The Role of Fe Species on NiOOH in Oxygen Evolution Reactions

  • Yecheng Zhou*
    Yecheng Zhou
    School of Materials Science & Engineering, Sun Yat-Sen University, Guangzhou 510275, Guangdong, People’s Republic of China
    The Barcelona Institute of Science and Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, 43007 Tarragona, Spain
    *E-mail: [email protected] (Y. Zhou).
    More by Yecheng Zhou
  •  and 
  • Núria López*
    Núria López
    The Barcelona Institute of Science and Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, 43007 Tarragona, Spain
    *E-mail: [email protected] (N. López).
Cite this: ACS Catal. 2020, 10, 11, 6254–6261
Publication Date (Web):May 5, 2020
Copyright © 2020 American Chemical Society
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The Pourbaix diagram of Ni electrodes under reaction conditions presents several metastable NiOxHy phases and Fe doping enlarges the stability area of oxyhydroxo species. For the Ni-only phase, water adsorption and intercalation can significantly lower both the surface and interface energies, and even introduce “negative surface energy”. Thus, water can exfoliate layers, leading to Fe ion adsorption on inner layers, as demonstrated by ab initio molecular dynamics. These single atoms have been carefully speciated (i.e., initially prepared as Fe2+ and Fe3+) and proton coupled electron transfer between the H2O–Fe and lattice oxygen ions has been observed in all ab initio molecular dynamics simulations, which is attributed to the Fe incorporation, since no proton coupled electron transfer occurs under free water conditions. Furthermore, 15 possible oxygen evolution reaction mechanisms near Fe ions show that the main active species corresponds to the Ni2+, which is reduced from Ni3+ via H transfer when a Fe2+ iron adsorbs nearby, and the overpotential can be significantly reduced to 0.23 V.

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  2. Jinlong Liu, Juanxiu Xiao, Zhenyu Wang, Huimin Yuan, Zhouguang Lu, Bingcheng Luo, Enke Tian, Geoffrey I. N. Waterhouse. Structural and Electronic Engineering of Ir-Doped Ni-(Oxy)hydroxide Nanosheets for Enhanced Oxygen Evolution Activity. ACS Catalysis 2021, 11 (9) , 5386-5395.
  3. Huixia Hu, Xiang Lei, Shumei Li, Ruzhen Peng, Jinliang Wang. Rapid mass production of iron nickel oxalate nanorods for efficient oxygen evolution reaction catalysis. New Journal of Chemistry 2022, 19
  4. Hyeonjung Jung, Seokhyun Choung, Jeong Woo Han. Design principles of noble metal-free electrocatalysts for hydrogen production in alkaline media: combining theory and experiment. Nanoscale Advances 2021, 3 (24) , 6797-6826.
  5. Huibing Liu, Xinchen Xu, Haoxiang Xu, Shitao Wang, Ziqiang Niu, Qiaohuan Jia, Liu Yang, Rui Cao, Lirong Zheng, Dapeng Cao. Dual active site tandem catalysis of metal hydroxyl oxides and single atoms for boosting oxygen evolution reaction. Applied Catalysis B: Environmental 2021, 297 , 120451.
  6. Zhihao Zhang, Chunli Wang, Xuelu Ma, Feng Liu, Hai Xiao, Jing Zhang, Zhang Lin, Zhengping Hao. Engineering Ultrafine NiFe‐LDH into Self‐Supporting Nanosheets: Separation‐and‐Reunion Strategy to Expose Additional Edge Sites for Oxygen Evolution. Small 2021, 17 (47) , 2103785.
  7. Mukesh Jakhar, Ashok Kumar. Tunable photocatalytic water splitting and solar-to-hydrogen efficiency in β-PdSe 2 monolayer. Catalysis Science & Technology 2021, 11 (19) , 6445-6454.
  8. Shilong Jiao, Xianwei Fu, Shuangchen Ruan, Yu-Jia Zeng, Hongwen Huang. Breaking the periodic arrangement of atoms for the enhanced electrochemical reduction of nitrogen and water oxidation. Science China Materials 2021, 10
  9. Jingqi Guan, Xue Bai, Tianmi Tang. Recent progress and prospect of carbon-free single-site catalysts for the hydrogen and oxygen evolution reactions. Nano Research 2021, 9
  10. Sinwoo Kang, Kahyun Ham, Hyung-Kyu Lim, Jaeyoung Lee. Dischargeable nickel matrix charges iron species for oxygen evolution electrocatalysis. Electrochimica Acta 2021, 386 , 138401.
  11. Ramón Arcas, Yuuki Koshino, Elena Mas-Marzá, Ryuki Tsuji, Hideaki Masutani, Eri Miura-Fujiwara, Yuichi Haruyama, Seiji Nakashima, Seigo Ito, Francisco Fabregat-Santiago. Pencil graphite rods decorated with nickel and nickel–iron as low-cost oxygen evolution reaction electrodes. Sustainable Energy & Fuels 2021, 5 (15) , 3929-3938.
