Operando Raman Spectroscopy Reveals Cr-Induced-Phase Reconstruction of NiFe and CoFe Oxyhydroxides for Enhanced Electrocatalytic Water Oxidation

  • Xin Bo
    Xin Bo
    School of Chemistry, Faculty of Science, The University of New South Wales, Sydney, NSW 2052 Australia
    More by Xin Bo
  • Yibing Li
    Yibing Li
    School of Chemistry, Faculty of Science, The University of New South Wales, Sydney, NSW 2052 Australia
    More by Yibing Li
  • Xianjue Chen
    Xianjue Chen
    School of Chemistry, Faculty of Science, The University of New South Wales, Sydney, NSW 2052 Australia
    More by Xianjue Chen
  • , and 
  • Chuan Zhao*
    Chuan Zhao
    School of Chemistry, Faculty of Science, The University of New South Wales, Sydney, NSW 2052 Australia
    *Email: [email protected]
    More by Chuan Zhao
Cite this: Chem. Mater. 2020, 32, 10, 4303–4311
Publication Date (Web):April 24, 2020
Copyright © 2020 American Chemical Society
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Nonprecious NiFe and CoFe oxyhydroxides are among the most active materials for oxygen evolution reaction (OER) in basic media. However, the phase separation in these composites during water oxidation remains a critical issue that often results in degradation of electrochemical performance and debate on the mechanism and the active intermediates. In this study, we show that the introduction of Cr can efficiently transform the crystalline multiphase NiFe and CoFe oxides/hydroxides into homogeneous amorphous nanodots with sharply reduced nanoparticle size from tens of nanometers to merely 2–3 nm. Serving as an OER catalyst, the ternary NiFeCr and CoFeCr catalysts exhibit a smaller onset potential of ∼1.51 V vs reversible hydrogen electrode (RHE) and a stable OER performance during long-term water electrolysis. The impact of Cr on the NiFe and CoFe catalysts for OER kinetics was systematically investigated by operando electrochemical Raman spectroscopy. It is found that, for the NiFeCr compound, Cr can promote the generation of a more active β-NiOOH phase than that of the NiFe composite during water oxidation. For the CoFe and CoFeCr systems, the introduction of Cr only disturbs the lattice crystallization. However, active CoOOH is spontaneously present on the surface of the composites upon making contact with KOH electrolyte, even without applying a potential. Thus, Co-based catalysts can easily achieve the “ready-to-serve” state for high-performance water oxidation without preactivation.

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  • Photos of obtained catalysts, XRD patterns, TEM images, optimization of OER performance, cyclic voltammetries, EIS plots, Raman spectra, LSV, XPS data, HRTEM images, ICP-OES, and simulated parameters of relevant equivalent circuits (PDF)

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  2. Kun Jiang, Wenjun Liu, Wei Lai, Menglian Wang, Qian Li, Zhaolong Wang, Junjie Yuan, Yilin Deng, Jian Bao, Hongbing Ji. NiFe Layered Double Hydroxide/FeOOH Heterostructure Nanosheets as an Efficient and Durable Bifunctional Electrocatalyst for Overall Seawater Splitting. Inorganic Chemistry 2021, 60 (22) , 17371-17378. https://doi.org/10.1021/acs.inorgchem.1c02903
  3. Ahmed Badreldin, Ahmed Nabeeh, Ebtihal Youssef, Noor Mubarak, Hania ElSayed, Rana Mohsen, Fatma Ahmed, Yiming Wubulikasimu, Khaled Elsaid, Ahmed Abdel-Wahab. Adapting Early Transition Metal and Nonmetallic Dopants on CoFe Oxyhydroxides for Enhanced Alkaline and Neutral pH Saline Water Oxidation. ACS Applied Energy Materials 2021, 4 (7) , 6942-6956. https://doi.org/10.1021/acsaem.1c01036
