Continuous-flow electrosynthesis of urea and oxalic acid by CO2-nitrate reduction and glycerol oxidation

doi:10.1016/S1872-2067(24)60085-9

Abstract

Abstract:

Urea and oxalic acid are critical component in various chemical manufacturing industries. However, achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge. Herein, we report a continuous-flow electrolyzer equipped with 9-square centimeter-effective area gas diffusion electrodes (GDE) which can simultaneously catalyze the glycerol oxidation reaction in the anode region and the reduction reaction of CO₂ and nitrate in the cathode region, producing oxalic acid and urea at both the anode and cathode, respectively. The current density at low cell voltage (0.9 V) remained above 18.7 mA cm^-2 for 10 consecutive electrolysis cycles (120 h in total), and the Faraday efficiency of oxalic acid (67.1%) and urea (70.9%) did not decay. Experimental and theoretical studies show that in terms of the formation of C-N bond at the cathode, Pd-sites can provide protons for the hydrogenation process of CO₂ and NO₃^-, Cu-sites can promote the generation of *COOH and Bi-sites can stabilize *COOH. In addition, in terms of glycerol oxidation, the introduction of Cu and Bi into Pd metallene promotes the oxidation of hydroxyl groups and the cleavage of C-C bond in glycerol molecules, respectively.

Key words: Urea, Oxalic acid, CO₂, C-N bond, Metallene

Shuanglong Zhou, Yue Shi, Yu Dai, Tianrong Zhan, Jianping Lai, Lei Wang. Continuous-flow electrosynthesis of urea and oxalic acid by CO₂-nitrate reduction and glycerol oxidation[J]. Chinese Journal of Catalysis, 2024, 63: 270-281.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60085-9

https://www.cjcatal.com/EN/Y2024/V63/I8/270

Figures/Tables 5

Fig. 1. The synthesis process of catalysts and morphology of Pd70Cu12Bi18 metallene. (a) Low resolution TEM images of catalysts. (b) Test results of atomic force microscope for Pd70Cu12Bi18 metallene. (c) High resolution TEM images of catalysts. (d) Mapping results of catalyst.

Fig. 2. Electronic structure characterization of synthesized catalysts. (a) Comparison of Fine XPS for Pd 3d. (b) Comparison of Fine XPS for Cu 2p. (c) Comparison of Fine XPS for Bi 4f. (d) XANES spectra for Pd K-edge. (e) XANES spectra for Cu K-edge. (f) XANES spectra for Bi LIII-edge.

Fig. 3. Properties of electrocatalytic CNRR. (a) The LSV curves of synthetized catalysts. (b) Faraday efficiency of products in potassium nitrate solutions of different concentrations. (c) Faraday efficiency distribution of urea at different nitrate concentrations and potentials. (d) NMR spectroscopy of ammonia produced by urease driven isotope labeling urea. (e) NMR spectroscopy of isotope labeled urea and products. (f) Comparison of results of three methods for detecting urea. (g) Comparison of recent advanced catalysts.

Fig. 4. Experimental and theoretical research on the reaction mechanism. In situ FTIR spectroscopy of Pd71Cu29 (a), Pd70Bi30 (b) and Pd70Cu12Bi18 (c) metallene. (d) The comparison of the peak integral area of *COOH under different applied potentials. (e) Comparison of Faraday efficiency of urea under different carbon or nitrogen sources. Free energy diagrams of carbon dioxide (f), nitrate (g) and nitrate and carbon dioxide (h) reduction pathways on Pd70Bi30, Pd71Cu29 and Pd70Cu12Bi18 metallene.

Fig. 5. Performance of electrooxidized glycerol and performance of GOR coupled CNRR. (a) CV curves of synthesized catalysts. (b) Comparison of GOR activity of catalysts. (c) Faraday efficiency under different applied potentials. (d) Free energy diagrams of GOR on Pd70Bi30, Pd71Cu29 and Pd70Cu12Bi18 metallene. (e) Flow electrolytic cell model. (f) Faraday efficiency of urea and oxalic acid at different cell voltages. (g) 120 h of stability testing and corresponding Faraday efficiency.

