Citation: Chuan-Wang ZENG, Xiao-Xiao LI, Jin-Ming ZENG, Cao LIU, Jia-Jun LAI, Xiao-Peng QI. Synergistic enhancement of catalytic water electrolysis performance of iron-cobalt-based materials by oxygen vacancies and phosphorus doping[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(2): 202-210. doi: 10.11862/CJIC.2023.006 shu

Synergistic enhancement of catalytic water electrolysis performance of iron-cobalt-based materials by oxygen vacancies and phosphorus doping

Chuan-Wang ZENG ^{1, 2} ,
Xiao-Xiao LI ^{1, 2} ,
Jin-Ming ZENG ^{1, 2} ,
Cao LIU ^{1, 2} ,
Jia-Jun LAI ^{1, 2} ,
Xiao-Peng QI ^{1, 2,,}

1.
Rare Earth College, Jiangxi University of Science and Technology, Ganzhou, Jiangxi 341400, China
2.
Ganzhou Key Laboratory of Hydrogen Materials and Devices, Ganzhou, Jiangxi 341000, China

Corresponding author: Xiao-Peng QI, qxpai@163.com
Received Date: 21 June 2022
Revised Date: 5 December 2022

Figures(7)

Oxygen vacancies and hetero atom filling play an important role in the catalytic performance of materials. To develop an efficient and stable water electrolysis catalyst, based on the oxygen vacancies and phosphorus doping, nanoflower structures with oxygen vacancy and phosphorus doping were synthesized on iron foam by in-situ immersion growth and two-step heat treatment as hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts. CoFe₂O₄ has been reported as a promising electrocatalyst for OER and oxygen reduction reaction (ORR). However, CoFe₂O₄ exhibits poor conductivity and slow electrocatalytic reaction in HER. The formation of oxygen vacancy (Ov) in CoFe₂O₄ can effectively regulate the electronic structure of the catalyst surface and contribute to the formation of more defects and vacancies, thus improving the activity of OER. Then, we added phosphorus atoms to fill the vacancy, and the prepared P-Ov-CoFe₂O₄/IF showed excellent performance of HER and OER in the alkaline electrocatalytic test. At the current density of 10 mA·cm^-2, the overpotentials of HER and OER were only 54 and 191 mV, and the Tafel slopes were 57 and 54 mV·dec^-1, respectively. The prepared electrocatalyst also dem-onstrated excellent cycling stability.
- oxygen vacancy,
- electrolysis,
- phosphorus doping,
- hydrogen evolution reaction,
- oxygen evolution reaction
1. [1]
  YUAN H F, MA Z Z, WANG S M, LI J P, WANG X G. Engineering oxygen vacancy-rich Co₃O₄ nanowire as high- efficiency and durable bifunctional electrocatalyst for overall alkaline water splitting[J]. CIESC Journal, 2020,71(12):5831-5841.
2. [2]
  Xu Q C, Jiang H, Zhang H X, Jiang H B, Li C Z. Phosphorus-driven mesoporous Co₃O₄ nanosheets with tunable oxygen vacancies for the enhanced oxygen evolution reaction[J]. Electrochim. Acta, 2018,259962967.
3. [3]
  FENG J W, ZHOU Q. Effect of different Co contents on structure of nanoporous Ni - Co and catalytic performance of hydrogen evolution[J]. Chinese J. Inorg. Chem., 2019,35(10):1746-1754. doi: 10.11862/CJIC.2019.215
4. [4]
  Zhu J, Hu L S, Zhao P X, Lee L Y S, Wong K Y. Recent advances in electrocatalytic hydrogen evolution using nanoparticles[J]. CrystEngComm, 2019,120(2):851-918.
5. [5]
