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
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