Simultaneous electrosynthesis of nitrate and hydrogen by integrating ammonia oxidation and water reduction

doi:10.1016/S1872-2067(23)64561-9

Abstract

Abstract:

Electrosynthesis of nitrate powered by renewable energy sources under mild conditions is an attractive alternative to the Oswald process for avoiding consuming large amounts of fossil fuels and eliminating associated greenhouse gas emissions. Here, we present an energy-saving and environmentally friendly strategy for efficient electrosynthesis of nitrate from ammonia oxidation by integrating hydrogen production from water reduction. We design a superior stable CuO nanosheet array catalyst and realize a total NO_x^- Faradaic efficiency of 98.7% via ammonia oxidation reaction (AOR) in an aqueous electrolyte. Hydrogen generation with a high Faradaic efficiency of 97.7% at the cathodic side is a concomitant AOR process. 0.2 mol L^-1 NO_x^- can be produced after a long-term stability testing for 108 h, suggesting a potential practical application in decentralized nitrate and green hydrogen production.

Key words: Ammonia oxidation, CuO nanosheet array, Nitrate electrosynthesis, Water reduction, Hydrogen production

Kehan Zhu, Haifeng Jiang, Gao-Feng Chen, Hao Wu, Liang-Xin Ding, Haihui Wang. Simultaneous electrosynthesis of nitrate and hydrogen by integrating ammonia oxidation and water reduction[J]. Chinese Journal of Catalysis, 2023, 55: 216-226.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64561-9

https://www.cjcatal.com/EN/Y2023/V55/I12/216

Figures/Tables 6

Fig. 1. (a) Schematics illustrating the industrial nitric acid synthesis by the Ostwald process. (b) Electrochemical technology for nitrate production at the anodic part with assisted green hydrogen production at the cathodic part.

Fig. 2. Physical characterization of synthesis CuO nanosheet covered vertical Cu nanorod arrays substrate (Cu-OX-KOH). SEM images at two scale bars of 5 μm (a) and 500 nm (b). (c) SAED pattern. TEM image (d) and corresponding HR-TEM image (e). (f) STEM and corresponding elemental mapping images.

Fig. 3. Comparison with electrocatalytic AOR performance and identification of active sites. (a) XRD patterns of Cu-NA, Cu-OX-PBS, and Cu-OX-KOH. (b) High-resolution Cu 2p XPS spectrum. (c) Comparison NO2- and NO3- yield rate for AOR process by employing Cu-OX-KOH and Cu-OX-PBS at 1.7, 1.8 and 1.9 V vs. RHE in 137 ppm NH3/0.1 mol L?1 KOH electrolyte. (d) Total Faradaic efficiency yielding NO2- and NO3- at three potentials.

Fig. 4. Electrochemical ammonia oxidation activities. (a) LSV curves of Cu-OX-KOH recorded in three electrolytes at a scan rate of 5 mV s-1. (b) NOx- yield rate and total Faradaic efficiency in 137 ppm NH3/0.1 mol L-1 KOH at various applied potentials. (c) The corresponding NH3 conversion at different applied potentials. (d) Time-dependent initial NH3 and NOx- yield change profiles at 1.8 V vs. RHE when using 137 pm NH3/0.1 mol L-1 KOH as reactant. (e) The cyclic stability of Cu-OX-KOH at 1.8 V vs. RHE. (f) Hydrogen yield and Faradaic efficiency at cathodic side during AOR process at 1.8 V vs. RHE. (g) Long-term stability of Cu-OX-KOH for large-scale production of nitric acid in 70 mL 200 ppm NH3/0.1 mol L-1 KOH working at 1.8 V vs. RHE. (h) Cu 2p XPS spectrum before and after long-term stability testing.

Fig. 5. Electrochemical in-situ FTIR spectra of the AOR on the Cu-OX-KOH electrode at 2.1 V vs. RHE under 200 ppm/0.1 mol L?1 KOH.

Fig. 6. DFT calculations for AOR processes. (a) DFT-calculated bonding energy of NH3 on Cu2O (111), CuO (111), CuO (002) and Cu (111) facet, respectively. (b) Gibbs free energy profiles of NH3 oxidation to NO3? reaction on CuO (002) surface of Cu-OX-KOH with an applied potential of U = 2.1 V vs. RHE. (c) Schematic diagram of pathways for the electrochemical oxidation of NH3 to NO3- and the corresponding transition state (TS) barriers.