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  5. Hainan Sun, Wei Zhou. Progress on X-ray Absorption Spectroscopy for the Characterization of Perovskite-Type Oxide Electrocatalysts. Energy & Fuels 2021, 35 (7) , 5716-5737. https://doi.org/10.1021/acs.energyfuels.1c00534
  6. Thanh Tran-Phu, Rahman Daiyan, Joshua Leverett, Zelio Fusco, Anton Tadich, Iolanda Di Bernardo, Alexander Kiy, Thien N. Truong, Qingran Zhang, Hongjun Chen, Patrick Kluth, Rose Amal, Antonio Tricoli. Understanding the activity and stability of flame-made Co3O4 spinels: A route towards the scalable production of highly performing OER electrocatalysts. Chemical Engineering Journal 2022, 429 , 132180. https://doi.org/10.1016/j.cej.2021.132180
  7. Jinzhen Huang, Hongyuan Sheng, R. Dominic Ross, Jiecai Han, Xianjie Wang, Bo Song, Song Jin. Modifying redox properties and local bonding of Co3O4 by CeO2 enhances oxygen evolution catalysis in acid. Nature Communications 2021, 12 (1) https://doi.org/10.1038/s41467-021-23390-8
  8. Wenjun Liu, Kun Jiang, Yiming Hu, Qian Li, Yilin Deng, Jian Bao, Yucheng Lei. Zr-doped CoFe-layered double hydroxides for highly efficient seawater electrolysis. Journal of Colloid and Interface Science 2021, 604 , 767-775. https://doi.org/10.1016/j.jcis.2021.07.022
  9. Wanfeng Li, Yong Jiang, Yurong Li, Qin Gao, Wei Shen, Yimin Jiang, Rongxing He, Ming Li. Electronic modulation of CoP nanoarrays by Cr-doping for efficient overall water splitting. Chemical Engineering Journal 2021, 425 , 130651. https://doi.org/10.1016/j.cej.2021.130651
  10. Yi‐jin Wu, Jian Yang, Teng‐xiu Tu, Wei‐qiong Li, Peng‐fang Zhang, Yao Zhou, Jian‐feng Li, Jun‐tao Li, Shi‐Gang Sun. Evolution of Cationic Vacancy Defects: A Motif for Surface Restructuration of OER Precatalyst. Angewandte Chemie International Edition 2021, 13 https://doi.org/10.1002/anie.202112447
  11. Yi‐jin Wu, Jian Yang, Teng‐xiu Tu, Wei‐qiong Li, Peng‐fang Zhang, Yao Zhou, Jian‐feng Li, Jun‐tao Li, Shi‐Gang Sun. Evolution of Cationic Vacancy Defects: A Motif for Surface Restructuration of OER Precatalyst. Angewandte Chemie 2021, 13 https://doi.org/10.1002/ange.202112447
  12. Lei Ding, Kui Li, Zhiqiang Xie, Gaoqiang Yang, Shule Yu, Weitian Wang, David A. Cullen, Haoran Yu, FengYuan Zhang. W-induced morphological modification of NiFe layered double hydroxides as efficient electrocatalysts for overall water splitting. Electrochimica Acta 2021, 395 , 139199. https://doi.org/10.1016/j.electacta.2021.139199
  13. Ruiqin Gao, Meng Deng, Qing Yan, Zhenxing Fang, Lichun Li, Haoyu Shen, Zhengfei Chen. Structural Variations of Metal Oxide‐Based Electrocatalysts for Oxygen Evolution Reaction. Small Methods 2021, 218 , 2100834. https://doi.org/10.1002/smtd.202100834
  14. Kamran Dastafkan, Shuhao Wang, Chengli Rong, Quentin Meyer, Yibing Li, Qiang Zhang, Chuan Zhao. Cosynergistic Molybdate Oxo‐Anionic Modification of FeNi‐Based Electrocatalysts for Efficient Oxygen Evolution Reaction. Advanced Functional Materials 2021, , 2107342. https://doi.org/10.1002/adfm.202107342
  15. Lei Ye, Yeqing Zhang, Buwen Guo, Duanlin Cao, Yaqiong Gong. Ru doping induces the construction of a unique core–shell microflower self-supporting electrocatalyst for highly efficient overall water splitting. Dalton Transactions 2021, 50 (39) , 13951-13960. https://doi.org/10.1039/D1DT02341A
  16. William Adamson, Chen Jia, Yibing Li, Chuan Zhao. Vanadium-induced fragmentation of crystalline CoFe hydr(oxy)oxide electrocatalysts for enhanced oxygen evolution reaction. International Journal of Hydrogen Energy 2021, 46 (71) , 35230-35238. https://doi.org/10.1016/j.ijhydene.2021.08.080
