单原子催化剂电催化氧还原产过氧化氢研究进展

doi:10.16180/j.cnki.issn1007-7820.2022.11.013

摘要/Abstract

摘要：

通过电催化两电子氧还原反应生产过氧化氢是替代传统集中式蒽醌工艺的一种有效方法,但这种工艺依赖一种低成本、高活性和高选择性的催化剂。近年来,单原子催化剂由于其近100%的原子利用效率、可调控的电子结构和优异的催化性能,被认为是一种潜在的氧还原产过氧化氢催化剂。然而,对单原子催化剂活性的调控仍然是一个挑战。文中从氧还原反应的机理出发,阐明了活性金属中心与*OOH的结合强度对氧还原反应途径的影响,并从金属中心原子、配位原子和活性中心周围环境等3个方面来系统性地说明调控单原子催化剂的结构对金属中心与*OOH结合的影响,揭示了产过氧化氢的活性和选择性来源。

关键词: 电催化, 氧还原反应, 过氧化氢, 活性, 选择性, 单原子催化剂, *OOH中间体, 结构调控

Abstract:

Hydrogen peroxide production via electrocatalytic two-electron oxygen reduction is an effective alternative to traditional centralized anthraquinone processes. However, this process depends on a catalyst with low cost, high activity and high selectivity. In recent years, SACs have been considered as potential catalysts for oxygen reduction and hydrogen peroxide production due to their nearly 100% atom utilization efficiency, tunable electronic structure, and excellent catalytic performance, but the regulation of SAC activity remains a challenge. Starting from the mechanism of the ORR, the influence of the binding strength of the active metal center and *OOH on the oxygen reduction reaction pathway is elucidated. This study systematically illustrates the effect of adjusting the structure of the SAC on the binding of the metal center to *OOH from three aspects: metal center atom, coordination atom and the surrounding environment of the active center, and reveals the activity and selectivity of H₂O₂ production.

Key words: electrocatalysis, oxygen reduction reaction, hydrogen peroxide, activity, selectivity, single-atom catalyst, *OOH intermediate, structure regulation

中图分类号:

TN948.64

金韬,胡霞,喻兰兰,赵文军,杨麒,托娅. 单原子催化剂电催化氧还原产过氧化氢研究进展[J]. 电子科技, 2022, 35(11): 90-97.

JIN Tao,HU Xia,YU Lanlan,ZHAO Wenjun,YANG Qi,TUO Ya. Progress in Electrocatalysis Oxygen Reduction for Hydrogen Peroxide Production over Single-Atom Catalysts[J]. Electronic Science and Technology, 2022, 35(11): 90-97.