References

[1]	J. G. Chen, R. M. Crooks, L. C. Seefeldt, K. L. Bren, R. M. Bullock, M. Y. Darensbourg, P. L. Darensbourg, B. Hoffman, M. J. Janik, A. K. Jones, M. G. Kanatzidis, P. King, K. M. Lancaster, S. V. Lymar, P. Pfromm, W. F. Schneider, R. R. Schrock, Science, 2018, 360, eaar6611.
[2]	S. Li, Y. Zhou, K. Li, M. Saccoccio, R. Sažinas, S. Z. Andersen, J. B. Pedersen, X. Fu, V. Shadravan, D. Chakraborty, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov, I. Chorkendorff, Joule, 2022, 6, 2083-2101.
[3]	W. Guo, K. Zhang, Z. Liang, R. Zou, Q. Xu, Chem. Soc. Rev., 2019, 48, 5658-5716.
[4]	L. Ouyang, J. Liang, Y. Luo, D. Zheng, S. Sun, Q. Liu, M. S. Hamdy, X. Sun, B. Ying, Chin. J. Catal., 2023, 50, 6-44.
[5]	L. Zhang, M. Cong, X. Ding, Y. Jin, F. Xu, Y. Wang, L. Chen, L. Zhang, Angew. Chem. Int. Ed., 2020, 59, 10888-10893.
[6]	C. A. Grande, K. A. Andreassen, J. H. Cavka, D. Waller, O.-A. Lorentsen, H. Øien, H.-J. Zander, S. Poulston, S. Garcia, D. Modeshia, Ind. Eng. Chem. Res., 2018, 57, 10180-10186.
[7]	H.-Y. Liu, H. M. C. Lant, J. L. Troiano, G. Hu, B. Q. Mercado, R. H. Crabtree, G. W. Brudvig, J. Am. Chem. Soc., 2022, 144, 8449-8453.
[8]	C. Dai, Y. Sun, G. Chen, A. C. Fisher, Z. J. Xu, Angew. Chem. Int. Ed., 2020, 59, 9418-9422.
[9]	S. Han, C. Wang, Y. Wang, Y. Yu, B. Zhang, Angew. Chem. Int. Ed., 2021, 60, 4474-4478.
[10]	M. Kuang, Y. Wang, W. Fang, H. Tan, M. Chen, J. Yao, C. Liu, J. Xu, K. Zhou, Q. Yan, Adv. Mater., 2020, 32, 2002189.
[11]	G. Lu, S. Gao, Q. Liu, S. Zhang, J. Luo, X. Liu, Nat. Sci., 2023, 3, e20220047.
[12]	J. Liang, Z. Li, L. Zhang, X. He, Y. Luo, D. Zheng, Y. Wang, T. Li, H. Yan, B. Ying, S. Sun, Q. Liu, M. S. Hamdy, B. Tang, X. Sun, Chem, 2023, 9, 1768-1827.
[13]	Y. Wang, Y. Yu, R. Jia, C. Zhang, B. Zhang, Natl. Sci. Rev., 2019, 6, 730-738.
[14]	K. Yao, Y. F. Cheng, J. Power Sources, 2007, 173, 96-101.
[15]	F. Vitse, M. Cooper, G. G. Botte, J. Power Sources, 2005, 142, 18-26.
[16]	Y. Yuan, L. Zhou, H. Robatjazi, J. L. Bao, J. Zhou, A. Bayles, L. Yuan, M. Lou, M. Lou, S. Khatiwada, E. A. Carter, P. Nordlander, N. J. Halas, Science, 2022, 378, 889-893.
[17]	Y. Zhao, B. P. Setzler, J. Wang, J. Nash, T. Wang, B. Xu, Y. Yan, Joule, 2019, 3, 2472-2484.
[18]	L. Ouyang, X. He, Y. Sun, L. Zhang, D. Zhao, S. Sun, Y. Luo, D. Zheng, A. M. Asiri, Q. Liu, J. Zhao, X. Sun, Inorg. Chem. Front., 2022, 9, 6602-6607.
[19]	Q. Liu, S. Sun, L. Zhang, Y. Luo, Q. Yang, K. Dong, X. Fang, D. Zheng, A. A. Alshehri, X. Sun, Nano Res., 2022, 15, 8922-8927.
[20]	K. Zhang, X. Liang, L. Wang, K. Sun, Y. Wang, Z. Xie, Q. Wu, X. Bai, M. S. Hamdy, H. Chen, X. Zou, Nano Res. Energy, 2022, 1, e9120032.
[21]	V. Rosca, M. Duca, M. T. de Groot, M. T. M. Koper, Chem. Rev., 2009, 109, 2209-2244.
[22]	D. Kilee, Environ. Sci. Technol., 2003, 37, 5745-5749.
[23]	J. Huang, Z. Chen, J. Cai, Y. Jin, T. Wang, J. Wang, Nano Res., 2022, 15, 5987-5994.
[24]	A. C. A. de Vooys, M. T. M. Koper, R. A. van Santen, J. A. R. van Veen, J. Electroanal. Chem., 2001, 506, 127-137.
[25]	J.-Y. Ye, J.-L. Lin, Z.-Y. Zhou, Y.-H. Hong, T. Sheng, M. Rauf, S.-G. Sun, J. Electroanal. Chem., 2018, 819, 495-501.
