Abstract
Developing cost-effective and high-performance oxygen evolution reaction (OER) electrocatalysts has become the intense research on pursuing emerging renewable energy conversion, in which exploring and investigating the intrinsic nature of efficient and stable CuCo spinel catalysts toward OER in alkaline media is highly desirable. Herein, Cu1−xCo2+xO4 oxy-spinel nanoflakes are fabricated by a facile hydrothermal method with the oxidation of ammonia water. In the same condition, Cu1−x-Co2+xS4 thio-spinel nanospheres are formed without oxidation. In OER process, the as-obtained Cu1−xCo2+xO4 nanoflakes and Cu1−xCo2+xS4 nanospheres possess the anodic overpotential of 267 and 297 mV in alkaline media to drive the current density of 10 mA/cm2, respectively, outperforming the state-of-the-art noble metal catalyst of RuO2. X-ray photoelectron spectroscopy analysis exhibits the higher ratio value of Co(III)/Co(II) in Cu1−xCo2+xO4 than that in Cu1−xCo2+xS4, suggesting that the strongly-electronegative oxygen efficiently predominates in regulating valence states of Co active sites in spinel structures. Remarkably, density functional theory simulation further reveals that the increased valence state of Co could accelerate the electron exchange between catalysts and oxygen adsorbates during electrocatalysis, thus contributing to the higher OER activity of Cu1−xCo2+xO4 catalysts. This work provides deep insight regarding the significance of non-metal element (O and S) in CuCo spinel structure catalysts, as well as presents a promising approach to exploit higher performance and grasp the mechanism of various non-noble-metal spinel catalysts for water oxidation.
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Song Z, Ding J, Liu B, Liu X, Han X, Deng Y, Hu W, Zhong C. Adv Mater, 2020, 32: 1908127
Kou T, Yang Y, Yao B, Li Y. Small Methods, 2018, 2: 1800152
Wang J, Han L, Huang B, Shao Q, Xin HL, Huang X. Nat Commun, 2019, 10: 5692
Chen LN, Yu WS, Wang T, Yang XD, Yang HJ, Chen ZX, Wang T, Tian N, Zhou ZY, Sun SG. Sci China Chem, 2020, 63: 198–202
Fu Y, Cao F, Wu F, Diao Z, Chen J, Shen S, Li L. Adv Funct Mater, 2018, 28: 1706785
Meng L, Wang S, Cao F, Tian W, Long R, Li L. Angew Chem Int Ed, 2019, 58: 6761–6765
Zhou P, He J, Zou Y, Wang Y, Xie C, Chen R, Zang S, Wang S. Sci China Chem, 2019, 62: 1365–1370
Deng X, Tüysüz H. ACS Catal, 2014, 4: 3701–3714
Reier T, Nong HN, Teschner D, Schlögl R, Strasser P. Adv Energy Mater, 2017, 7: 1601275
Buvat G, Eslamibidgoli MJ, Youssef AH, Garbarino S, Ruediger A, Eikerling M, Guay D. ACS Catal, 2020, 10: 806–817
Wang B, Huang H, Huang M, Yan P, Isimjan TT, Yang X. Sci China Chem, 2020, 63: 841–849
Yuan X, Ge H, Wang X, Dong C, Dong W, Riaz MS, Xu Z, Zhang J, Huang F. ACS Energy Lett, 2017, 2: 1208–1213
Liu Q, Wang L, Liu X, Yu P, Tian C, Fu H. Sci China Mater, 2019, 62: 624–632
Li Y, Li FM, Meng XY, Li SN, Zeng JH, Chen Y. ACS Catal, 2018, 8: 1913–1920
Shenghai C, Liping S, Fanhao K, Lihua H, Hui Z. J Power Sources, 2019, 430: 25–31
Wang W, Kuai L, Cao W, Huttula M, Ollikkala S, Ahopelto T, Honkanen AP, Huotari S, Yu M, Geng B. Angew Chem Int Ed, 2017, 56: 14977–14981
Wang XT, Ouyang T, Wang L, Zhong JH, Ma T, Liu ZQ. Angew Chem Int Ed, 2019, 58: 13291–13296
Gao X, Zhang H, Li Q, Yu X, Hong Z, Zhang X, Liang C, Lin Z. Angew Chem Int Ed, 2016, 55: 6290–6294
Chen Z, Zhao H, Zhang J, Xu J. Sci China Mater, 2017, 60: 119–130
