Toward enhanced alkaline hydrogen electrocatalysis with transition metal-functionalized nitrogen-doped carbon supports

doi:10.1016/S1872-2067(21)63935-9

Abstract

Abstract:

Superior catalyst supports are crucial to developing advanced electrocatalysts toward heterogeneous catalytic reactions. Herein, we systematically investigate the role of transition metal-functionalized N-doped carbon nanosheets (M-N-C, M = Mn, Fe, Co, Ni, Cu, Mo, and Ag) as the multifunctional electrocatalyst supports toward hydrogen evolution/oxidation reactions (HER/HOR) in alkaline media. The results demonstrate that all the M-N-C nanosheets, except Cu-N-C and Ag-N-C, can promote the alkaline HER/HOR electrocatalytic activity of Pt by accelerating the sluggish Volmer step, among which Mn plays a more significant role. Analyses reveal that the promotion effect of M-N-C support is closely associated with the electronegativity of the metal dopants and the relative filling degree of their d-orbitals. For one, the metal dopant in M-N-C with smaller electronegativity would provide more electrons to oxygen and hence tune the electronic structure of Pt via the M-O-Pt bonds at the interface. For another, the transition metal in M-N₄ moieties with more empty d orbitals would hybridize with O 2p orbitals more strongly that promotes the adsorption of water/hydroxyl species. The results demonstrate the conceptual significance of multifunctional supports and would inspire the future development of advanced electrocatalysts.

Key words: Multifunctional support, Hydrogen oxidation reaction, Hydrogen evolution reaction, Metal-support interaction, Electrocatalysis

Peng Li, Guoqiang Zhao, Ningyan Cheng, Lixue Xia, Xiaoning Li, Yaping Chen, Mengmeng Lao, Zhenxiang Cheng, Yan Zhao, Xun Xu, Yinzhu Jiang, Hongge Pan, Shi Xue Dou, Wenping Sun. Toward enhanced alkaline hydrogen electrocatalysis with transition metal-functionalized nitrogen-doped carbon supports[J]. Chinese Journal of Catalysis, 2022, 43(5): 1351-1359.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63935-9

https://www.cjcatal.com/EN/Y2022/V43/I5/1351

Figures/Tables 5

Fig. 1. HAADF-STEM images of Mn-N-C (a), Co-N-C (b), and Cu-N-C (c) nanosheets; HAADF-STEM images (d,e) and the EDS elemental mapping images (f) of Mn-N-C/Pt.

Fig. 2. XANES spectra of the samples at Mn K-edge (a), Co K-edge (b), Cu K-edge (c), C K-edge (d), and N K-edge (e); (f) N1s XPS spectra of the samples; FT-EXAFS spectra and the corresponding fitting results of the samples at Mn K-edge (g), Co K-edge (h), and Cu K-edge (i).

Fig. 3. XANES (a) and EXAFS (b) spectra of the samples at Pt L3-edge; (c) EXAFS spectra of M-N-C/Pt at Pt L3-edge and the corresponding fitting results; WT of Mn-N-C/Pt (d), Pt foil (e), and PtO2 (f); (g) Pt 4f XPS spectra of the samples; (h) BEs of PtII 4f7/2 species in the samples; (i) Illustration of Pt NP on Mn-N-C.

Fig. 4. Electrochemical performance of the samples. (a) HOR polarization curves normalized to the diffusion-limited current density jlim; (b) The kinetic current density and the fitting curves are calculated based on the Volmer-Butler equation; (c) The exchange current density of the samples; ECSA-normalized HER polarization LSV curves (d) and the corresponding Tafel plots (e); (f) The ECSA-normalized current density of the samples at 200 mV.

Fig. 5. (a) The illustration of electron occupation of metal 3d orbitals for Pt-O-M-N4 structure, with the eg orbital filling degree for M-N4 (M = Mn, Fe, Co, Ni, and Cu); (b) The Gibbs free energy of water adsorption on M-N-C support; (c) The OH binding energy on M-N-C support; (d) The schematic illustration of HER/HOR reaction mechanism on M-N-C/Pt heterostructured electrocatalysts; (e) The HER/HOR activity using Mo-N-C and Ag-N-C as supports.