  17. Yi Zhou, Jialai Hu, Lichun Yang, Qingsheng Gao. Recent advances of two-dimensional CoFe layered-double-hydroxides for electrocatalytic water oxidation. Chinese Chemical Letters 2021, 265 https://doi.org/10.1016/j.cclet.2021.10.034
  18. Han Zhu, Zhenfeng Zhu, Jiace Hao, Shuhui Sun, Shuanglong Lu, Chan Wang, Piming Ma, Weifu Dong, Mingliang Du. High-entropy alloy stabilized active Ir for highly efficient acidic oxygen evolution. Chemical Engineering Journal 2021, 9 , 133251. https://doi.org/10.1016/j.cej.2021.133251
  19. Zhaolong Wang, Wenjun Liu, Jian Bao, Yanhua Song, Xiaojie She, Yingjie Hua, Guoai Lv, Junjie Yuan, Huaming Li, Hui Xu. Modulating electronic structure of ternary NiMoV LDH nanosheet array induced by doping engineering to promote urea oxidation reaction. Chemical Engineering Journal 2021, 286 , 133100. https://doi.org/10.1016/j.cej.2021.133100
  20. Andrei Cristian Kuncser, Ioana Dorina Vlaicu, Octavian Dumitru Pavel, Rodica Zavoianu, Mihaela Badea, Dana Radu, Daniela Cristina Culita, Arpad Mihai Rostas, Rodica Olar. Soft synthesis and characterization of goethite-based nanocomposites as promising cyclooctene oxidation catalysts. RSC Advances 2021, 11 (44) , 27589-27602. https://doi.org/10.1039/D1RA04211D
  21. Lei Yang, Hongye Qin, Zihao Dong, Tongzhou Wang, Guichang Wang, Lifang Jiao. Metallic S‐CoTe with Surface Reconstruction Activated by Electrochemical Oxidation for Oxygen Evolution Catalysis. Small 2021, 17 (31) , 2102027. https://doi.org/10.1002/smll.202102027
  22. Yan He, Tao Yu, Hui Wen, Rui Guo. Boosting the charge transfer of FeOOH/Ni(OH) 2 for excellent oxygen evolution reaction via Cr modification. Dalton Transactions 2021, 50 (28) , 9746-9753. https://doi.org/10.1039/D1DT01469B
  23. Jianqing Zhou, Luo Yu, Qiancheng Zhou, Chuqiang Huang, Yuanlu Zhang, Bo Yu, Ying Yu. Ultrafast fabrication of porous transition metal foams for efficient electrocatalytic water splitting. Applied Catalysis B: Environmental 2021, 288 , 120002. https://doi.org/10.1016/j.apcatb.2021.120002
  24. Lingxing Zan, Hongling Zhang, Xin Bo, Yuyue Zhao, Huanqing Tian, Hao Chen, Qingbo Wei, Haoqing Tang, Feng Fu. Investigation of the synergistic effect on cobalt oxide modified silver surface for electrocatalytic hydrogen evolution reaction. Journal of Alloys and Compounds 2021, 869 , 159324. https://doi.org/10.1016/j.jallcom.2021.159324
  25. Peili Zhang, Tao Song, Dehua Zheng, Fusheng Li, Xiujuan Wu, Ke Fan, Licheng Sun. Ni III ‐rich NiFeBa as an Efficient Catalyst for Water Oxidation. ChemSusChem 2021, 14 (12) , 2516-2520. https://doi.org/10.1002/cssc.202100833
  26. Rahman Daiyan, Thanh Tran-Phu, Priyank Kumar, Kevin Iputera, Zizheng Tong, Joshua Leverett, Muhammad Haider Ali Khan, Ali Asghar Esmailpour, Ali Jalili, Maggie Lim, Antonio Tricoli, Ru-Shi Liu, Xunyu Lu, Emma Lovell, Rose Amal. Nitrate reduction to ammonium: from CuO defect engineering to waste NO x -to-NH 3 economic feasibility. Energy & Environmental Science 2021, 14 (6) , 3588-3598. https://doi.org/10.1039/D1EE00594D
  27. Yinling Wang, Wujian Tang, Xue Li, Dandan Wei. Improving the electrocatalytic activity of NiFe bimetal-organic framework toward oxygen evolution reaction by Zr doping. Electrochimica Acta 2021, 381 , 138292. https://doi.org/10.1016/j.electacta.2021.138292
  28. Gaowei Zhang, Junrong Zeng, Jing Yin, Chunyan Zuo, Peng Wen, Hongtao Chen, Yejun Qiu. Iron-facilitated surface reconstruction to in-situ generate nickel–iron oxyhydroxide on self-supported FeNi alloy fiber paper for efficient oxygen evolution reaction. Applied Catalysis B: Environmental 2021, 286 , 119902. https://doi.org/10.1016/j.apcatb.2021.119902
