过渡金属基催化剂用于氧析出反应的研究进展

doi:10.19799/j.cnki.2095-4239.2021.0441

摘要/Abstract

摘要：

由于动力学缓慢，在能源转换和储存过程中，特别是在电解水过程，氧析出反应(OER)是一个关键的限制性反应。目前该领域所面临的主要挑战是探索不含贵金属的催化剂，以促进OER反应过程。由于独特的化学、物理特性和低廉的使用成本，过渡金属基化合物在水的电化学分解过程中的应用得到了广泛关注。本文综述了尖晶石、钙钛矿和层状双金属氢氧化物(LDH)三种过渡金属化合物作为OER电催化剂的最新研究现状和进展，重点介绍了提高OER催化活性和催化剂稳定性的策略以及相应催化剂的催化性能和效果。综合当前文献的研究结果可以发现，OER催化活性的提高主要有两种措施：一是在催化剂中引入更多的催化活性位点，并且保证这些活性位点尽可能暴露在催化剂的表面；二是优化催化剂的导电性能。通过控制尺寸、形态、晶格缺陷、氧空位、相态及化学组成，或者与导电材料相复合，可以在一定程度上满足上述两种要求。最后，对OER电催化剂的未来发展方向进行简要讨论。

关键词: 尖晶石, 钙钛矿, 层状金属氢氧化物, 氧析出反应

Abstract:

Oxygen evolution reaction (OER) is a limiting process in energy conversion and storage due to its sluggish kinetics, especially in water electrolysis. The critical challenge in this area is to explore alternative precious-metal-free catalysts to promote the OER process. Transition metal-based compounds have attracted much attention in electrochemical water splitting because of their unique chemical and physical properties, as well as low cost. In this review, we summarize the recent research status and progress of spinel, perovskite and layered double hydroxides as electrocatalysts for OER, which have been extensively studied in recent years. The researcher strategies developed to promote electrocatalytic activities and stability are described, along with the electrochemical properties of theses developed catalysts. Based on related references, we observed that there are generally two strategies to improve OER catalyst activities: (1) introduce more active sites and expose them to the catalyst surface and (2) optimize the conductivity of OER catalysts. These requirements can be met to some extent by the controlling size, morphology, intrinsic and lattice defects, oxygen vacancies, phase and composition of OER catalysts, and by the incorporation of conducting materials in composites. Finally, the future development of OER electrocatalysts is briefly discussed.

Key words: spinel, perovskite, layered double, oxygen evolution reaction

中图分类号:

O 643.36

宋乃建, 郭明媛, 南皓雄, 喻嘉. 过渡金属基催化剂用于氧析出反应的研究进展[J]. 储能科学与技术, 2021, 10(6): 1906-1917.

Naijian SONG, Mingyuan GUO, Haoxiong NAN, Jia YU. Recent advances in transition metal-based catalysts for oxygen evolution reaction[J]. Energy Storage Science and Technology, 2021, 10(6): 1906-1917.