  12. Ioannis Spanos, Justus Masa, Aleksandar Zeradjanin, Robert Schlögl. The Effect of Iron Impurities on Transition Metal Catalysts for the Oxygen Evolution Reaction in Alkaline Environment: Activity Mediators or Active Sites?. Catalysis Letters 2021, 151 (7) , 1843-1856.
  13. Lei Wang, Jiayao Fan, Ying Liu, Mingyu Chen, Yue Lin, Hengchang Bi, Bingxue Liu, Naien Shi, Dongdong Xu, Jianchun Bao, Min Han. Phase‐Modulation of Iron/Nickel Phosphides Nanocrystals “Armored” with Porous P‐Doped Carbon and Anchored on P‐Doped Graphene Nanohybrids for Enhanced Overall Water Splitting. Advanced Functional Materials 2021, 31 (30) , 2010912.
  14. Zunhang Lv, Zihan Li, Xiao Tan, Zhengmin Li, Rui Wang, Mengjin Wen, Xin Liu, Guixue Wang, Guangwen Xie, Luhua Jiang. One-step electrodeposited NiFeMo hybrid film for efficient hydrogen production via urea electrolysis and water splitting. Applied Surface Science 2021, 552 , 149514.
  15. Adèle Peugeot, Charles E. Creissen, Dilan Karapinar, Huan Ngoc Tran, Moritz Schreiber, Marc Fontecave. Benchmarking of oxygen evolution catalysts on porous nickel supports. Joule 2021, 5 (5) , 1281-1300.
  16. Joel Sanchez, Michaela Burke Stevens, Alexandra R. Young, Alessandro Gallo, Meng Zhao, Yunzhi Liu, Mario V. Ramos‐Garcés, Micha Ben‐Naim, Jorge L. Colón, Robert Sinclair, Laurie A. King, Michal Bajdich, Thomas F. Jaramillo. Isolating the Electrocatalytic Activity of a Confined NiFe Motif within Zirconium Phosphate. Advanced Energy Materials 2021, 11 (20) , 2003545.
  17. Felipe Andrés Garcés‐Pineda, Huu Chuong Nguyën, Marta Blasco‐Ahicart, Miguel García‐Tecedor, Mabel Fez Febré, Peng‐Yi Tang, Jordi Arbiol, Sixto Giménez, José Ramón Galán‐Mascarós, Núria López. Push‐Pull Electronic Effects in Surface‐Active Sites Enhance Electrocatalytic Oxygen Evolution on Transition Metal Oxides. ChemSusChem 2021, 14 (6) , 1595-1601.
  18. Jordi Morales-Vidal, Rodrigo García-Muelas, Manuel A. Ortuño. Defects as catalytic sites for the oxygen evolution reaction in Earth-abundant MOF-74 revealed by DFT. Catalysis Science & Technology 2021, 11 (4) , 1443-1450.
  19. Duanduan Liu, Wei Wei, Maidina Mahemu, Hao Qin, Kai Zhu, Shicheng Yan, Zhigang Zou. Solid-state redox couple mediated water splitting. Dalton Transactions 2021, 50 (8) , 2722-2725.
  20. N. Clament Sagaya Selvam, Lijie Du, Bao Yu Xia, Pil J. Yoo, Bo You. Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities. Advanced Functional Materials 2021, 31 (12) , 2008190.
  21. Patrick Gono, Alfredo Pasquarello. High-performance NiOOH/FeOOH electrode for OER catalysis. The Journal of Chemical Physics 2021, 154 (2) , 024706.
  22. Ananth Govind Rajan, Emily A. Carter. Microkinetic model for pH- and potential-dependent oxygen evolution during water splitting on Fe-doped β-NiOOH. Energy & Environmental Science 2020, 13 (12) , 4962-4976.
  23. Choel-Hwan Shin, Yi Wei, Gisang Park, Joonhee Kang, Jong-Sung Yu. High performance binder-free Fe–Ni hydroxides on nickel foam prepared in piranha solution for the oxygen evolution reaction. Sustainable Energy & Fuels 2020, 4 (12) , 6311-6320.
  24. Suli Liu, Xueqin Mu, Pengxia Ji, Yun Lv, Lei Wang, Quan Zhou, Changyun Chen, Shichun Mu. Constructing a Rod‐like [email protected] Heterostructure with Additive Active Sites for Water Splitting. ChemCatChem 2020, 12 (20) , 5149-5155.
  25. Matthias Vandichel, Kari Laasonen, Ivan Kondov. Oxygen Evolution and Reduction on Fe-doped NiOOH: Influence of Solvent, Dopant Position and Reaction Mechanism. Topics in Catalysis 2020, 63 (9-10) , 833-845.