[26]	J. Chen, L. Zhang, J. Li, X. He, Y. Zheng, S. Sun, X. Fang, D. Zheng, Y. Luo, Y. Wang, J. Zhang, L. Xie, Z. Cai, Y. Sun, A. A. Alshehri, Q. Kong, C. Tang, X. Sun, J. Mater. Chem. A, 2023, 11, 1116-1122.
[27]	C. L. Wright, A. Schatteman, A. T. Crombie, J. C. Murrell, L. E. Lehtovirta-Morley, Appl. Environ. Microbiol., 2020, 86, e02388-e02319.
[28]	R. W. Mayer, M. Hävecker, A. Knop-Gericke, R. Schlögl, Catal. Lett., 2001, 74, 115-119.
[29]	X. Jiang, D. Ying, X. Liu, M. Liu, S. Zhou, C. Guo, G. Zhao, Y. Wang, J. Jia, Electrochim. Acta, 2020, 345,136157.
[30]	W. Xu, D. Du, R. Lan, J. Humphreys, D. N. Miller, M. Walker, Z. Wu, J. T. S. Irvine, S. Tao, Appl. Catal. B, 2018, 237, 1101-1109.
[31]	H. Jiang, G. Chen, O. Savateev, J. Xue, L. X. Ding, Z. Liang, M. Antonietti, H. Wang, Angew. Chem. Int. Ed., 2023, 62, e202218717.
[32]	M. Segall, P. J. Lindan, M. A. Probert, C. J. Pickard, P. J. Hasnip, S. Clark, M. Payne, J. Phys.: Condens. Matter, 2002, 14, 2717-2744.
[33]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[34]	D. Hamann, M. Schlüter, C. Chiang, Phys. Rev. Lett., 1979, 43, 1494-1497.
[35]	Y. Wu, C. Li, W. Liu, H. Li, Y. Gong, L. Niu, X. Liu, C. Sun, S. Xu, Nanoscale, 2019, 11, 5064-5071.
[36]	M. Bajdich, M. Garcia-Mota, A. Vojvodic, J. K. Nørskov, A. T. Bell, J. Am. Chem. Soc., 2013, 135, 13521-13530.
[37]	J. Yang, H. Qi, A. Li, X. Liu, X. Yang, S. Zhang, Q. Zhao, Q. Jiang, Y. Su, L. Zhang, J.-F. Li, Z.-Q. Tian, W. Liu, A. Wang, T. Zhang, J. Am. Chem. Soc., 2022, 144, 12062-12071.
[38]	T. Waechtler, S. Oswald, N. Roth, A. Jakob, H. Lang, R. Ecke, S. E. Schulz, T. Gessner, A. Moskvinova, S. Schulze, M. Hietscholde, J. Electrochem. Soc., 2009, 156, H453-H459.
[39]	Z. Zhang, L. Sun, Z. Wu, Y. Liu, S. Li, New J. Chem., 2020, 44, 6420-6427.
[40]	L. A. Diaz, G. G. Botte, Electrochim. Acta, 2015, 179, 519-528.
[41]	A. Kapałka, A. Cally, S. Neodo, C. Comninellis, M. Wächter, K. M. Udert, Electrochem. Commun., 2010, 12, 18-21.
[42]	S. G. Bratsch, J. Phys. Chem. Ref. Data, 1989, 18, 1-21.
[43]	W. Wang, Y.-B. Zhu, Q. Wen, Y. Wang, J. Xia, C. Li, M.-W. Chen, Y. Liu, H. Li, H.-A. Wu, T. Zhai, Adv. Mater., 2019, 31, 1900528.
[44]	B. You, X. Liu, N. Jiang, Y. Sun, J. Am. Chem. Soc., 2016, 138, 13639-13646.
[45]	Y. Huang, X. Chong, C. Liu, Y. Liang, B. Zhang, Angew. Chem. Int. Ed., 2018, 57, 13163-13166.
[46]	X. Zhu, X. Dou, J. Dai, X. An, Y. Guo, L. Zhang, S. Tao, J. Zhao, W. Chu, X. C. Zeng, C. Wu, Y. Xie. Angew. Chem. Int. Ed., 2016, 55, 12465-12469.
[47]	C. Tang, R. Zhang, W. Lu, Z. Wang, D. Liu, S. Hao, G. Du, A. M. Asiri, X. Sun, Angew. Chem. Int. Ed., 2017, 56, 842-846.
[48]	Z. Meng, J.-X. Yao, C.-N. Sun, X. Kang, R. Gao, H.-R. Li, B. Bi, Y.-F. Zhu, J.-M. Yan, Q. Jiang, Adv. Energy Mater., 2022, 12, 2202105.
[49]	A. D. Handoko, F. Wei, Jenndy, B. S. Yeo, Z. W. Seh, Nat. Catal., 2018, 1, 922-934.
[50]	X. Li, G. Hai, J. Liu, F. Zhao, Z. Peng, H. Liu, M. K. H. Leung, H. Wang, Appl. Catal. B, 2022, 314, 121531.
[51]	Y. Wang, H. Yin, F. Dong, X. Zhao, Y. Qu, L. Wang, Y. Peng, D. Wang, W. Fang, J. Li, Small, 2023, 19, 2207695.
[52]	R.-L. Wei, Y. Liu, Z. Chen, W.-S. Jia, Y.-Y. Yang, W.-B. Cai, J. Electroanal. Chem., 2021, 896, 115254.