References

[1]	A. Buttler, H. Spliethoff, Renew. Sust. Energy Rev., 2018, 82, 2440-2454.
[2]	S. Lu, J. Pan, A. Huang, L. Zhuang, J. Lu, Proc. Natl. Acad. Sci. USA, 2008, 105, 20611-20614.
[3]	S. Gottesfeld, D. R. Dekel, M. Page, C. Bae, Y. Yan, P. Zelenay, Y. S. Kim, J. Power Sources, 2018, 375, 170-184.
[4]	G. Zhao, K. Rui, S. X. Dou, W. Sun, Adv. Funct. Mater., 2018, 28, 1803291.
[5]	H. Peng, Q. Li, M. Hu, L. Xiao, J. Lu, L. Zhuang, J. Power Sources, 2018, 390, 165-167.
[6]	L. Xie, X. Ren, Q. Liu, G. Cui, R. Ge, A. M. Asiri, X. Sun, Q. Zhang, L. Chen, J. Mater. Chem. A, 2018, 6, 1967-1970.
[7]	L. Zeng, H. Peng, W. Liu, J. Yin, L. Xiao, J. Lu, L. Zhuang, J. Power Sources, 2020, 461, 228147.
[8]	S. Xu, H. Zhao, T. Li, J. Liang, S. Lu, G. Chen, S. Gao, A. M. Asiri, Q. Wu, X. Sun, J. Mater. Chem. A, 2020, 8, 19729-19745.
[9]	G. Zhao, J. Chen, W. Sun, H. Pan, Adv. Funct. Mater., 2021, 31, 2010633.
[10]	J. Mahmood, F. Li, S. M. Jung, M. S. Okyay, I. Ahmad, S. J. Kim, N. Park, H. Y. Jeong, J. B. Baek, Nat. Nanotechnol., 2017, 12, 441-446.
[11]	X. Zheng, P. Cui, Y. Qian, G. Zhao, X. Zheng, X. Xu, Z. Cheng, Y. Liu, S. X. Dou, W. Sun, Angew. Chem. Int. Ed., 2020, 59, 14533-14540.
[12]	G. Zhao, Y. Jiang, S.-X. Dou, W. Sun, H. Pan, Sci. Bull., 2020, 66, 85-96.
[13]	X. Wu, B. Feng, W. Li, Y. Niu, Y. Yu, S. Lu, C. Zhong, P. Liu, Z. Tian, L. Chen, W. Hu, C. M. Li, Nano Energy, 2019, 62, 117-126.
[14]	E. R. Hamo, R. K. Singh, J. C. Douglin, S. Chen, M. B. Hassine, E. Carbo-Argibay, S. Lu, H. Wang, P. J. Ferreira, B. A. Rosen, D. R. Dekel, ACS Catal., 2021, 11, 932-947.
[15]	D. H. Kweon, M. S. Okyay, S.-J. Kim, J.-P. Jeon, H.-J. Noh, N. Park, J. Mahmood, J.-B. Baek, Nat. Commun., 2020, 11, 1278.
[16]	M. Lao, G. Zhao, P. Li, T. Ma, Y. Jiang, H. Pan, S.X. Dou, W. Sun, Adv. Funct. Mater., 2021, 31, 2100698.
[17]	X. Li, R. Zhang, Y. Luo, Q. Liu, S. Lu, G. Chen, S. Gao, S. Chen, X. Sun, Sustain. Energy Fuels, 2020, 4, 3884-3887.
[18]	S. Niu, Y. Fang, J. Zhou, J. Cai, Y. Zang, Y. Wu, J. Ye, Y. Xie, Y. Liu, X. Zheng, W. Qu, X. Liu, G. Wang, Y. Qian, J. Mater. Chem. A, 2019, 7, 10924-10929.
[19]	C. Xie, Z. Niu, D. Kim, M. Li, P. Yang, Chem. Rev., 2020, 120, 1184-1249.
[20]	F. Yang, X. Bao, Y. Zhao, X. Wang, G. Cheng, W. Luo, J. Mater. Chem. A, 2019, 7, 10936-10941.
[21]	Y. Chen, J. Cai, P. Li, G. Zhao, G. Wang, Y. Jiang, J. Chen, S. X. Dou, H. Pan, W. Sun, Nano Lett., 2020, 20, 6807-6814.
[22]	H. Liu, Y. Liu, D. Zhu, J. Mater. Chem., 2011, 21, 3335-3345.
[23]	I. C. Gerber, P. Serp, Chem. Rev., 2020, 120, 1250-1349.
[24]	I.-Y. Jeon, H.-J. Noh, J.-B. Baek, Chem. Asian J., 2020, 15, 2282-2293.
[25]	P. Li, G. Zhao, P. Cui, N. Cheng, M. Lao, X. Xu, S. X. Dou, W. Sun, Nano Energy, 2021, 83, 105850.
[26]	B. Ravel, M. Newville, J. Synchrotron Radiat., 2005, 12, 537-541.
[27]	Z. Xia, H. Zhang, K. Shen, Y. Qu, Z. Jiang, Phys. B Condens. Matter, 2018, 542, 12-19.
[28]	C. Wei, R. R. Rao, J. Peng, B. Huang, I. E. L. Stephens, M. Risch, Z. J. Xu, Y. Shao-Horn, Adv. Mater., 2019, 31, 1806296.
[29]	J. Durst, C. Simon, F. Hasche, H. A. Gasteiger, J. Electrochem. Soc., 2014, 162, F190-F203.
