Tuning Double Layer Structure of WO3 Nanobelt for Promoting the Electrochemical Nitrogen Reduction Reaction in Water

Abstract
Figure/Table
References (0)
Related Citation (0)

Download: PDF (1271 KB) HTML (1 KB)
Export: BibTeX | EndNote (RIS)

Abstract Electrochemical fixation of nitrogen to ammonia with highly active, highly selective and low cost electrocatalysts is a sustainable alternative to the extremely energy- and capital-intensive Haber-Bosch process. Herein, we demonstrate a near electroneutral WO3 nanobelt catalyst to be a promising electrocatalyst for selective and efficient nitrogen reduction. The concept of near electroneutral interface is demonstrated by fabricating WO3 nanobelts with small zeta potential value on carbon fiber paper, which ensures a loose double layer structure of the electrode/ electrolyte interface and allows nitrogen molecules access the active sites more easily and regulates proton transfer to increase the catalytic selectivity. The WO3/CFP electrode with optimal surface charge achieves a NH3 yield rate of 4.3 μg·h−1·mg−1 and a faradaic efficiency of 37.3% at −0.3 V vs. RHE, rivalling the performance of the state-of-the-art nitrogen reduction reaction electrocatalysts. The result reveals that an unobstructed gas-diffusion pathway for continually supplying enough nitrogen to the active catalytic sites is of great importance to the overall catalytic performance.

Key words： electrochemical nitrogen reduction reaction zeta potential nitrogen diffusionand transport process WO3 nanobelts first-principles calculations

Received: 02 September 2020 Published: 13 April 2021

Fund:This work was supported by Shenzhen Science and Technology Research Grant (ZDSYS201707281026184) and Natural Science Foundation of Shenzhen (JCYJ20190813110605381)

Corresponding Authors: panfeng@pkusz.edu.cn E-mail: panfeng@pkusz.edu.cn

	Service

	E-mail this article
	Add to my bookshelf
	Add to citation manager
	E-mail Alert
	RSS
	Articles by authors
	HONG Qing-Shui
	LI Tang-Yi
	ZHENG Shi-Sheng
	CHEN Hai-Biao
	CHU Hong-Hao
	XU Kuan-Da
	LI Shun-Ning
	MEI Zong-Wei
	ZHAO Qing-He
	REN Wen-Ju
	ZHAO Wen-Guang
	PAN Feng

Cite this article:

HONG Qing-Shui,LI Tang-Yi,ZHENG Shi-Sheng, et al. Tuning Double Layer Structure of WO3 Nanobelt for Promoting the Electrochemical Nitrogen Reduction Reaction in Water[J]. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2021, 40(4): 519-526.

URL:

http://manu30.magtech.com.cn/jghx/EN/ OR http://manu30.magtech.com.cn/jghx/EN/Y2021/V40/I4/519