  Jiang S H, Zhang R Y, Liu H X, Rao Y, Yu Y N, Chen S, Yue Q, Zhang Y N, Kang Y J. Promoting formation of oxygen vacancies in twodimensional cobalt-doped ceria nanosheets for efficient hydrogen evolution[J]. J. Am. Chem. Soc., 2020,142(14):6461-6466. doi: 10.1021/jacs.9b13915
6. [6]
  LI C, TIAN P, PANG H C, YE J W, NING G L. Tungsten doped ironnickel layered hydroxide for oxygen evolution and hydrogen evolution reaction[J]. Chinese J. Inorg. Chem., 2020,36(8)14921498.
7. [7]
  Huang Y R, Yang W W, Yu Y S, Hao S. Ordered mesoporous spinel CoFe₂O₄ as efficient electrocatalyst for the oxygen evolution reaction[J]. J. Electroanal. Chem., 2019,840:409-414. doi: 10.1016/j.jelechem.2019.04.010
8. [8]
  Yan Y T, Wang P C, Lin J H, Cao J, Qi J L. Modification strategies on transition metal-based electrocatalysts for efficient water splitting[J]. J. Energy Chem., 2021,58:446-462. doi: 10.1016/j.jechem.2020.10.010
9. [9]
  Zhang S F, Wei N, Yao Z J, Zhao X Y, Du M, Zhou Q S. Oxygen vacancy-based ultrathin Co₃O₄ nanosheets as a high-efficiency electrocatalyst for oxygen evolution reaction[J]. Int. J. Hydrog. Energy, 2021,46(7):5286-5295. doi: 10.1016/j.ijhydene.2020.11.072
10. [10]
  Zhang L H, Wei T, Jiang Z M, Liu C Q, Jiang H, Chang J, Sheng L Z, Zhou Q H, Yuan L B, Fan Z J. Electrostatic interaction in electrospun nanofibers: Double - layer carbon protection of CoFe₂O₄ nanosheets enabling ultralong-life and ultrahigh-rate lithium ion storage[J]. Nano Energy, 2018,48:238-247. doi: 10.1016/j.nanoen.2018.03.053
11. [11]
  Liu T T, Ma X, Liu D N, Hao S, Du G, Ma Y J, Asiri A M, Sun X P, Chen L. Mn doping of CoP nanosheets array: An efficient electrocatalyst for hydrogen evolution reaction with enhanced activity at all pH values[J]. ACS Catal., 2017,7(1):98-102. doi: 10.1021/acscatal.6b02849
12. [12]
  Nemiwal M, Gosu V, Zhang T C, Kumar D. Metal organic frameworks as electrocatalysts: Hydrogen evolution reactions and overall water splitting[J]. Int. J. Hydrog. Energy, 2021,46(17):10216-10238. doi: 10.1016/j.ijhydene.2020.12.146
13. [13]
  Zhang T W, Li Z F, Wang L K, Zhang Z X, Wang S W. Spinel CoFe₂O₄ supported by three dimensional graphene as high - performance bi-functional electrocatalysts for oxygen reduction and evolution reaction[J]. Int. J. Hydrog. Energy, 2019,44(3):1610-1619. doi: 10.1016/j.ijhydene.2018.11.120
14. [14]
  Wang Z Y, Chen J Y, Song E H, Wang N, Dong J C, Zhang X, Ajayan P M, Yao W, Wang C F, Liu J J, Shen J F, Ye M X. Manipulation on active electronic states of metastable phase β-NiMoO₄ for large current density hydrogen evolution[J]. Nat. Commun., 2021,12(1)5960. doi: 10.1038/s41467-021-26256-1
15. [15]
  Li Z H, Lv Z H, Liu X, Wang G X, Lin Y S, Xie G W, Jiang L H. Magnetic-field guided synthesis of highly active Ni-S-CoFe₂O₄ electrocatalysts for oxygen evolution reaction[J]. Renew. Energy, 2021,165:612-618. doi: 10.1016/j.renene.2020.11.083
16. [16]
  Bi J L, Zhai X J, Liu G S, Chi J Q, Wang X Y, Chen S J, Xiao Z Y, Wang L. Low loading of P modified Rh nanoparticles encapsulated in N, P-doped carbon for boosted and pH-universal hydrogen evolution reaction[J]. Int. J. Hydrog. Energy, 2022,47(6):3791-3800. doi: 10.1016/j.ijhydene.2021.11.036
17. [17]
