Citation: Qing-Shui HONG, Tang-Yi LI, Shi-Sheng ZHENG, Hai-Biao CHEN, Hong-Hao CHU, Kuan-Da XU, Shun-Ning LI, Zong-Wei MEI, Qing-He ZHAO, Wen-Ju REN, Wen-Guang ZHAO, Feng PAN. 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. doi: 10.14102/j.cnki.0254–5861.2011–2975 shu

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

School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, Guangdong 518055, China

Corresponding author: Feng PAN, panfeng@pkusz.edu.cn
Received Date: 2 September 2020
Accepted Date: 28 October 2020

Fund Project: Shenzhen Science and Technology Research Grant ZDSYS201707281026184Natural Science Foundation of Shenzhen JCYJ20190813110605381

Figures(10)

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.
- electrochemical nitrogen reduction reaction,
- zeta potential,
- nitrogen diffusion and transport process,
- WO₃ nanobelts,
- first-principles calculations
1. [1]
  Jiao, D.; Iniguez, J. A.; Chong, L. Electrocatalytic nitrogen reduction at low temperature. Joule 2018, 2, 846−56. doi: 10.1016/j.joule.2018.04.014
2. [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. [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. doi: 10.1039/C4CS00085D
4. [4]
  Cao, N.; Zheng, G. Aqueous electrocatalytic N₂ reduction under ambient conditions. Nano Res. 2018, 11, 2992−3008. doi: 10.1007/s12274-018-1987-y
5. [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. doi: 10.1021/acsenergylett.8b00487
6. [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. doi: 10.1002/adma.201604799
7. [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. doi: 10.1021/jacs.7b12774
8. [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. doi: 10.1021/jacs.7b04393
9. [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. doi: 10.1002/aenm.201800124
10. [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. doi: 10.1002/advs.201801182
11. [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. doi: 10.1039/C8CC07186A
12. [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. doi: 10.1039/C9CC01703H
13. [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. doi: 10.1002/chem.201800535
14. [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. doi: 10.1016/j.chempr.2018.10.007
15. [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. doi: 10.1016/j.nanoen.2018.04.039
16. [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. doi: 10.1016/j.nanoen.2019.06.019
17. [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. doi: 10.1126/sciadv.1700336
18. [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. doi: 10.1038/s41929-019-0241-7
19. [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. [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. doi: 10.1039/C9TA01333D
21. [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. doi: 10.1039/C8TA12219A
22. [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. [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. doi: 10.1039/C9NR03678D
24. [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.
1. [1]
  Lumin Zheng , Ying Bai , Chuan Wu . Multi-electron reaction and fast Al ion diffusion of δ-MnO₂ cathode materials in rechargeable aluminum batteries via first-principle calculations. Chinese Chemical Letters, 2024, 35(4): 108589-. doi: 10.1016/j.cclet.2023.108589
2. [2]
  Shaohua Zhang , Xiaojuan Dai , Wei Hao , Liyao Liu , Yingqiao Ma , Ye Zou , Jia Zhu , Chong-an Di . A first-principles study of the Nernst effect in doped polymer. Chinese Chemical Letters, 2024, 35(12): 109837-. doi: 10.1016/j.cclet.2024.109837
3. [3]
  Chaozheng He , Jia Wang , Ling Fu , Wei Wei . Nitric oxide assists nitrogen reduction reaction on 2D MBene: A theoretical study. Chinese Chemical Letters, 2024, 35(5): 109037-. doi: 10.1016/j.cclet.2023.109037
4. [4]
  Chaozheng He , Pei Shi , Donglin Pang , Zhanying Zhang , Long Lin , Yingchun Ding . First-principles study of the relationship between the formation of single atom catalysts and lattice thermal conductivity. Chinese Chemical Letters, 2024, 35(6): 109116-. doi: 10.1016/j.cclet.2023.109116
5. [5]
  Zhenfei Tang , Yunwu Zhang , Zhiyuan Yang , Haifeng Yuan , Tong Wu , Yue Li , Guixiang Zhang , Xingzhi Wang , Bin Chang , Dehui Sun , Hong Liu , Lili Zhao , Weijia Zhou . Iron-doping regulated light absorption and active sites in LiTaO₃ single crystal for photocatalytic nitrogen reduction. Chinese Chemical Letters, 2025, 36(3): 110107-. doi: 10.1016/j.cclet.2024.110107
6. [6]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
7. [7]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
8. [8]
  Bingwei Wang , Yihong Ding , Xiao Tian . Benchmarking model chemistry composite calculations for vertical ionization potential of molecular systems. Chinese Chemical Letters, 2025, 36(2): 109721-. doi: 10.1016/j.cclet.2024.109721
9. [9]
  Rui PAN , Yuting MENG , Ruigang XIE , Daixiang CHEN , Jiefa SHEN , Shenghu YAN , Jianwu LIU , Yue ZHANG . Selective electrocatalytic reduction of Sn(Ⅳ) by carbon nitrogen materials prepared with different precursors. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 1015-1024. doi: 10.11862/CJIC.20230433
10. [10]
  Sajid Mahmood , Haiyan Wang , Fang Chen , Yijun Zhong , Yong Hu . Recent progress and prospects of electrolytes for electrocatalytic nitrogen reduction toward ammonia. Chinese Chemical Letters, 2024, 35(4): 108550-. doi: 10.1016/j.cclet.2023.108550
11. [11]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
12. [12]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
13. [13]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
14. [14]
  Xue Xin , Qiming Qu , Islam E. Khalil , Yuting Huang , Mo Wei , Jie Chen , Weina Zhang , Fengwei Huo , Wenjing Liu . Hetero-phase zirconia encapsulated with Au nanoparticles for boosting electrocatalytic nitrogen reduction. Chinese Chemical Letters, 2024, 35(5): 108654-. doi: 10.1016/j.cclet.2023.108654
15. [15]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
16. [16]
  Yan Wang , Jiaqi Zhang , Xiaofeng Wu , Sibo Wang , Masakazu Anpo , Yuanxing Fang . Elucidating oxygen evolution and reduction mechanisms in nitrogen-doped carbon-based photocatalysts. Chinese Chemical Letters, 2025, 36(2): 110439-. doi: 10.1016/j.cclet.2024.110439
17. [17]
  Xiao Li , Wanqiang Yu , Yujie Wang , Ruiying Liu , Qingquan Yu , Riming Hu , Xuchuan Jiang , Qingsheng Gao , Hong Liu , Jiayuan Yu , Weijia Zhou . Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption. Chinese Chemical Letters, 2024, 35(8): 109166-. doi: 10.1016/j.cclet.2023.109166
18. [18]
  Sanmei Wang , Yong Zhou , Hengxin Fang , Chunyang Nie , Chang Q Sun , Biao Wang . Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts. Chinese Chemical Letters, 2025, 36(3): 110476-. doi: 10.1016/j.cclet.2024.110476
19. [19]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
20. [20]
  Yu Yao , Jinqiang Zhang , Yantao Wang , Kunsheng Hu , Yangyang Yang , Zhongshuai Zhu , Shuang Zhong , Huayang Zhang , Shaobin Wang , Xiaoguang Duan . Nitrogen-rich carbon for catalytic activation of peroxymonosulfate towards green synthesis. Chinese Chemical Letters, 2024, 35(11): 109633-. doi: 10.1016/j.cclet.2024.109633

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(309)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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