REFERENCES
(1) Jiao, D.; Iniguez, J. A.; Chong, L. Electrocatalytic nitrogen reduction at low temperature. Joule 2018, 2, 84656.
(2) Cui, X.; Tang, C.; Zhang, Q. A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Adv. Energy Mater. 2018, 8. 180036925.
(3) van der Ham, C. J. M.; Koper, M. T. M.; Hetterscheid, D. G. H. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev. 2014, 43, 51835191.
(4) Cao, N.; Zheng, G. Aqueous electrocatalytic N2 reduction under ambient conditions. Nano Res. 2018, 11, 29923008.
(5) Suryanto, B. H. R.; Kang, C. S. M.; Wang, D.; Xiao, C.; Zhou, F.; Azofra, L. M.; Cavallo, L.; Zhang, X.; MacFarlane, D. R. Rational electrode-electrolyte design for efficient ammonia electrosynthesis under ambient conditions. ACS Energy Lett. 2018, 3, 12191224.
(6) Bao, D.; Zhang, Q.; Meng, F. L.; Zhong, H. X.; Shi, M. M.; Zhang, Y.; Yan, J. M.; Jiang, Q.; Zhang, X. B. Electrochemical reduction of N2 under ambient conditions for artificial N2 fixation and renewable energy storage using N2/NH3 cycle. Adv. Mater. 2017, 29, 16047995.
(7) He, D.; Li, Y.; Ookap, H.; Go, Y. K.; Jin, F.; Kim, S. H.; Nakamura, R. Selective electrocatalytic reduction of nitrite to dinitrogen based on decoupled proton-electron transfer. J. Am. Chem. Soc. 2018, 140, 20122015.
(8) Chen, G. F.; Cao, X.; Wu, S.; Zeng, X.; Ding, L. X.; Zhu, M.; Wang, H. Ammonia electrosynthesis with high selectivity under ambient conditions via a Li+ incorporation strategy. J. Am. Chem. Soc. 2017, 139, 97719774.
(9) Shi, M. M.; Bao, D.; Li, S. J.; Wulan, B. R.; Yan, J. M.; Jiang, Q. Anchoring PdCu amorphous nanocluster on graphene for electrochemical reduction of N2 to NH3 under ambient conditions in aqueous solution. Adv. Energy Mater. 2018, 8, 18001246.
(10) Wang, Z.; Gong, F.; Zhang, L.; Wang, R.; Ji, L.; Liu, Q.; Luo, Y.; Guo, H.; Li, Y.; Gao, P.; Shi, X.; Li, B.; Tang, B.; Sun, X. Electrocatalytic hydrogenation of N2 to NH3 by MnO: experimental and theoretical investigations. Adv. Sci. 2019, 6, 18011828.
(11) Du, H.; Guo, X.; Kong, R. M.; Qu, F. Cr2O3 nanofiber: a high-performance electrocatalyst toward artificial N fixation to NH3 under ambient conditions. Chem. Commun. 2018, 54, 1284812851.
(12) Zhang, R.; Ji, L.; Kong, W.; Wang, H.; Zhao, R.; Chen, H.; Li, T.; Li, B.; Luo, Y.; Sun, X. Electrocatalytic N2-to-NH3 conversion with high faradaic efficiency enabled using a Bi nanosheet array. Chem. Commun. 2019, 55, 52635266.
(13) Cui, X.; Tang, C.; Liu, X. M.; Wang, C.; Ma, W.; Zhang, Q. Highly selective electrochemical reduction of dinitrogen to ammonia at ambient temperature and pressure over iron oxide catalysts. Chem. Eur. J. 2018, 24, 1849418501.
(14) Tao, H.; Choi, C.; Ding, L. X.; Jiang, Z.; Hang, Z.; Jia, M.; Fan, Q.; Gao, Y.; Wang, H.; Robertson, A. W.; Hong, S.; Jung, Y.; Liu, S.; Sun, Z. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem. 2019, 5, 204214.
(15) Nazemi, M.; Panikkanvalappil, S. R.; El-Sayed, M. A. Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages. Nano Energy 2018, 49, 316323.
(16) Sun, Z.; Huo, R.; Choi, C.; Hong, S.; Wu, T. S.; Qiu, J.; Yan, C.; Han, Z.; Liu, Y.; Soo, Y. L.; Jung, Y. Oxygen vacancy enables electrochemical N2 fixation over WO3 with tailored structure. Nano Energy 2019, 62, 869875.
(17) Song, Y.; Johnson, D.; Peng, R.; Hensley, D. K.; Bonnesen, P. V.; Liang, L.; Huang, J.; Yang, F.; Zhang, F.; Qiao, R.; Baddorf, A. P.; Tschaplinski, T. J.; Engle, N. L.; Hatzell, M. C.; Wu, Z.; Cullen, D. A.; Meyer, H. M. III; Sumpter, B. G.; Rondinone, A. J. A physical catalyst for the electrolysis of nitrogen to ammonia. Sci. Adv. 2018, 4, e17003368.
(18) Hao, Y. C.; Guo, Y.; Chen, L. W.; Shu, M.; Wang, X. Y.; Bu, T. A.; Gao, W. Y.; Zhang, N.; Su, X.; Feng, X.; Zhou, J. W.; Wang, B.; Hu, C. W.; Yin, A. X.; Si, R.; Zhang, Y. W.; Yan, C. H. Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water. Nat. Catal. 2019, 2, 448456.
(19) Wang, J.; Yu, L.; Hu, L.; Chen, G.; Xin, H.; Feng, X. Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential. Nat. Commun. 2018, 9, 17957.
(20) Pan, J.; Wang, Y.; Zheng, R.; Wang, M.; Wan, Z.; Jia, C.; Weng, X.; Xie, J.; Deng, L. Directly grown high-performance WO3 films by a novel one-step hydrothermal method with significantly improved stability for electrochromic applications. J. Mater. Chem. A 2019, 7, 1395613967.
(21) Tian, H.; Cui, X.; Zeng, L.; Su, L.; Song, Y.; Shi, J. Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO3 electrocatalyst. J. Mater. Chem. A 2019, 7, 62856293.
(22) Diao, J.; Yuan, W.; Qiu, Y.; Cheng, L.; Guo, X. A hierarchical oxygen vacancy-rich WO3 with nanowire-array-on-nanosheet-array structure for highly efficient oxygen evolution reaction. J. Mater. Chem. A 2019, 7, 67306739.
(23) Kong, W.; Zhang, R.; Zhang, X.; Ji, L.; Yu, G.; Wang, T.; Luo, Y.; Shi, X.; Xu, Y.; Sun, X. WO3 nanosheets rich in oxygen vacancies for enhanced electrocatalytic N2 reduction to NH3. Nanoscale 2019, 11, 1927419277.
(24) Zhang, L.; Ji, X.; Ren, X.; Ma, Y.; Shi, X.; Tian, Z.; Asiri, A. M.; Chen, L.; Tang, B.; Sun, X. Electrochemical ammonia synthesis via nitrogen reduction reaction on a MoS2 catalyst: theoretical and experimental studies. Adv. Mater. 2018, 30, 2018001916.