Cobalt-regulation-induced dual active sites in Ni2P for hydrazine electrooxidation

doi:10.1016/S1872-2067(21)63951-7

Abstract

Abstract:

Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable. Herein, the dehydrogenation kinetics of hydrazine electrooxidation at Ni₂P is adjusted by Co as the (Ni_0.6Co_0.4)₂P catalyzes HzOR effectively with onset potential of -45 mV and only 113 mV is needed to drive the current density of 50 mA cm^‒2, showing over 60 mV lower than Ni₂P and Co₂P. It also delivers the maximum power density of 263.0 mW cm^‒2for direct hydrazine fuel cell. Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N₂H₄ on Ni sites, lowering the energy barrier for dehydrogenation, but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics. This work represents a breakthrough in improving the catalytic performance of non-precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy-saving electrochemical hydrogen production method.

Key words: Hydrazine electrooxidation reaction, Direct hydrazine fuel cell, Electrocatalyst, Activity, Nickel phosphide

Bo Zhou, Mengyu Li, Yingying Li, Yanbo Liu, Yuxuan Lu, Wei Li, Yujie Wu, Jia Huo, Yanyong Wang, Li Tao, Shuangyin Wang. Cobalt-regulation-induced dual active sites in Ni₂P for hydrazine electrooxidation[J]. Chinese Journal of Catalysis, 2022, 43(4): 1131-1138.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63951-7

https://www.cjcatal.com/EN/Y2022/V43/I4/1131

Figures/Tables 4

Fig. 1. Morphological and structural characterization of (Ni0.6Co0.4)2P electrode. (a) SEM image of (Ni0.6Co0.4)2P precursor; (b) SEM and TEM images of (Ni0.6Co0.4)2P; (c) XRD patterns of as synthesized (Ni0.6Co0.4)2P and Ni2P; High-resolution XPS spectra of Ni 2p (d), Co 2p (e) and P 2p (f).

Fig. 2. Electrocatalytic activity towards HzOR in 1.0 mol/L KOH/0.1 mol/L N2H4 electrolyte. (a) CV diagrams of Ni2P, (Ni0.6Co0.4)2P and Co2P in 1 mol/L KOH with 0.1 mol/L N2H4 with scan rate of 20 mV s-1; (b) Comparison of the overpotential of Ni2P, Co2P and (Ni0.6Co0.4)2P electrode at the j of 50 mA cm-2; (c) Calculated Tafel plots of Ni2P, (Ni0.6Co0.4)2P and Co2P electrode; (d) CV diagrams of (Ni0.6Co0.4)2P, (Ni0.6Co0.4)2P precursor, commercial Pt/C and bare GCE; (e) CV diagrams of Ni2P and (Ni0.6Co0.4)2P electrodes before and after stability test and the inset is the corresponding potentiostatic electrolysis curves; (f) The fitted Rct from the in situ EIS at Ni2P and (Ni0.6Co0.4)2P electrodes.

Fig. 3. Demonstration of energy releasing from hydrazine. Schematic diagram (a) and the polarization curves (c) of DHFCs with Pt/C cathode and (Ni0.6Co0.4)2P anode. GDL denotes as gas diffusion layer and AEM denotes as anion exchange membrane; Schematic diagram (b) and the polarization curves (d) of overall water splitting (black line) and hydrazine assisted water splitting (red line) in two-electrode system with Co2P cathode and (Ni0.6Co0.4)2P anode.

Fig. 4. DFT calculated profiles of free energy. (a) Optimized structure of hydrazine on (Ni0.6Co0.4)2P surface; (b) Density of states plots of (Ni0.6Co0.4)2P; (c) The most stable configurations of the adsorbed intermediates on the metal sites of (Ni0.6Co0.4)2P; (d) The free-energy profiles of HzOR on the (Ni0.6Co0.4)2P surface; (e?g) Top view of differential charge densities for Ni2P, Co2P and (Ni0.6Co0.4)2P with hydrazine, cyan region represents electron depletion and yellow region represents electron accumulation.