References

[1]	J. Li, Y. Zhang, K. Kuruvinashetti, N. Kornienko, Nat. Rev. Chem., 2022, 6, 303-319.
[2]	D. Zhang, Y. Xue, X. Zheng, C. Zhang, Y. Li, Natl. Sci. Rev., 2023, 10, nwac209.
[3]	X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li, Z. Li, B. Yang, L. Lei, L. Dai, Y. Hou, Chem. Soc. Rev., 2023, 52, 2193-2237.
[4]	M. Yuan, J. Chen, Y. Xu, R. Liu, T. Zhao, J. Zhang, Z. Ren, Z. Liu, C. Streb, H. He, C. Yang, S. Zhang, G. Zhang, Energy Environ. Sci., 2021, 14, 6605-6615.
[5]	Y. Zhao, Y. Ding, W. Li, C. Liu, Y. Li, Z. Zhao, Y. Shan, F. Li, L. Sun, F. Li,, Nat. Commun., 2023, 14, 4491.
[6]	X. Cao, D. Zhang, Y. Gao, O. V. Prezhdo, L. Xu, J. Am. Chem. Soc., 2024, 146, 1042-1052.
[7]	S. Liu, M. Wang, Q. Cheng, Y. He, J. Ni, J. Liu, C. Yan, T. Qian, ACS Nano, 2022, 16, 17911-17930.
[8]	Y. Mao, Y. Jiang, Q. Gou, S. Lv, Z. Song, Y. Jiang, W. Wang, M. Li, L. Zheng, W. Su, R. He, Appl. Catal. B, 2024, 340, 123189.
[9]	C. Guo, W. Zhou, X. Lan, Y. Wang, T. Li, S. Han, Y. Yu, B. Zhang, J. Am. Chem. Soc., 2022, 144, 16006-16011.
[10]	N. Meng, J. Shao, H. Li, Y. Wang, X. Fu, C. Liu, Y. Yu, B. Zhang, Nat. Commun., 2022, 13, 5452.
[11]	Z. Tao, C. L. Rooney, Y. Liang, H. Wang, J. Am. Chem. Soc., 2021, 143, 19630-19642.
[12]	X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie, D. Wang, M. Qiu, N. He, P. Zhou, W. Chen, J. Cheng, H. Lin, J. Jia, X. Z. Fu, S. Wang, J. Am. Chem. Soc., 2022, 144, 11530-11535.
[13]	R. Miao, D. Chen, Z. Guo, Y. Zhou, C. Chen, S. Wang, Appl. Catal. B, 2024, 344, 123662.
[14]	M. Sun, G. Wu, J. Jiang, Y. Yang, A. Du, L. Dai, X. Mao, Q. Qin, Angew. Chem. Int. Ed., 2023, 62, e202301957.
[15]	Y. Jiao, H. Li, Y. Jiao, S. Z. Qiao, J. Am. Chem. Soc., 2023, 145, 15572-15580.
[16]	J. Geng, S. Ji, M. Jin, C. Zhang, M. Xu, G. Wang, C. Liang, H. Zhang, Angew. Chem. Int. Ed., 2023, 62, e202210958.
[17]	J. Mukherjee, S. Paul, A. Adalder, S. Kapse, R. Thapa, S. Mandal, B. Ghorai, S. Sarkar, U. K. Ghorai, Adv. Funct. Mater., 2022, 32, 2200882.
[18]	M. Jiang, M. Zhu, M. Wang, Y. He, X. Luo, C. Wu, L. Zhang, Z. Jin, ACS Nano, 2023, 17, 3209-3224.
[19]	G.-L. Yang, C.-T. Hsieh, Y.-S. Ho, T.-C. Kuo, Y. Kwon, Q. Lu, M.-J. Cheng, ACS Catal., 2022, 12, 11494-11504.
[20]	Z. Ma, Y. Luo, P. Wu, J. Zhong, C. Ling, Y. Yu, X. Xia, B. Song, L. Ning, Y. Huang, Adv. Funct. Mater., 2023, 33, 2302475.
[21]	M. Yuan, J. Chen, H. Zhang, Q. Li, L. Zhou, C. Yang, R. Liu, Z. Liu, S. Zhang, G. Zhang, Energy Environ. Sci., 2022, 15, 2084-2095.
[22]	J. Leverett, T. Tran‐Phu, J. A. Yuwono, P. Kumar, C. Kim, Q. Zhai, C. Han, J. Qu, J. Cairney, A. N. Simonov, R. K. Hocking, L. Dai, R. Daiyan, R. Amal, Adv. Energy Mater., 2022, 12, 2201500.
[23]	X. Zhu, X. Zhou, Y. Jing, Y. Li, Nat. Commun., 2021, 12, 4080.
[24]	M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang, T. Zhao, Q. Wang, S. Li, H. He, G. Zhang, Angew. Chem. Int. Ed., 2021, 60, 10910-10918.
[25]	X. Zhang, X. Zhu, S. Bo, C. Chen, M. Qiu, X. Wei, N. He, C. Xie, W. Chen, J. Zheng, P. Chen, S. P. Jiang, Y. Li, Q. Liu, S. Wang, Nat. Commun., 2022, 13, 5337.
[26]	S. Zhang, J. Geng, