8. https://doi.org/10.1016/j.nanoen.2019.104096
Guo D, Shibuya R, Akiba C, Saji S, Kondo T, Nakamura J. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science (1979) 2016; 351: 361-5. https://doi.org/10.1126/science.aad0832
Zhao Y, Wan J, Yao H, Zhang L, Lin K, Wang L, et al. Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis. Nat Chem. 2018; 10: 924-31. https://doi.org/10.1038/s41557-018-0100-1
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
Copyright (c) 2022 Ruiquan Zhang, Zhou Zhang, Qing Chen, Maocong Hu, Zhenhua Yao