[30]	J. Zheng, Y. Yan, B. Xu, J. Electrochem. Soc., 2015, 162, F1470-F1481.
[31]	M. D. Segall, P. J. D. Lindan, M. J. Probert, C. J. Pickard, P. J. Hasnip, S. J. Clark, M. C. Payne, J. Phys.: Condens. Matter, 2002, 14, 2717-2744.
[32]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[33]	P. Yang, X. Yuan, H. Hu, Y. Liu, H. Zheng, D. Yang, L. Chen, M. Cao, Y. Xu, Y. Min, Y. Li, Q. Zhang, Adv. Funct. Mater., 2018, 28, 1704774.
[34]	H. Fei, J. Dong, C. Wan, Z. Zhao, X. Xu, Z. Lin, Y. Wang, H. Liu, K. Zang, J. Luo, S. Zhao, W. Hu, W. Yan, I. Shakir, Y. Huang, X. Duan, Adv. Mater., 2018, 30, 1802146.
[35]	H. B. Yang, S.-F. Hung, S. Liu, K. Yuan, S. Miao, L. Zhang, X. Huang, H.-Y. Wang, W. Cai, R. Chen, J. Gao, X. Yang, W. Chen, Y. Huang, H. M. Chen, C. M. Li, T. Zhang, B. Liu, Nat. Energy, 2018, 3, 140-147.
[36]	H. Fei, J. Dong, M. J. Arellano-Jimenez, G. Ye, N. Dong Kim, E. L. G. Samuel, Z. Peng, Z. Zhu, F. Qin, J. Bao, M. J. Yacaman, P. M. Ajayan, D. Chen, J. M. Tour, Nat. Commun., 2015, 6, 8668.
[37]	L. Jiao, G. Wan, R. Zhang, H. Zhou, S.-H. Yu, H.-L. Jiang, Angew. Chem. Int. Ed., 2018, 57, 8525-8529.
[38]	D. Zheng, Z. Gao, X. He, F. Zhang, L. Liu, Appl. Surf. Sci., 2003, 211, 24-30.
[39]	W. Ju, A. Bagger, G.-P. Hao, A. S. Varela, I. Sinev, V. Bon, B. Roldan Cuenya, S. Kaskel, J. Rossmeisl, P. Strasser, Nat. Commun., 2017, 8, 944.
[40]	H. Shang, X. Zhou, J. Dong, A. Li, X. Zhao, Q. Liu, Y. Lin, J. Pei, Z. Li, Z. Jiang, D. Zhou, L. Zheng, Y. Wang, J. Zhou, Z. Yang, R. Cao, R. Sarangi, T. Sun, X. Yang, X. Zheng, W. Yan, Z. Zhuang, J. Li, W. Chen, D. Wang, J. Zhang, Y. Li, Nat. Commun., 2020, 11, 3049.
[41]	X. Zheng, P. Li, S. Dou, W. Sun, H. Pan, D. Wang, Y. Li, Energy Environ. Sci., 2021, 14, 2809-2858.
[42]	F. Li, G.-F. Han, H.-J. Noh, S.-J. Kim, Y. Lu, H.Y. Jeong, Z. Fu, J.-B. Baek, Energy Environ. Sci., 2018, 11, 2263-2269.
[43]	Z. Yang, Y. Wang, M. Zhu, Z. Li, W. Chen, W. Wei, T. Yuan, Y. Qu, Q. Xu, C. Zhao, X. Wang, P. Li, Y. Li, Y. Wu, Y. Li, ACS Catal., 2019, 9, 2158-2163.
[44]	K. Rui, G. Zhao, M. Lao, P. Cui, X. Zheng, X. Zheng, J. Zhu, W. Huang, S. X. Dou, W. Sun, Nano Lett., 2019, 19, 8447-8453.
[45]	S. Fang, X. Zhu, X. Liu, J. Gu, W. Liu, D. Wang, W. Zhang, Y. Lin, J. Lu, S. Wei, Nat. Commun., 2020, 11, 1029.
[46]	H. Zhang, P. An, W. Zhou, B. Y. Guan, P. Zhang, J. Dong, X. W. Lou, Sci. Adv., 2018, 4, eaao6657.
[47]	X. Zeng, J. Shui, X. Liu, Q. Liu, Y. Li, J. Shang, L. Zheng, R. Yu, Adv. Energy Mater., 2018, 8, 1701345.
[48]	J. Li, P. Prslja, T. Shinagawa, A.J. Martin Fernandez, F. Krumeich, K. Artyushkova, P. Atanassov, A. Zitolo, Y. Zhou, R. Garcia-Muelas, J. Perez-Ramirez, F. Jaouen, ACS Catal., 2019, 9, 10426-10439.
[49]	J. H. Zagal, M. T. M. Koper, Angew. Chem. Int. Ed., 2016, 55, 14510-14521.
[50]	J. Van Vleck, J. Chem. Phys., 1935, 3, 807-813.
[51]	R. Schlapp, W. G. Penney, Phys. Rev., 1932, 42, 666-686.
[52]	J. Van Vleck, Phys. Rev., 1932, 41, 208-215.
[53]	J. Suntivich, K. J. May, A. Gasteiger, J. B. Goodenough, Y. Shao-Horn, Science, 2011, 334, 1383-1385.
[54]	T. Maiyalagan, K. A. Jarvis, S. Therese, P. J. Ferreira, A. Manthiram, Nat. Commun., 2014, 5, 3949.