Liu ZQ, Cheng H, Li N, Ma TY, Su YZ. Adv Mater, 2016, 28: 3777–3784
Zhang X, Si C, Guo X, Kong R, Qu F. J Mater Chem A, 2017, 5: 17211–17215
Hu X, Wang R, Sun P, Xiang Z, Wang X. ACS Sustain Chem Eng, 2019, 7: 19426–19433
Liu D, Lu Q, Luo Y, Sun X, Asiri AM. Nanoscale, 2015, 7: 15122–15126
Han X, Zhang W, Ma X, Zhong C, Zhao N, Hu W, Deng Y. Adv Mater, 2019, 31: 1808281
Song G, Wang Z, Sun J, Sun J, Yuan D, Zhang L. Electrochem Commun, 2019, 105: 106487
Luo H, Lei H, Yuan Y, Liang Y, Qiu Y, Zhu Z, Wang Z. Catalysts, 2019, 9: 459
Zhang H, Wang X, Yang Z, Yan S, Zhang C, Liu S. ACS Sustain Chem Eng, 2020, 8: 1004–1014
Cheng H, Li ML, Su CY, Li N, Liu ZQ. Adv Funct Mater, 2017, 27: 1701833
Wang X, Li Y, Jin T, Meng J, Jiao L, Zhu M, Chen J. Nano Lett, 2017, 17: 7989–7994
Jin W, Chen J, Wu Z, Maduraiveeran G. Int J Hydrogen Energy, 2019, 44: 11421–11430
Pawar SM, Pawar BS, Babar PT, Ahmed ATA, Chavan HS, Jo Y, Cho S, Kim J, Hou B, Inamdar AI, Cha SN, Kim JH, Kim TG, Kim H, Im H. Appl Surf Sci, 2019, 470: 360–367
Chauhan M, Reddy KP, Gopinath CS, Deka S. ACS Catal, 2017, 7: 5871–5879
Kuang M, Han P, Wang Q, Li J, Zheng G. Adv Funct Mater, 2016, 26: 8555–8561
Zheng J, Chen X, Zhong X, Li S, Liu T, Zhuang G, Li X, Deng S, Mei D, Wang JG. Adv Funct Mater, 2017, 27: 1704169
Wang J, Li K, Zhang L, Ge B, Liu Y, Yang T, Liu D. Int J Hydrogen Energy, 2017, 42: 3316–3324
Czioska S, Wang J, Teng X, Chen Z. ACS Sustain Chem Eng, 2018, 6: 11877–11883
Wang Z, Liu H, Ge R, Ren X, Ren J, Yang D, Zhang L, Sun X. ACS Catal, 2018, 8: 2236–2241
Zhao Q, Yan Z, Chen C, Chen J. Chem Rev, 2017, 117: 10121–10211
Zhou Y, Sun S, Wei C, Sun Y, Xi P, Feng Z, Xu ZJ. Adv Mater, 2019, 31: 1902509
Zhou M, Zhang R, Huang M, Lu W, Song S, Melancon MP, Tian M, Liang D, Li C. J Am Chem Soc, 2010, 132: 15351–15358
Kresse G, Furthmüller J. Phys Rev B, 1996, 54: 11169–11186
Blöchl PE. Phys Rev B, 1994, 50: 17953–17979
Kresse G, Joubert D. Phys Rev B, 1999, 59: 1758–1775
Grimme S, Antony J, Ehrlich S, Krieg H. J Chem Phys, 2010, 132: 154104
Liu Y, Ying Y, Fei L, Liu Y, Hu Q, Zhang G, Pang SY, Lu W, Mak CL, Luo X, Zhou L, Wei M, Huang H. J Am Chem Soc, 2019, 141: 8136–8145
Lu Y, Dong CL, Huang YC, Zou Y, Liu Y, Li Y, Zhang N, Chen W, Zhou L, Lin H, Wang S. Sci China Chem, 2020, 63: 980–986
Shi Y, Ndione PF, Lim LY, Sokaras D, Weng TC, Nagaraja AR, Karydas AG, Perkins JD, Mason TO, Ginley DS, Zunger A, Toney MF. Chem Mater, 2014, 26: 1867–1873
Li B, Xue H, Pang H, Xu Q. Sci China Chem, 2020, 63: 475–482
Hao P, Xin Y, Tian J, Li L, Xie J, Lei F, Tong L, Liu H, Tang B. Sci China Chem, 2020, 63: 1030–1039
Lee M, Oh HS, Cho MK, Ahn JP, Hwang YJ, Min BK. Appl Catal B-Environ, 2018, 233: 130–135
Acknowledgements
We acknowledge the support from the National Natural Science Foundation of China (91750112, 51801075) and Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX 19_1591). D Rao gratefully acknowledges the support of Jiangsu Overseas Visiting Scholar Program for University Prominent Young and Mid-aged Teachers and Presidents.
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Yang, H., Gao, S., Rao, D. et al. Non-metallic electronic regulation in CuCo oxy-/thio-spinel as advanced oxygen evolution electrocatalysts. Sci. China Chem. 64, 101–108 (2021). https://doi.org/10.1007/s11426-020-9895-2
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DOI: https://doi.org/10.1007/s11426-020-9895-2