Research Progress on Defect Engineering of Nickel⁃Iron⁃Based Transition Metal Catalysts for Oxygen Evolution Reaction Performance Enhancement

doi:10.12422/j.issn.1006-396X.2025.03.005

Abstract

Abstract:

Nickel?iron (NiFe)?based transition metal catalysts have garnered significant attention in recent years for their excellent electrocatalytic performance,particularly in the oxygen evolution reaction (OER).However, the catalytic efficiency of NiFe?based transition metal catalysts still has a certain gap compared with precious metal Ru or Ir, so it is necessary to modify it.Research has shown that defect engineering can effectively enhance the OER catalytic activity of NiFe?based transition metal catalysts.The types of defects in NiFe?based transition metal catalysts, the characterization methods, and the methods for constructing defect materials are summarized, and an overview the research progress of the OER study of defect?type NiFe?based transition metal catalysts is given; the challenges of defect engineering to improve the OER performance are discussed and prospects for future development are proposed.

Key words: Nickel?iron?based transition metals, Defect engineering, Construction, Electrocatalysts, Oxygen evolution reaction

摘要：

镍铁（NiFe）基过渡金属催化剂因其优异的电催化性能，近年来在析氧反应（OER）中受到了广泛关注。然而，与贵金属Ru或Ir相比，NiFe基过渡金属催化剂的催化效率仍存在一定差距，因此对其改性十分必要。通过缺陷工程能够有效提升NiFe基过渡金属催化剂的OER催化活性。总结了NiFe基过渡金属催化剂的缺陷类型、表征方法，并概述了缺陷材料的构筑方法、缺陷型NiFe基过渡金属催化剂OER的研究进展；针对缺陷工程提升OER性能所面临的挑战进行了探讨，并对未来的发展提出了展望。

关键词: 镍铁基过渡金属, 缺陷工程, 构筑, 电催化剂, 析氧反应

CLC Number:

TQ136.1

Meixia CHEN, Tianfeng CAI, Qiao HAN, Zhanxu YANG. Research Progress on Defect Engineering of Nickel⁃Iron⁃Based Transition Metal Catalysts for Oxygen Evolution Reaction Performance Enhancement[J]. Journal of Petrochemical Universities, 2025, 38(3): 44-53.

陈梅霞, 蔡天凤, 韩乔, 杨占旭. 镍铁基过渡金属催化剂缺陷调控析氧反应性能研究进展[J]. 石油化工高等学校学报, 2025, 38(3): 44-53.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2025.03.005

https://journal.lnpu.edu.cn/syhg/EN/Y2025/V38/I3/44

Figures/Tables 4

Fig.1 Schematic illustration of introducing oxygen vacancy defects to NiFe LDH nanoarray electrode[19]

Fig.2 The density of states and d-band center of Ni and Fe atoms without VO and with VO[22]

Fig.3 The synthesis of porous monolayer LDH and monolayer LDH[30]

Fig.4 The synthesis of NiFe LDHs-VFe and NiFe LDHs-VNi by strong alkali etching LDHs[43]