  Guo J Q, Zhan Z X, Lei T, Yin P. Facile synthesis of self-supported intertwined columnar NiCoP as a high efficient electrocatalyst for hydrogen evolution reaction[J]. Int. J. Hydrog. Energy, 2022,47(9)59745989.
18. [18]
  Li J G, Sun H C, Lv L, Li Z S, Ao X, Xu C H, Li Y, Wang C D. Metalorganic framework - derived hierarchical (Co, Ni)Se₂@NiFe LDH hollow nanocages for enhanced oxygen evolution[J]. ACS Appl. Mater. Interfaces, 2019,11(8):8106-8114. doi: 10.1021/acsami.8b22133
19. [19]
  Wang F M, Chen J W, Qi X P, Yang H, Jiang H H, Deng Y Q, Liang T X. Increased nucleation sites in nickel foam for the synthesis of MoP@Ni₃P/NF nanosheets for bifunctional water splitting[J]. Appl. Surf. Sci., 2019,481:1403-1411. doi: 10.1016/j.apsusc.2019.03.200
20. [20]
  Wang H Q, Zhang X W, Wang J G, Liu H L, Hu S X, Zhou W J, Liu H, Wang X. Puffing quaternary Fe_xCo_yNi_1-x-yP nanoarray via kinetically controlled alkaline etching for robust overall water splitting[J]. Sci. China-Mater., 2020,63(6):1054-1064. doi: 10.1007/s40843-019-1268-7
21. [21]
  Zhuang L H, Ge L, Yang Y S, Li M R, Jia Y, Yao X D, Zhu Z H. Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction[J]. Adv. Mater., 2017,29(17)1606793. doi: 10.1002/adma.201606793
22. [22]
  Yan K L, Shang X, Liu Z Z, Dong B, Lu S S, Chi J Q, Gao W K, Chai Y M, Liu C G. A facile method for reduced CoFe₂O₄ nanosheets with rich oxygen vacancies for efficient oxygen evolution reaction[J]. Int. J. Hydrog. Energy, 2017,42(38):24150-24158. doi: 10.1016/j.ijhydene.2017.07.165
23. [23]
  Xiao Z H, Wang Y, Huang Y C, Wei Z X, Dong C L, Ma J M, Shen S H, Li Y F, Wang S Y. Filling the oxygen vacancies in Co₃O₄ with phosphorus: An ultra-efficient electrocatalyst for overall water splitting[J]. Energy Environ. Sci., 2017,10(12):2563-2569. doi: 10.1039/C7EE01917C
24. [24]
  Murthy A P, Theerthagiri J, Madhavan J, Murugan K. Highly active MoS₂/carbon electrocatalysts for the hydrogen evolution reaction— Insight into the effect of the internal resistance and roughness factor on the Tafel slope[J]. Phys. Chem. Chem. Phys., 2017,19(3):1988-1998. doi: 10.1039/C6CP07416B
25. [25]
  Huang L B, Zhao L, Zhang Y, Chen Y Y, Zhang Q H, Luo H, Zhang X, Tang T, Gu L, Hu J S. Self-limited on-site conversion of MoO₃ Nanodots into vertically aligned ultrasmall monolayer MoS₂ for efficient hydrogen evolution[J]. Adv. Energy Mater., 2018,8(21)1800734. doi: 10.1002/aenm.201800734
26. [26]
  Liang H F, Gandi A N, Anjum D H, Wang X B, Schwingenschlögl U, Alshareef H N. Plasma-assisted synthesis of NiCoP for efficient overall water splitting[J]. Nano Lett., 2016,16(12):7718-7725. doi: 10.1021/acs.nanolett.6b03803
1. [1]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
2. [2]
  Weicheng Feng , Jingcheng Yu , Yilan Yang , Yige Guo , Geng Zou , Xiaoju Liu , Zhou Chen , Kun Dong , Yuefeng Song , Guoxiong Wang , Xinhe Bao . Regulating the High Entropy Component of Double Perovskite for High-Temperature Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(6): 2306013-0. doi: 10.3866/PKU.WHXB202306013
3. [3]