  29. Tingwen Zhao, Xiangjian Shen, Yuan Wang, Rosalie K. Hocking, Yibing Li, Chengli Rong, Kamran Dastafkan, Zhen Su, Chuan Zhao. In Situ Reconstruction of V‐Doped Ni 2 P Pre‐Catalysts with Tunable Electronic Structures for Water Oxidation. Advanced Functional Materials 2021, 31 (25) , 2100614. https://doi.org/10.1002/adfm.202100614
  30. 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. https://doi.org/10.1016/j.apsusc.2021.149514
  31. Zihao Liu, Shifeng Li, Fangfang Wang, Mingxia Li, Yonghong Ni. Hierarchically porous FeNi 3 @FeNi layered double hydroxide nanostructures: one-step fast electrodeposition and highly efficient electrocatalytic performances for overall water splitting. Dalton Transactions 2021, 50 (18) , 6306-6314. https://doi.org/10.1039/D0DT04366D
  32. Yuan Wang, Borui Liu, Xiangjian Shen, Hamidreza Arandiyan, Tingwen Zhao, Yibing Li, Magnus Garbrecht, Zhen Su, Li Han, Antonio Tricoli, Chuan Zhao. Engineering the Activity and Stability of MOF‐Nanocomposites for Efficient Water Oxidation. Advanced Energy Materials 2021, 11 (16) , 2003759. https://doi.org/10.1002/aenm.202003759
  33. Animesh Roy, Kwang-Mo Kang, Yoon-Chae Nah, Moonwoo La, Dongwhi Choi, Sung Jea Park. Improved electrocatalytic water oxidation with cobalt hydroxide nano-flakes supported on copper-modified nickel foam. Electrochimica Acta 2021, 10 , 138368. https://doi.org/10.1016/j.electacta.2021.138368
  34. Junsheng Chen, Hao Li, Shuangming Chen, Jingyuan Fei, Chang Liu, Zixun Yu, Kihyun Shin, Zongwen Liu, Li Song, Graeme Henkelman, Li Wei, Yuan Chen. Co–Fe–Cr (oxy)Hydroxides as Efficient Oxygen Evolution Reaction Catalysts. Advanced Energy Materials 2021, 11 (11) , 2003412. https://doi.org/10.1002/aenm.202003412
  35. Jin‐Bo Pan, Bing‐Hao Wang, Jin‐Bo Wang, Hong‐Zhi Ding, Wei Zhou, Xuan Liu, Jin‐Rong Zhang, Sheng Shen, Jun‐Kang Guo, Lang Chen, Chak‐Tong Au, Li‐Long Jiang, Shuang‐Feng Yin. Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO 4 Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation. Angewandte Chemie 2021, 133 (3) , 1453-1460. https://doi.org/10.1002/ange.202012550
  36. Jin‐Bo Pan, Bing‐Hao Wang, Jin‐Bo Wang, Hong‐Zhi Ding, Wei Zhou, Xuan Liu, Jin‐Rong Zhang, Sheng Shen, Jun‐Kang Guo, Lang Chen, Chak‐Tong Au, Li‐Long Jiang, Shuang‐Feng Yin. Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO 4 Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation. Angewandte Chemie International Edition 2021, 60 (3) , 1433-1440. https://doi.org/10.1002/anie.202012550
  37. Sixuan She, Yinlong Zhu, Hassan A. Tahini, Xinhao Wu, Daqin Guan, Yu Chen, Jie Dai, Yubo Chen, Wanqi Tang, Sean C. Smith, Huanting Wang, Wei Zhou, Zongping Shao. Efficient Water Splitting Actualized through an Electrochemistry‐Induced Hetero‐Structured Antiperovskite/(Oxy)Hydroxide Hybrid. Small 2020, 16 (51) , 2006800. https://doi.org/10.1002/smll.202006800
  38. Tingwen Zhao, Yuan Wang, Siva Karuturi, Kylie Catchpole, Qiang Zhang, Chuan Zhao. Design and operando/in situ characterization of precious‐metal‐free electrocatalysts for alkaline water splitting. Carbon Energy 2020, 2 (4) , 582-613. https://doi.org/10.1002/cey2.79
  39. Xin Bo, Rosalie K Hocking, Si Zhou, Yibing Li, Xianjue Chen, Jincheng Zhuang, Yi Du, Chuan Zhao. Capturing the active sites of multimetallic (oxy)hydroxides for the oxygen evolution reaction. Energy & Environmental Science 2020, 13 (11) , 4225-4237. https://doi.org/10.1039/D0EE01609H
  40. Ran Duan, Yejun Li, Shen Gong, Yonggang Tong, Zhou Li, Weihong Qi. Hierarchical CoFe oxyhydroxides nanosheets and Co2P nanoparticles grown on Ni foam for overall water splitting. Electrochimica Acta 2020, 360 , 136994. https://doi.org/10.1016/j.electacta.2020.136994