References 60

1	HASSAN Q， SAMEEN A Z， SALMAN H M， et al. Hydrogen energy future： Advancements in storage technologies and implications for sustainability［J］. Journal of Energy Storage， 2023， 72（Part B）： 108404.
2	宋楗，韩乔，杨占旭. NiMoP/C复合材料的制备及其电催化析氢性能［J］. 石油化工高等学校学报， 2022， 35（1）： 1⁃9.
	SONG J， HAN Q， YANG Z X. Preparation of NiMoP/C composite material and electrocatalytic hydrogen evolution performance［J］. Journal of Petrochemical Universities， 2022， 35（1）： 1⁃9.
3	张瑀净，张宝山，孙洁. 电解水制氢技术及其催化剂研究进展［J］. 石油化工高等学校学报， 2022， 35（6）： 19⁃27.
	ZHANG Y J， ZHANG B S， SUN J. Progress in hydrogen production by water electrolysis and its electrocatalysts［J］. Journal of Petrochemical Universities， 2022， 35（6）： 19⁃27.
4	王佳乐，武宏大，韩乔，等. 钼基量子点制备的研究进展［J］. 石油化工高等学校学报， 2023， 36（5）： 52⁃59.
	WANG J L， WU H D， HAN Q， et al. Research progress in preparation of molybdenum⁃based quantum dots［J］. Journal of Petrochemical Universities， 2023， 36（5）： 52⁃59.
5	WANG S， LU A L， ZHONG C J. Hydrogen production from water electrolysis： Role of catalysts［J］. Nano Convergence， 2021， 8（1）： 4.
6	YOU B， SUN Y J. Innovative strategies for electrocatalytic water splitting［J］. Accounts of Chemical Research， 2018， 51（7）： 1571⁃1580.
7	LIU X， CHI J Q， DONG B， et al. Recent progress in decoupled H₂ and O₂ production from electrolytic water splitting［J］. ChemElectroChem， 2019， 6（8）： 2157⁃2166.
8	LIU Y Y， ZHOU D J， DENG T Y， et al. Research progress of oxygen evolution reaction catalysts for electrochemical water splitting［J］. ChemSusChem， 2021， 14（24）： 5359⁃5383.
9	XIE Q X， REN D， BAI L C， et al. Investigation of nickel iron layered double hydroxide for water oxidation in different pH electrolytes［J］. Chinese Journal of Catalysis， 2023， 44： 127⁃138.
10	WANG H， JIANG H M， GAO C， et al. Self supported FeS/Fe₅Ni₄S₈ heterostructure catalyst for efficient water splitting［J］. Chemical Engineering Journal， 2024， 501： 157738.
11	QIAN Z X， LIANG G H， SHEN L F， et al. Phase engineering facilitates O-O coupling via lattice oxygen mechanism for enhanced oxygen evolution on nickel–iron phosphide［J］. Journal of the American Chemical Society， 2025， 147（1）： 1334⁃1343.
12	HAN Y J， WANG J Y， LIU Y H， et al. Stability challenges and opportunities of NiFe⁃based electrocatalysts for oxygen evolution reaction in alkaline media［J］. Carbon Neutralization， 2024， 3（2）： 172⁃198.
13	WANG J Y， XING Z Y， KANG R Y， et al. Metal nitride controlled atomic doping of Mox+ in NiFe（Oxy）hydroxide to trigger lattice oxygen‐mediated mechanism for superior oxygen evolution［J］. Advanced Functional Materials， 2025， 35（14）： 2418439.
14	MU L， YING J F， OU Y Y， et al. Cation⁃anion modification and heterostructure for cooperative regulation of electron distribution in NiMoS/NiFeMn⁃LDH electrocatalyst to enhance water splitting［J］. Journal of Colloid and Interface Science， 2025， 688： 106⁃117.
15	LIU F X， LIANG Q， LI Z Y， et al. Hierarchical FeOxHy@Ni₃B hybrid for efficient alkaline oxygen evolution at high current density［J］. Journal of Energy Chemistry， 2024， 94： 599⁃607.
16	WU F Y， TIAN F Y， LI M G， et al. Engineering lattice oxygen regeneration of NiFe layered double hydroxide enhances oxygen evolution catalysis durability［J］. Angewandte Chemie International Edition， 2025， 64（1）： e202413250.
17	CHEN M X， ZHANG Y Y， CHEN J， et al. In situ raman study of surface reconstruction of FeOOH/Ni₃S₂ oxygen evolution reaction electrocatalysts［J］. Small， 2024， 20（23）： 2309371.
18	WU L B， NING M H， XING X X， et al. Boosting oxygen evolution reaction of （Fe， Ni）OOH via defect engineering for anion exchange membrane water electrolysis under industrial conditions［J］. Advanced Materials， 2023， 35（44）： e2306097.
19	XIONG X Y， CAI Z， ZHOU D J， et al. A highly⁃efficient oxygen evolution electrode based on defective nickel⁃iron layered double hydroxide［J］. Science China Materials， 2018， 61（7）： 939⁃947.
20	ZHANG H Y，WU L L，FENG R H，et al.Oxygen vacancies unfold the catalytic potential of NiFe⁃layered double hydroxides by promoting their electronic transport for oxygen evolution reaction［J］.ACS Catalysis，2023，13（9）： 6000⁃6012.
21	LIU R N， YAN Y T， DUN L， et al. Oxygen vacancy⁃mediated high⁃entropy oxide electrocatalysts for efficient oxygen evolution reaction［J］. Materials Today Catalysis， 2025， 8： 100086.
