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In Situ Coordination Environment Tuning of Cobalt Sites for Efficient Water Oxidation

  • Qianbao Wu
    Qianbao Wu
    Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
    More by Qianbao Wu
  • Mengjun Xiao
    Mengjun Xiao
    Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
    More by Mengjun Xiao
  • Wei Wang
    Wei Wang
    School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 610054, China
    More by Wei Wang
  • , and 
  • Chunhua Cui*
    Chunhua Cui
    Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
    *E-mail: [email protected]
    More by Chunhua Cui
Cite this: ACS Catal. 2019, 9, 12, 11734–11742
Publication Date (Web):November 11, 2019
https://doi.org/10.1021/acscatal.9b03762
Copyright © 2019 American Chemical Society
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Abstract

Most transition-metal-based oxygen-evolving catalyst surfaces typically experience irreversible compositional and structural variations during oxygen evolution reaction (OER) in hydrolytic and corrosive alkaline media, degrading the coordination environment of active metal sites into unified (oxy)hydroxides. Here, we present an in situ electrochemical coordination tuning of cobalt sites for OER in a strong base, where an electrolyzing soluble cobalt-2,2′-bipyridine (Co-bpy) complex partially splits the bpy ligand, leading to the deposition of active Co sites with fine coordination at room temperature. We deposited the Co sites while catalyzing water oxidation at the same condition so that this catalyst can adapt the hostile alkaline condition. This robust coordination environment involving the remaining bpy and generated (oxy)hydroxide ligands (Co–BH catalyst) sustains the highly improved OER activity over 500 h at 200 mA cm–2, outperforming other fragile Co sites with only (oxy)hydroxides. In addition, this work presents an efficient tuning of metal coordination environments to in situ generate highly active and stable metal sites in alkaline electrolytes for water splitting.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.9b03762.

  • Experimental section; coordination and ratio between Co and bpy; in situ deposition; anion effects on solution coordination; morphology of Co-BH; impedance; evolution process of Co-BH; element mappings and EDX; SEM images; phase of Co-BH; Raman shift; UV–vis spectrum; XPS of Co-BH; home-made cell; loading of the catalyst; potential-dependent absorbance; electrochemical operations; stability of Co-BH; surface morphology and element distribution; roles of Co-bpy in the electrolyte; XRD patterns; HRTEM and SAED images; Co 2p of Co-BH; XPS survey; η–t curves; detachment of CoPi film; CV curves and Tafel slopes; R2 of different precursors; R2 of different deposited times; amounts of Co 2p and N 1s; increased Co/N ratio; comparison of OER performance; and references 1–16 (PDF)

  • Violent gas bubble evolving observed from the reaction window at 200 mA cm–2 at real playing speed (MP4)

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Cited By


This article is cited by 19 publications.