图/表 8

参考文献 53

1	QADIR S A, AL-MOTAIRI H, TAHIR F, et al. Incentives and strategies for financing the renewable energy transition: A review[J]. Energy Reports, 2021, 7: 3590-3606.
2	CHEN X L, PAUL R, DAI L M. Carbon-based supercapacitors for efficient energy storage[J]. National Science Review, 2017, 4(3): 453-489.
3	RAHMAN S T, RHEE K Y, PARK S J. Nanostructured multifunctional electrocatalysts for efficient energy conversion systems: Recent perspectives[J]. Nanotechnology Reviews, 2021, 10(1): 137-157.
4	RATNAKAR R R, GUPTA N, ZHANG K, et al. Hydrogen supply chain and challenges in large-scale LH₂ storage and transportation[J]. International Journal of Hydrogen Energy, 2021, 46(47): 24149-24168.
5	ANWAR S, KHAN F, ZHANG Y H, et al. Recent development in electrocatalysts for hydrogen production through water electrolysis[J]. International Journal of Hydrogen Energy, 2021, 46(63): 32284-32317.
6	WEI T, LIU B, JIA L C, et al. Perovskite materials for highly efficient catalytic CH₄ fuel reforming in solid oxide fuel cell[J]. International Journal of Hydrogen Energy, 2021, 46(48): 24441-24460.
7	LIU Q F, PAN Z F, WANG E D, et al. Aqueous metal-air batteries: Fundamentals and applications[J]. Energy Storage Materials, 2020, 27: 478-505.
8	CHEN F Y, WU Z Y, ADLER Z, et al. Stability challenges of electrocatalytic oxygen evolution reaction: From mechanistic understanding to reactor design[J]. Joule, 2021, 5(7): 1704-1731.
9	CAO D F, SHOU H W, CHEN S M, et al. Manipulating and probing the structural self-optimization in oxygen evolution reaction catalysts[J]. Current Opinion in Electrochemistry, 2021, 30: doi: 10.1016/j.coelec.2021.100788.
10	WANG X Y, HUO P Y, LIU Y, et al. High-throughput screening of ternary vanadate photoanodes for efficient oxygen evolution reactions: A review of band-gap engineering[J]. Applied Catalysis A: General, 2021, 616: doi: 10.1016/j.apcata.2021.118073.
11	MAZZEO A, SANTALLA S, GAVIGLIO C, et al. Recent progress in homogeneous light-driven hydrogen evolution using first-row transition metal catalysts[J]. Inorganica Chimica Acta, 2021, 517: doi: 10.1016/j.ica.2020.119950.
12	KUMBHAR V S, LEE H, LEE J, et al. Recent advances in water-splitting electrocatalysts based on manganese oxide[J]. Carbon Resources Conversion, 2019, 2(3): 242-255.
13	SUN H N, HE J, HU Z W, et al. Multi-active sites derived from a single/double perovskite hybrid for highly efficient water oxidation[J]. Electrochimica Acta, 2019, 299: 926-932.
14	LIU Z, WANG G, ZHU X, et al. Optimal geometrical configuration of cobalt cations in spinel oxides to promote oxygen evolution reaction[J]. Angewandte Chemie International Edition, 2020, 59(12): 4736-4742.
15	CHEN R, HUNG S F, ZHOU D, et al. Layered structure causes bulk NiFe layered double hydroxide unstable in alkaline oxygen evolution reaction[J]. Advanced Materials, 2019, 31(41): doi: 10.1002/adma.201903909.
16	PENG L S, SHAH S S A, WEI Z D. Recent developments in metal phosphide and sulfide electrocatalysts for oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2018, 39(10): 1575-1593.
17	KANG T, KIM J. Optimal cobalt-based catalyst containing high-ratio of oxygen vacancy synthesized from metal-organic-framework (MOF) for oxygen evolution reaction (OER) enhancement[J]. Applied Surface Science, 2021, 560: doi: 10.1016/j.apsusc.2021.150035.
18	LIU X M, CUI X Y, DASTAFKAN K, et al. Recent advances in spinel-type electrocatalysts for bifunctional oxygen reduction and oxygen evolution reactions[J]. Journal of Energy Chemistry, 2021, 53: 290-302.
19	SRINIVASA N, SHREENIVASA L, ADARAKATTI P S, et al. Functionalized Co₃O₄ graphitic nanoparticles: A high performance electrocatalyst for the oxygen evolution reaction[J]. International Journal of Hydrogen Energy, 2020, 45(56): 31380-31388.
20	LENG M, HUANG X L, XIAO W, et al. Enhanced oxygen evolution reaction by Co-O-C bonds in rationally designed Co₃O₄/graphene nanocomposites[J]. Nano Energy, 2017, 33: 445-452.
21	NAGAJYOTHI P C, RAMARAGHAVULU R, MUNIRATHNAM K, et al. One-pot hydrothermal synthesis: Enhanced MOR and OER performance using low-cost Mn₃O₄ electrocatalyst[J]. International Journal of Hydrogen Energy, 2021, 46(27): 13946-13951.
22	RANI B J, RAVI G, YUVAKKUMAR R, et al. Neutral and alkaline chemical environment dependent synthesis of Mn₃O₄ for oxygen evolution reaction (OER)[J]. Materials Chemistry and Physics, 2020, 247: doi: 10.1016/j.matchemphys.2020.122864.
23	WEI M M, HAN Y Q, LIU Y, et al. Green preparation of Fe₃O₄ coral-like nanomaterials with outstanding magnetic and OER properties[J]. Journal of Alloys and Compounds, 2020, 831: doi: 10.1016/j.jallcom.2020.154702.
24	ISHIHARA T, YOKOE K, MIYANO T, et al. Mesoporous MnCo₂O₄ spinel oxide for a highly active and stable air electrode for Zn-air rechargeable battery[J]. Electrochimica Acta, 2019, 300: 455-460.
25	ZENG K, LI W, ZHOU Y, et al. Multilayer hollow MnCo₂O₄ microsphere with oxygen vacancies as efficient electrocatalyst for oxygen evolution reaction[J]. Chemical Engineering Journal, 2021, 421: doi: 10.1016/j.cej.2020.127831.
26	YIN J, JIN J, LIU H B, et al. NiCo₂O₄-based nanosheets with uniform 4 nm mesopores for excellent Zn-air battery performance[J]. Advanced Materials, 2020, 32(39): doi: 10.1002/adma.202001651.
27	FARIA E R, RIBEIRO F M, FRANCO D V, et al. Fabrication and characterisation of a mixed oxide-covered mesh electrode composed of NiCo₂O₄ and its capability of generating hydroxyl radicals during the oxygen evolution reaction in electrolyte-free water[J]. Journal of Solid State Electrochemistry, 2018, 22(5): 1289-1302.