图/表 6

图1

图2

图3

图4

图5

表1

参考文献 40

[1]	Puértolas B, Hill A K, García T, et al. In-situ synthesis of hydrogen peroxide in tandem with selective oxidation reactions: A mini-review[J]. Catalysis Today, 2015, 248(25):115-127. doi: 10.1016/j.cattod.2014.03.054
[2]	Yi Y, Wang L, Li G, et al. A review on research progress in the direct synthesis of hydrogen peroxide from hydrogen and oxygen: Noble-metal catalytic method, fuel-cell method and plasma method[J]. Catalysis Science & Technology, 2016, 6(6):1593-1610.
[3]	Campos-Martin J M, Blanco-Brieva G, Fierro J L G. Hydrogen peroxide synthesis: An outlook beyond the anthraquinone process[J]. Angew Chemistry International Edition of England, 2006, 45(42):6962-6984.
[4]	Jiang Y, Ni P, Chen C, et al. Selective electrochemical H₂O₂ production through two-electron oxygen electrochemistry[J]. Advanced Energy Materials, 2018, 8(31):1614-6832.
[5]	Yamanaka I, Onizawa T, Takenaka S, et al. Direct and continuous production of hydrogen peroxide with 93% selectivity using a fuel-cell system[J]. Angewandte Chemise, 2003, 115(31):3781-3783.
[6]	Mounfield III W P, Garg A, Shao-Horn Y, et al. Electrochemical oxygen reduction for the production of hydrogen peroxide[J]. Chemistry, 2018, 4(1):18-19. doi: 10.3390/chemistry4010002
[7]	Guo X, Lin S, Gu J, et al. Simultaneously achieving high activity and selectivity toward two-electron O₂ electroreduction: The power of single-atom catalysts[J]. ACS Catalysis, 2019, 9(12):11042-11054. doi: 10.1021/acscatal.9b02778
[8]	Su J, Ge R, Dong Y, et al. Recent progress in single-atom electrocatalysts: concept, synthesis, and applications in clean energy conversion[J]. Journal of Materials Chemistry A, 2018, 6(29):14025-14042. doi: 10.1039/C8TA04064H
[9]	Gan G, Li X, Wang L, et al. Active sites in single-atom Fe-Nx-C nanosheets for selective electrochemical dechlorination of 1,2-Dichloroethane to ethylene[J]. ACS Nano, 2020, 14(8):9929-9937. doi: 10.1021/acsnano.0c02783
[10]	Huang K, Zhang L, Xu T, et al. -60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance[J]. Nature Communications, 2019, 10(1):1-10. doi: 10.1038/s41467-018-07882-8
[11]	Zhang L, Han L, Liu H, et al. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media[J]. Angewandte Chemise International Edition in English, 2017, 56(44):13694-13698.
[12]	Zhang J, Liu J, Xi L, et al. Single-atom Au/NiFe layered double hydroxide electrocatalyst:Probing the origin of activity for oxygen evolution reaction[J]. Journal of the America Chemistry Society, 2018, 140(11):3876-3879. doi: 10.1021/jacs.8b00752
[13]	Yang S, Verdaguer-Casadevall A, Arnarson L, et al. Toward the decentralized electrochemical production of H₂O₂-a focus on the catalysis[J]. ACS Catalysis, 2018, 8(5):4064-4081. doi: 10.1021/acscatal.8b00217
[14]	Kim H W, Ross M B, Kornienko N, et al. Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts[J]. Nature Catalysis, 2018, 1(4):282-290. doi: 10.1038/s41929-018-0044-2
[15]	Viswanathan V, Hansen H A, Rossmeisl J, et al. Unifying the 2e (-) and 4e (-) reduction of oxygen on metal surfaces[J]. Journal of Physics Chemistry Letter, 2012, 3(20):2948-2951.
[16]	Jirkovsky J S, Panas I, Ahlberg E, et al. Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H₂O₂ production[J]. Journal of the America Chemistry Society, 2011, 133(48):19432-19441. doi: 10.1021/ja206477z
[17]	Zhang J, Yang H, Liu B. Coordination engineering of single-atom catalysts for the oxygen reduction reaction: A review[J]. Advanced Energy Materials, 2020, 3(11):1614-6832. doi: 10.1002/aenm.201300272
[18]	Chen Z, Gong W, Liu Z, et al. Coordination-controlled single-atom tungsten as a non-3d-metal oxygen reduction reaction electrocatalyst with ultrahigh mass activity[J]. Nano Energy, 2019, 60(42):394-403. doi: 10.1016/j.nanoen.2019.03.045
[19]	Wang X, Li Z, Qu Y, et al. Review of metal catalysts for oxygen reduction reaction: From nanoscale engineering to atomic design[J]. Chemistry, 2019, 5(6):1486-1511.
[20]	Gao J, Yang H, Huang X, et al. Enabling direct H₂O₂ production in acidic media through rational design of transition metal single atom catalyst[J]. Chemistry, 2020, 6 (3):658-674.
[21]	Chen M, He Y, Spendelow J S, et al. Atomically dispersed metal catalysts for oxygen reduction[J]. ACS Energy Letters, 2019, 4(7):1619-1633. doi: 10.1021/acsenergylett.9b00804
[22]	Sun K, Xu W, Lin X, et al. Electrochemical oxygen reduction to hydrogen peroxide via a two-electron transfer pathway on carbon-based single-atom catalysts[J]. Advanced Materials Interfaces, 2020, 8(8):2196-7350.