  1. Andraž Mavrič, Chunhua Cui. Advances and Challenges in Industrial-Scale Water Oxidation on Layered Double Hydroxides. ACS Applied Energy Materials 2021, 4 (11) , 12032-12055. https://doi.org/10.1021/acsaem.1c02604
  2. Peikun Zhang, Pai Wang, Wei Wang, Qianbao Wu, Mengjun Xiao, Roger Alberto, Yanning Zhang, Chunhua Cui. Efficient Alkaline Water Oxidation with a Regenerable Nickel Pseudo-Complex. ACS Applied Materials & Interfaces 2021, 13 (41) , 48661-48668. https://doi.org/10.1021/acsami.1c13609
  3. Mengjun Xiao, Qianbao Wu, Lei Li, Shijia Mu, Mads Nybo Sørensen, Wei Wang, Chunhua Cui. Regenerable Catalyst for Highly Alkaline Water Oxidation. ACS Energy Letters 2021, 6 (5) , 1677-1683. https://doi.org/10.1021/acsenergylett.1c00127
  4. Yue Zheng, Rui Gao, Yunsheng Qiu, Lirong Zheng, Zhongbo Hu, Xiangfeng Liu. Tuning Co2+ Coordination in Cobalt Layered Double Hydroxide Nanosheets via Fe3+ Doping for Efficient Oxygen Evolution. Inorganic Chemistry 2021, 60 (7) , 5252-5263. https://doi.org/10.1021/acs.inorgchem.1c00248
  5. Biswajit Mondal, Samir Chattopadhyay, Subal Dey, Atif Mahammed, Kaustuv Mittra, Atanu Rana, Zeev Gross, Abhishek Dey. Elucidation of Factors That Govern the 2e–/2H+ vs 4e–/4H+ Selectivity of Water Oxidation by a Cobalt Corrole. Journal of the American Chemical Society 2020, 142 (50) , 21040-21049. https://doi.org/10.1021/jacs.0c08654
  6. Wenchao Wan, Carlos A. Triana, Jinggang Lan, Jingguo Li, Christopher S. Allen, Yonggui Zhao, Marcella Iannuzzi, Greta R. Patzke. Bifunctional Single Atom Electrocatalysts: Coordination–Performance Correlations and Reaction Pathways. ACS Nano 2020, 14 (10) , 13279-13293. https://doi.org/10.1021/acsnano.0c05088
  7. Yuehong Xie, Chao Feng, Yuan Guo, Afaq Hassan, Shiang Li, Yi Zhang, Jide Wang. Dimethylimidazole and dicyandiamide assisted synthesized rich-defect and highly dispersed CuCo-Nx anchored hollow graphite carbon nanocages as efficient trifunctional electrocatalyst in the same electrolyte. Journal of Power Sources 2022, 517 , 230721. https://doi.org/10.1016/j.jpowsour.2021.230721
  8. Li Song, Haiyu Fan, Tao Wang, Tengfei Xiang, Mingdao Zhang, Chuangang Hu, Wei Zhou, Jianping He. Facile synthesis of Co, N enriched carbon nanotube and active site identifications for bifunctional oxygen reduction and evolution catalysis. Energy Storage Materials 2021, 43 , 365-374. https://doi.org/10.1016/j.ensm.2021.09.009
  9. Cheng‐Fei Li, Jia‐Wei Zhao, Ling‐Jie Xie, Jin‐Qi Wu, Qian Ren, Yu Wang, Gao‐Ren Li. Surface‐Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal–Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction. Angewandte Chemie 2021, 133 (33) , 18277-18285. https://doi.org/10.1002/ange.202104148
  10. Cheng‐Fei Li, Jia‐Wei Zhao, Ling‐Jie Xie, Jin‐Qi Wu, Qian Ren, Yu Wang, Gao‐Ren Li. Surface‐Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal–Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction. Angewandte Chemie International Edition 2021, 60 (33) , 18129-18137. https://doi.org/10.1002/anie.202104148
  11. Bingling He, Jiansheng Shen, Bin Wang, Zhansheng Lu, Dongwei Ma. Single-atom catalysts based on TiN for the electrocatalytic hydrogen evolution reaction: a theoretical study. Physical Chemistry Chemical Physics 2021, 23 (29) , 15685-15692. https://doi.org/10.1039/D1CP01861B
  12. Xue Jiang, Wen Zhang, Guang‐Rui Xu, Jianping Lai, Lei Wang. Interface engineering of metal nanomaterials enhance the electrocatalytic water splitting and fuel cell performance. Electrochemical Science Advances 2021, 355 https://doi.org/10.1002/elsa.202100066
  13. Thangjam Ibomcha Singh, Gaddam Rajeshkhanna, Uday Narayan Pan, Tolendra Kshetri, Han Lin, Nam Hoon Kim, Joong Hee Lee. Alkaline Water Splitting Enhancement by MOF‐Derived Fe–Co–Oxide/[email protected]‐mNS Heterostructure: Boosting OER and HER through Defect Engineering and In Situ Oxidation. Small 2021, 17 (29) , 2101312. https://doi.org/10.1002/smll.202101312
  14. Jing He, Zhufeng Hu, Kuan Deng, Renjun Zhao, Xingbin Lv, Wen Tian, Yu Xin Zhang, Junyi Ji. A triple-layered [email protected] LDH/FeCo 2 O 4 hybrid crystalline structure with high electron conductivity and abundant interfaces for supercapacitors and oxygen evolution. CrystEngComm 2021, 23 (11) , 2262-2268. https://doi.org/10.1039/D1CE00076D
  15. Swarnava Nandy, Qianbao Wu, S. David Tilley, Chunhua Cui. Improved water oxidation with metal oxide catalysts via a regenerable and redox-inactive ZnO x H y overlayer. Chemical Communications 2021, 116 https://doi.org/10.1039/D1CC03406E
  16. Jun Zhao, Wenqing Zhang, Jian Zhang, Xijie Chen, Yun Wu, Chuan Li, Xin Zhang, Fengchun Yang. The electropositive environment of Rh in Rh1Sn2/SWNTs for boosting trifunctional electrocatalysis. International Journal of Hydrogen Energy 2020, 45 (56) , 32050-32058. https://doi.org/10.1016/j.ijhydene.2020.08.283
  17. Jingsha Li, Tao Hu, Changhong Wang, Chunxian Guo. Surface-mediated iron on porous cobalt oxide with high energy state for efficient water oxidation electrocatalysis. Green Energy & Environment 2020, 19 https://doi.org/10.1016/j.gee.2020.11.009
  18. Wei Wang, Marc Heggen, Wei Cui, Benjamin Probst, Roger Alberto, Chunhua Cui. Synergizing hole accumulation and transfer on composite Ni/CoO x for photoelectrochemical water oxidation. Chemical Communications 2020, 56 (70) , 10179-10182. https://doi.org/10.1039/D0CC03717F
  19. Shu Xu, Shuaiqi Gong, Hua Jiang, Penghui Shi, Jinchen Fan, QunJie Xu, YuLin Min. Z-scheme heterojunction through interface engineering for broad spectrum photocatalytic water splitting. Applied Catalysis B: Environmental 2020, 267 , 118661. https://doi.org/10.1016/j.apcatb.2020.118661