  Shiqian WEI , Xinyu TIAN , Hong LIU , Maoxia CHEN , Fan TANG , Qiang FAN , Weifeng FAN , Yu HU . Oxygen reduction reaction/oxygen evolution reaction catalytic performances of different active sites on nitrogen-doped graphene loaded with iron single atoms. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1776-1788. doi: 10.11862/CJIC.20250102
4. [4]
  Hailang JIA , Pengcheng JI , Hongcheng LI . Preparation and performance of nickel doped ruthenium dioxide electrocatalyst for oxygen evolution. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1632-1640. doi: 10.11862/CJIC.20240398
5. [5]
  Wuxin Bai , Qianqian Zhou , Zhenjie Lu , Ye Song , Yongsheng Fu . Co-Ni Bimetallic Zeolitic Imidazolate Frameworks Supported on Carbon Cloth as Free-Standing Electrode for Highly Efficient Oxygen Evolution. Acta Physico-Chimica Sinica, 2024, 40(3): 2305041-0. doi: 10.3866/PKU.WHXB202305041
6. [6]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
7. [7]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
8. [8]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
9. [9]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
10. [10]
  Haodong JIN , Qingqing LIU , Chaoyang SHI , Danyang WEI , Jie YU , Xuhui XU , Mingli XU . NiCu/ZnO heterostructure photothermal electrocatalyst for efficient hydrogen evolution reaction. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1068-1082. doi: 10.11862/CJIC.20250048
11. [11]
  Huafeng SHI . Construction of MnCoNi layered double hydroxide@Co-Ni-S amorphous hollow polyhedron composite with excellent electrocatalytic oxygen evolution performance. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1380-1386. doi: 10.11862/CJIC.20240378
12. [12]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
13. [13]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
14. [14]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
15. [15]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-0. doi: 10.3866/PKU.WHXB202312010
16. [16]
  Yajuan Xing , Hui Xue , Jing Sun , Niankun Guo , Tianshan Song , Jiawen Sun , Yi-Ru Hao , Qin Wang . Cu₃P-Induced Charge-Oriented Transfer and Surface Reconstruction of Ni₂P to Achieve Efficient Oxygen Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(3): 2304046-0. doi: 10.3866/PKU.WHXB202304046
17. [17]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
18. [18]
  Xueting Cao , Shuangshuang Cha , Ming Gong . Interfacial Electrical Double Layer in Electrocatalytic Reactions: Fundamentals, Characterizations and Applications. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-0. doi: 10.1016/j.actphy.2024.100041
19. [19]
  Xinyi Zhang , Kai Ren , Yanning Liu , Zhenyi Gu , Zhixiong Huang , Shuohang Zheng , Xiaotong Wang , Jinzhi Guo , Igor V. Zatovsky , Junming Cao , Xinglong Wu . Progress on Entropy Production Engineering for Electrochemical Catalysis. Acta Physico-Chimica Sinica, 2024, 40(7): 2307057-0. doi: 10.3866/PKU.WHXB202307057
20. [20]
  Chunchun Wang , Changjun You , Ke Rong , Chuqi Shen , Fang Yang , Shijie Li . An S-Scheme MIL-101(Fe)-on-BiOCl Heterostructure with Oxygen Vacancies for Boosting Photocatalytic Removal of Cr(Ⅵ). Acta Physico-Chimica Sinica, 2024, 40(7): 2307045-0. doi: 10.3866/PKU.WHXB202307045

Get Citation

PDF

XML

Metrics

PDF Downloads(25)
Abstract views(2241)
HTML views(591)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142