References

[1]	D. Khalafallah, M. J. Zhi, Z. L. Hong, ChemCatChem, 2021, 13, 81-110.
[2]	X. Lin, H. Wen, D. X. Zhang, G. X. Cao, P. Wang, J. Mater. Chem. A, 2020, 8, 632-638.
[3]	Y. P. Li, J. H. Zhang, Y. Liu, Q. Z. Qian, Z. Y. Li, Y. Zhu, G. Q. Zhang, Sci. Adv., 2020, 6, eabb4197.
[4]	Y. Liu, J. H. Zhang, Y. P. Li, Q. Z. Qian, Z. Y. Li, Y. Zhu, G. Q. Zhang, Nat. Commun., 2020, 11, 1853.
[5]	Q. Z. Qian, J. H. Zhang, J. M. Li, Y. P. Li, X. Jin, Y. Zhu, Y. Liu, Z. Y. Li, A. El-Harairy, C. Xiao, G. Q. Zhang, Y. Xie, Angew. Chem. Int. Ed., 2021, 60, 5894-5993.
[6]	C. Tang, R. Zhang, W. B. Lu, Z. Wang, D. N. Liu, S. Hao, G. Du, A. M. Asiri, X. P. Sun, Angew. Chem. Int. Ed., 2017, 56, 842-846.
[7]	L. S. Wu, X. P. Wen, H. Wen, H. B. Dai, P. Wang, J. Power Sources, 2019, 412, 71-77.
[8]	G. H. Liu, Z. L. Wang, T. Y. Shen, X. S. Zheng, Y. F. Zhao, Y. F. Song, Nanoscale, 2021, 13, 1869-1874.
[9]	M. G. Hosseini, R. Mahmoodi, M. Abdolmaleki, New J. Chem., 2018, 42, 12222-12233.
[10]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. B. Chorkendorff, J. K. Norskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[11]	A. Serov, M. Padilla, A.J. Roy, P. Atanassov, T. Sakamoto, K. Asazawa, H. Tanaka, Angew. Chem. Int. Ed., 2014, 53, 10336-10339.
[12]	G. Kresse, J. Hafner, Phys. Rev. B, 1993, 48, 13115-13126.
[13]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[14]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[15]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[16]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[17]	S. Grimme, J. Comput. Chem., 2006, 27, 1787-1799.
[18]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[19]	J. Neugebauer, M. Scheffler, Phys. Rev. B, 1992, 46, 16067-16080.
[20]	H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192.
[21]	M. Methfessel, A. T. Paxton, Phys. Rev. B, 1989, 40, 3616-3621.
[22]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jonsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[23]	Z. L. Wang, S. M. Xu, Y. Q. Xu, L. Tan, X. Wang, Y. F. Zhao, H. H. Duan, Y. F. Song, Chem. Sci., 2019, 10, 378-384.
[24]	L. A. Stern, L. G. Feng, F. Song, X. L. Hu, Energy Environ. Sci., 2015, 8, 2347-2351.
[25]	N. N. Zhang, Y. Q. Zou, L. Tao, W. Chen, L. Zhou, Z. J. Liu, B. Zhou, G. Huang, H. Z. Lin, S. Y. Wang, Angew. Chem. Int. Ed., 2019, 58, 15895-15903.
[26]	Z. Q. Hou, C. Z. Shu, P. Hei, T. S. Yang, R. X. Zheng, Z. Q. Ran, J. P. Long, Nanoscale, 2020, 12, 6785-6794.
[27]	X. Y. Zhang, B. Y. Guo, Q. W. Chen, B. Dong, J. Q. Zhang, J. F. Qin, J. Y. Xie, M. Yang, L. Wang, Y. M. Chai, C. G. Liu, Int. J. Hydrogen Energy, 2019, 44, 14908-14917.
[28]	J. Y. Li, M. Yan, X. M. Zhou, Z. Q. Huang, Z. M. Xia, C. R. Chang, Y. Y. Ma, Y. Q. Qu, Adv. Funct. Mater., 2016, 26, 6785-6796.
[29]	D. Das, K. K. Nanda, Nano Energy, 2016, 30, 303-311.
[30]	W. Y. Ni, A. Krammer, C. S. Hsu, H. M. Chen, A. Schuler, X. L. Hu, Angew. Chem. Int. Ed., 2019, 58, 7445-7449.
[31]	X. J. Liu, J. He, S. Z. Zhao, Y. P. Liu, Z. Zhao, J. Luo, G. Z. Hu, X. M. Sun, Y. Ding, Nat. Commun., 2018, 9, 4365.
[32]	S. Chen, J. J. Duan, A. Vasileff, S. Z. Qiao, Angew. Chem. Int. Ed., 2016, 55, 3804-3808.
[33]	E. J. Popczun, J. R. McKone, C. G. Read, A. J. Biacchi, A. M. Wiltrout, N. S. Lewis, R. E. Schaak, J. Am. Chem. Soc., 2013, 135, 9267-9270.
[34]	W. Chen, C. Xie, Y. Y. Wang, Y. Q. Zou, C. L. Dong, Y. C. Huang, Z. H. Xiao, Z. X. Wei, S. Q. Du, C. Chen, B. Zhou, J. M. Ma, S. Y. Wang, Chem, 2020, 6, 2974-2993.
[35]	J. Yu, Q. Cao, Y. B. Li, X. Long, S. H. Yang, J. K. Clark, M. Nakabayashi, N. Shibata, J. J. Delaunay, ACS Catal., 2019, 9, 1605-1611.
[36]	K. Wan, J. S. Luo, C. Zhou, T. Zhang, J. Arbiol, X. H. Lu, B. W. Mao, X. Zhang, J. Fransaer, Adv. Funct. Mater., 2019, 29, 1900315.
[37]	T. Sakamoto, K. Asazawa, U. Martinez, B. Halevi, T. Suzuki, S. Arai, D. Matsumura, Y. Nishihata, P. Atanassov, H. Tanaka, J. Power Sources, 2013, 234, 252-259.
[38]	M. Tahir, L. Pan, F. Idrees, X. W. Zhang, L. Wang, J. J. Zou, Z. L. Wang, Nano Energy, 2017, 37, 136-157.
[39]	S. Z. Oener, M. J. Foster, S. W. Boettcher, Science, 2020, 369, 1099-1103.

Cobalt-regulation-induced dual active sites in Ni₂P for hydrazine electrooxidation

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