22	LI Z Y， WANG D， XU J L， et al. Constructing surface concave defects on NiFe layered double hydroxides by electrochemical reduction for efficient oxygen evolution reaction［J］. Chemical Engineering Journal， 2024， 482： 148858.
23	HE L X， WANG N， XIANG M L， et al. S⁃vacancy⁃rich NiFe⁃S nanosheets based on a fully electrochemical strategy for large⁃scale and quasi⁃industrial OER catalysts［J］. Applied Catalysis B： Environment and Energy， 2024， 345： 123686.
24	TAO Y R， YUAN J J， QIAN X Y， et al. Spinel⁃type FeNi₂S₄ with rich sulfur vacancies grown on reduced graphene oxide toward enhanced supercapacitive performance［J］. Inorganic Chemistry Frontiers， 2021， 8（9）： 2271⁃2279.
25	QI J L， XU T X， CAO J， et al. Fe doped Ni₅P₄ nanosheet arrays with rich P vacancies via phase transformation for efficient overall water splitting［J］. Nanoscale， 2020， 12（10）： 6204⁃6210.
26	CHEN X， YU M， YAN Z H， et al. Boosting electrocatalytic oxygen evolution by cation defect modulation via electrochemical etching［J］. CCS Chemistry， 2021， 3（1）： 675⁃685.
27	GE J J， ZHENG J Y， ZHANG J W， et al. Controllable atomic defect engineering in layered NixFe_1⁃ x（OH）₂ nanosheets for electrochemical overall water splitting［J］. Journal of Materials Chemistry A， 2021， 9（25）： 14432⁃14443.
28	PENG L S， YANG N， YANG Y Q， et al. Atomic cation⁃vacancy engineering of NiFe⁃layered double hydroxides for improved activity and stability towards the oxygen evolution reaction［J］. Angewandte Chemie International Edition， 2021， 60（46）： 24612⁃24619.
29	LI Z， ZHOU Y G， XIE M H， et al. High⁃density cationic defects coupling with local alkaline⁃enriched environment for efficient and stable water oxidation［J］. Angewandte Chemie International Edition， 2023， 62（26）： e202217815.
30	ZHANG X， ZHAO Y F， ZHAO Y X， et al. A simple synthetic strategy toward defect⁃rich porous monolayer NiFe⁃layered double hydroxide nanosheets for efficient electrocatalytic water oxidation［J］. Advanced Energy Materials， 2019， 9（24）： 1900881.
31	LIAO Y Y， HE R C， PAN W H， et al. Lattice distortion induced Ce⁃doped NiFe⁃LDH for efficient oxygen evolution［J］. Chemical Engineering Journal， 2023， 464： 142669.
32	WANG N， WANG X Y， SHAN Y， et al. Ce⁃doped NiFe layered double hydroxide coated NiMoOxS_4- x compounds： An efficient OER catalyst in alkaline solution［J］. Reaction Chemistry & Engineering， 2023， 8（11）： 2746⁃2756.
33	WU Q， HUANG L L， CHEN L， et al. Ce⁃doped NiFe layered double hydroxide grown on nickel foam for efficient oxygen evolution reaction［J］. Journal of Applied Electrochemistry， 2025，55（6）：1415⁃1428.
34	WANG J X， SUN X L， HU H B， et al. Electrodeposition of defect⁃rich ternary NiCoFe layered double hydroxides： Fine modulation of Co³⁺ for highly efficient oxygen evolution reaction［J］. Chemistry， 2022， 28（6）： e202103601.
35	SONG Y J，ZHANG B Z，LI T X，et al.Dynamic homogenization of internal strain in multi⁃principal element alloy via high⁃concentration doping of oxygen with large mobility［J］. Small Methods， 2024， 8（1）： 2300871.
36	HUANG L L， CHEN R， XIE C， et al. Rapid cationic defect and anion dual⁃regulated layered double hydroxides for efficient water oxidation［J］. Nanoscale， 2018， 10（28）： 13638⁃13644.
37	YE Y， GAN Y H， CAI R， et al. Oxygen vacancies and surface reconstruction on NiFe LDH@Ni（OH）₂ heterojunction synergistically triggering oxygen evolution and urea oxidation reaction［J］. Journal of Alloys and Compounds， 2022， 921： 166145.
38	WU K L， SHI L X， WANG Z D， et al. A general strategy to generate oxygen vacancies in bimetallic layered double hydroxides for water oxidation［J］. Chemical Communications， 2023， 59（21）： 3138⁃3141.
39	LI X T， LIU Y Z， SUN Q D， et al. Effects of cationic and anionic defects on NiFe LDH in electrocatalytic oxygen evolution［J］. ACS Sustainable Chemistry & Engineering， 2022， 10（44）： 14474⁃14485.
40	CAI Z Y， WANG P， ZHANG J J， et al. Reinforced layered double hydroxide oxygen⁃evolution electrocatalysts： A polyoxometallic acid wet⁃etching approach and synergistic mechanism［J］. Advanced Materials， 2022， 34（26）： e2110696.