[23]	Chen P, Zhang N, Zhou T, et al. Tailoring electronic structure of atomically dispersed metal-N₃S₁ active sites for highly efficient oxygen reduction catalysis[J]. ACS Materials Letters, 2019, 1(1):139-146. doi: 10.1021/acsmaterialslett.9b00094
[24]	Zhang J, Zhao Y, Chen C, et al. Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions[J]. Journal of the America Chemistry Society, 2019, 141(51):20118-20126. doi: 10.1021/jacs.9b09352
[25]	Xiang W, Zhao Y, Jiang Z, et al. Palladium single atoms supported by interwoven carbon nanotube and manganese oxide nanowire networks for enhanced electrocatalysis[J]. Journal of Materials Chemistry A, 2018, 46(6):23366-23377.
[26]	Jiang K, Back S, Akey A J, et al. Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination[J]. Nature Communications, 2019, 10(1):1-11. doi: 10.1038/s41467-018-07882-8
[27]	Song X, Li N, Zhang H, et al. Graphene-supported single nickel atom catalyst for highly selective and efficient hydrogen peroxide production[J]. ACS Applied Materials and Interfaces, 2020, 12(15):17519-17527. doi: 10.1021/acsami.0c01278
[28]	Choi C H, Kim M, Kwon H C, et al. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst[J]. Nature Communications, 2016, 7(7):1-9.
[29]	Ledendecker M, Pizzutilo E, Malta G, et al. Isolated Pd sites as selective catalysts for electrochemical and direct hydrogen peroxide synthesis[J]. ACS Catalysis, 2020, 10(10):5928-5938. doi: 10.1021/acscatal.0c01305
[30]	Wang Y, Shi R, Shang L, et al. High-efficiency oxygen reduction to hydrogen peroxide catalyzed by nickel single-atom catalysts with tetradentate N₂O₂ coordination in a three-phase flow cell[J]. Angewandte Chemie International Edition, 2020, 59(31):13057-13062. doi: 10.1002/anie.202004841
[31]	Tang C, Jiao Y, Shi B, et al. Coordination tunes selectivity: two-electron oxygen reduction on high-loading molybdenum single-atom catalysts[J]. Angewandte Chemie International Edition, 2020, 59(23):9171-9176. doi: 10.1002/anie.202003842
[32]	Hooe S L, Machan C W. Dioxygen reduction to hydrogen peroxide by a molecular Mn complex: Mechanistic divergence between homogeneous and heterogeneous reductants[J]. Journal of the America Chemistry Society, 2019, 141(10):4379-4387. doi: 10.1021/jacs.8b13373
[33]	Wang Y H, Goldsmith Z K, Schneider P E, et al. Kinetic and mechanistic characterization of low-overpotential, H₂O₂-selective reduction of O₂ catalyzed by N₂O₂-ligated cobalt complexes[J]. Journal of the America Chemistry Society, 2018, 140(34):10890-10899. doi: 10.1021/jacs.8b06394
[34]	Jung E, Shin H, Lee B H, et al. Atomic-level tuning of Co-N-C catalyst for high-performance electrochemical H₂O₂production[J]. Nature Materials, 2020,19(4):436-442.
[35]	Lu Z, Chen G, Siahrostami S, et al. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials[J]. Nature Catalysis, 2018, 1(2):156-162. doi: 10.1038/s41929-017-0017-x
[36]	Yin X P, Wang H J, Tang S F, et al. Engineering the coordination environment of single-atom platinum anchored on graphdiyne for optimizing electrocatalytic hydrogen evolution[J]. Angewandte Chemie International Edition, 2018, 57(30):9382-9386. doi: 10.1002/anie.201804817
[37]	Khataee A, Sajjadi S, Pouran S R, et al. A comparative study on electrogeneration of hydrogen peroxide through oxygen reduction over various plasma-treated graphite electrodes[J]. Electrochimica Acta, 2017, 244(13):38-46. doi: 10.1016/j.electacta.2017.05.069
[38]	Li B Q, Zhao C X, Liu J N, et al. Electrosynthesis of hydrogen peroxide synergistically catalyzed by atomic Co-Nx-C sites and oxygen functional groups in noble-metal-free electrocatalysts[J]. Advanced Materials, 2019, 31(35):935-964.
[39]	Su M, Chung M W, Han M H. Selective H₂O₂ production on surface-oxidized metal-nitrogen-carbon electrocatalysts[J]. Catalysis Today, 2021, 359(5):99-105. doi: 10.1016/j.cattod.2019.05.034
[40]	Kattel S, Wang G. Reaction pathway for oxygen reduction on FeN₄ embedded graphene[J]. Journal of Physics Chemistry Letters, 2014, 5(3):452-456. doi: 10.1021/jz402717r

单原子催化剂	金属负载量	选择性或产率	电解液	参考文献
Co-N-C	0.56 at%	90.9mmol·g^-1 cat·h^-1, 80%	0.5 mol·L^-1 H₂SO₄	[20]
Co-N-C and OFGs	0.60 at%	2.98 mg·cm^-2·h^-1, 80%	0.1 mol·L^-1 KOH	[38]
Surface-oxidized M-N-C (M = Fe, Co, Mn)	1.40 wt%	30~87%	0.1 mol·L^-1 HClO₄	[39]
Fe-C-O	0.10 at%	95%	0.1 mol·L^-1 KOH	[26]
Co-N4(O)-C	1.40 wt%	418± 19 mmol·g^-1 cat·h^-1	0.1 mol·L^-1 KOH	[34]
Mo-O₃S-C	13.47 wt%	95%	0.1 mol·L^-1 KOH	[31]
Ni-N₂O₂-C	2.00 wt%	5.9 mol·g^-1·h^-1, 96%	0.1 mol·L^-1 KOH	[30]
C@C₃N₄-Pa	0.50 wt%	94%	0.1 mol·L^-1 HClO₄	[29]