28	TAO L M, GUO P H, ZHU W L, et al. Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2020, 41(12): 1855-1863.
29	ALEGRE C, BUSACCA C, DI BLASI A, et al. Toward more efficient and stable bifunctional electrocatalysts for oxygen electrodes using FeCo₂O₄/carbon nanofiber prepared by electrospinning[J]. Materials Today Energy, 2020, 18: doi: 10.1016/j.mtener.2020. 100508.
30	TONG Y L, LIU H Q, DAI M Z, et al. Metal-organic framework derived Co₃O₄/PP_y bifunctional electrocatalysts for efficient overall water splitting[J]. Chinese Chemical Letters, 2020, 31(9): 2295-2299.
31	LIU W, HAN J, YAMADA I, et al. Effects of zinc ions at tetrahedral sites in spinel oxides on catalytic activity for oxygen evolution reaction[J]. Journal of Catalysis, 2021, 394: 50-57.
32	HUANG Y, ZHANG S L, LU X F, et al. Trimetallic spinel NiCo_2-xFexO₄ nanoboxes for highly efficient electrocatalytic oxygen evolution[J]. Angewandte Chemie International Edition, 2021, 60(21): 11841-11846.
33	LIU W J, RAO D W, BAO J, et al. Strong coupled spinel oxide with N-rGO for high-efficiency ORR/OER bifunctional electrocatalyst of Zn-air batteries[J]. Journal of Energy Chemistry, 2021, 57: 428-435.
34	SUEN N T, HUNG S F, QUAN Q, et al. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives[J]. Chemical Society Reviews, 2017, 46(2): 337-365.
35	NGUYEN T X, LIAO Y C, LIN C C, et al. Advanced high entropy perovskite oxide electrocatalyst for oxygen evolution reaction[J]. Advanced Functional Materials, 2021, 31(27): doi: 10.1002/adfm. 202101632.
36	KIM B J, FABBRI E, ABBOTT D F, et al. Functional role of Fe-doping in co-based perovskite oxide catalysts for oxygen evolution reaction[J]. Journal of the American Chemical Society, 2019, 141(13): 5231-5240.
37	WANG H, WANG J, PI Y, et al. Double perovskite LaFexNi_1-xO₃ nanorods enable efficient oxygen evolution electrocatalysis[J]. Angewandte Chemie International Edition, 2019, 58(8): 2316-2320.
38	XIONG J, ZHONG H, LI J, et al. Engineering highly active oxygen sites in perovskite oxides for stable and efficient oxygen evolution[J]. Applied Catalysis B: Environmental, 2019, 256: doi: 10.1016/j.apcatb.2019.117817.
39	POROKHIN S V, NIKITINA V A, AKSYONOV D A, et al. Mixed-cation perovskite La_0.6Ca_0.4Fe_0.7Ni_0.3O_2.9 as a stable and efficient catalyst for the oxygen evolution reaction[J]. ACS Catalysis, 2021, 11(13): 8338-8348.
40	ZHU K Y, WU T, LI M R, et al. Perovskites decorated with oxygen vacancies and Fe-Ni alloy nanoparticles as high-efficiency electrocatalysts for the oxygen evolution reaction[J]. Journal of Materials Chemistry A, 2017, 5(37): 19836-19845.
41	KOU Z K, YU Y, LIU X M, et al. Potential-dependent phase transition and Mo-enriched surface reconstruction of γ-CoOOH in a heterostructured co-Mo₂C precatalyst enable water oxidation[J]. ACS Catalysis, 2020, 10(7): 4411-4419.
42	HU W K, LIU Q, LV T, et al. Impact of interfacial CoOOH on OER catalytic activities and electrochemical behaviors of bimetallic CoxNi-LDH nanosheet catalysts[J]. Electrochimica Acta, 2021, 381: doi: 10.1016/j.electacta.2021.138276.
43	WANG Q, O'HARE D. Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets[J]. Chemical Reviews, 2012, 112(7): 4124-4155.
44	YIN H, TANG Z. Ultrathin two-dimensional layered metal hydroxides: An emerging platform for advanced catalysis, energy conversion and storage[J]. Chemical Society Reviews, 2016, 45(18): 4873-4891.
45	ZHU W J, CHEN W X, YU H H, et al. NiCo/NiCo-OH and NiFe/NiFe-OH core shell nanostructures for water splitting electrocatalysis at large currents[J]. Applied Catalysis B: Environmental, 2020, 278: doi: 10.1016/j.apcatb.2020.119326.
46	DIONIGI F, ZHU J, ZENG Z, et al. Intrinsic electrocatalytic activity for oxygen evolution of crystalline 3d-transition metal layered double hydroxides[J]. Angewandte Chemie International Edition, 2021, 60(26): 14446-14457.
47	LEE S, BAI L, HU X. Deciphering iron-dependent activity in oxygen evolution catalyzed by nickel-iron layered double hydroxide[J]. Angewandte Chemie International Edition, 2020, 59(21): 8072-8077.
48	FERREIRA DE A J, DIONIGI F, MERZDORF T, et al. Evidence of Mars-van-krevelen mechanism in the electrochemical oxygen evolution on Ni-based catalysts[J]. Angew Chem Int Ed Engl, 2021, 60(27): 14981-14988.
49	ZHU G X, LI X Y, LIU Y J, et al. Scalable surface engineering of commercial metal foams for defect-rich hydroxides towards improved oxygen evolution[J]. Journal of Materials Chemistry A, 2020, 8(25): 12603-12612.
50	LIU Z J, HUANG Y C, WANG Y Y, et al. Quinary defect-rich ultrathin bimetal hydroxide nanosheets for water oxidation[J]. ACS Applied Materials & Interfaces, 2019, 11(47): 44018-44025.
51	WANG B, SHANG J, GUO C, et al. A general method to ultrathin bimetal-MOF nanosheets arrays via in situ transformation of layered double hydroxides arrays[J]. Small, 2019, 15(6): doi: 10.1002/smll.201804761.
52	ZHANG J F, ZHANG H J, HUANG Y. Electron-rich NiFe layered double hydroxides via interface engineering for boosting electrocatalytic oxygen evolution[J]. Applied Catalysis B: Environmental, 2021, 297: doi: 10.1016/j.apcatb.2021.120453.
53	GU H Y, SHI G S, CHEN H C, et al. Strong catalyst-support interactions in electrochemical oxygen evolution on Ni-Fe layered double hydroxide[J]. ACS Energy Letters, 2020, 5(10): 3185-3194.