41	LIU S X， ZHANG H W， HU E L， et al. Boosting oxygen evolution activity of NiFe⁃LDH using oxygen vacancies and morphological engineering［J］. Journal of Materials Chemistry A， 2021， 9（41）： 23697⁃23702.
42	WANG L M，ZHANG L L，MA W，et al.In situ anchoring massive isolated Pt atoms at cationic vacancies of α⁃NixFe_1- x（OH）₂ to regulate the electronic structure for overall water splitting［J］. Advanced Functional Materials， 2022， 32（31）： 2203342.
43	WANG Y Y，QIAO M，LI Y F，et al.Tuning surface electronic configuration of NiFe LDHs nanosheets by introducing cation vacancies （Fe or Ni） as highly efficient electrocatalysts for oxygen evolution reaction［J］.Small，2018，14（17）：e1800136.
44	XIE Q X， CAI Z， LI P S， et al. Layered double hydroxides with atomic⁃scale defects for superior electrocatalysis［J］. Nano Research， 2018， 11（9）： 4524⁃4534.
45	ZHU Z X， YANG X T， LIU J， et al. Handily etching nickel foams into catalyst⁃substrate fusion self⁃stabilized electrodes toward industrial⁃level water electrolysis［J］. Carbon Energy， 2023， 5（10）： e327.
46	SHI J M， LIU X R， BAI X F. Effect of N⁃doping， exfoliation， defect⁃inducing of Ni⁃Fe layered double hydroxide （Ni⁃Fe LDH） nanosheets on catalytic hydrogen storage of N⁃ethylcarbazole over Ru/Ni⁃Fe LDH［J］. Fuel， 2021， 306： 121688.
47	WEN D Y， LI Y C， ZHAO J W， et al. High⁃precision and high⁃speed etching of diamond surfaces using Fe⁃Ni alloy catalyzed H-O plasma etching［J］. Carbon， 2024， 218： 118733.
48	ZHANG Y， HUANG H M， XIE W Q， et al. Radio frequency plasma⁃engraved vacancy engineering towards robust hydrogen⁃evolving catalysts with large⁃current stable catalytic activity for over 1 000 h［J］. Science China Materials， 2025， 68（4）： 1129⁃1137.
49	TANG Y H， LIU Q， DONG L， et al. Activating the hydrogen evolution and overall water splitting performance of NiFe LDH by cation doping and plasma reduction［J］. Applied Catalysis B： Environmental， 2020， 266： 118627.
50	DOU S， TAO L， WANG R L， et al. Plasma⁃assisted synthesis and surface modification of electrode materials for renewable energy［J］. Advanced Materials， 2018， 30（21）： e1705850.
51	WANG T H， FU X Z， WANG S Y. Etching oxide overlayers of NiFe phosphide to facilitate surface reconstruction for oxygen evolution reaction［J］. Green Energy & Environment， 2022， 7（3）： 365⁃371.
52	WEI Y P， YI L Y， WANG R F， et al. A unique etching⁃doping route to Fe/Mo Co⁃doped Ni oxyhydroxide catalyst for enhanced oxygen evolution reaction［J］. Small， 2023， 19（37）： 2301267.
53	YUAN Z J， BAK S M， LI P S， et al. Activating layered double hydroxide with multivacancies by memory effect for energy⁃efficient hydrogen production at neutral pH［J］. ACS Energy Letters， 2019， 4（6）： 1412⁃1418.
54	ZHOU D J， XIONG X Y， CAI Z， et al. Flame⁃engraved nickel⁃iron layered double hydroxide nanosheets for boosting oxygen evolution reactivity［J］. Small Methods， 2018， 2（7）： 1800083.
55	WU Y J， YANG J， TU T X， et al. Evolution of cationic vacancy defects：A motif for surface restructuration of OER precatalyst［J］. Angewandte Chemie International Edition， 2021， 60（51）： 26829⁃26836.
56	ZHAO Z Y， SHAO Q， XUE J Y， et al. Multiple structural defects in ultrathin NiFe⁃LDH nanosheets synergistically and remarkably boost water oxidation reaction［J］. Nano Research， 2022， 15（1）： 310⁃316.
57	ZHANG X B， DONG H H， JIANG H M， et al. Trivalent cation defect optimization spin state of nickel（Ⅱ） in NiFe⁃layered double hydroxide nanosheets for oxygen evolution［J］. ACS Applied Nano Materials， 2024， 7（14）： 17092⁃17100.
58	CHEN Y H， XU J， CHEN Y J， et al. Rapid defect engineering in FeCoNi/FeAl₂O₄ hybrid for enhanced oxygen evolution catalysis： A pathway to high⁃performance electrocatalysts［J］. Angewandte Chemie International Edition， 2024， 63（28）： e202405372.
59	JIANG L B， JIANG L T， LUO X， et al. Iron⁃induced vacancy and electronic regulation of nickle phosphides for ampere⁃level alkaline water/seawater splitting［J］. Chemical Engineering Journal， 2024， 502： 157952.
60	ZHAO Y X， WEN Q L， HUANG D J， et al. Operando reconstruction toward dual‐cation‐defects Co⁃containing NiFe oxyhydroxide for ultralow energy consumption industrial water splitting electrolyzer［J］. Advanced Energy Materials， 2023， 13（10）： 2203595.

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