[1]	王培灿, 万磊, 徐子昂, 许琴, 庞茂斌, 陈金勋, 王保国. 基于界面工程的自支撑催化电极用于电解水制氢[J]. 储能科学与技术, 2022, 11(6): 1934-1946.
[2]	邹文午, 蒋国星, 杜丽. 共价有机框架材料（COFs）在氧电极电催化中的研究进展[J]. 储能科学与技术, 2021, 10(6): 1891-1905.
[3]	朱子岳, 符冬菊, 陈建军, 曾燮榕. 锌空气电池非贵金属双功能阴极催化剂研究进展[J]. 储能科学与技术, 2020, 9(5): 1489-1496.
[4]	董旭, 杜志鸿, 张旸, 李科云, 赵海雷. 固体氧化物燃料电池高催化活性阴极材料SrFeF _x O_3- _x _- _δ [J]. 储能科学与技术, 2020, 9(2): 415-424.
[5]	熊小琳, 岳金明, 周安行, 索鎏敏, 胡勇胜, 李泓, 黄学杰. 尖晶石锰酸锂正极在Water-in-salt电解液中的电化学性能[J]. 储能科学与技术, 2020, 9(2): 375-384.
[6]	陈祥，雷凯翔，孙洪明，程方益，陈军. 尖晶石型氧化物催化剂与金属-空气电池[J]. 储能科学与技术, 2017, 6(5): 904-923.
[7]	王雪龙，肖睿娟，李泓，陈立泉. 反钙钛矿Li3OX(X=F,Cl,Br)快离子导体的密度泛函研究[J]. 储能科学与技术, 2016, 5(5): 725-729.
[8]	金玉红, 王莉, 尚玉明, 高剑, 李建军, 何向明. 尖晶石结构NiCo₂O₄材料在超级电容器中的应用进展[J]. 储能科学与技术, 2015, 4(1): 44-54.
[9]	徐长志, 靳映霞, 柳清菊. 钙钛矿型太阳能电池的研究进展[J]. 储能科学与技术, 2014, 3(6): 597-601.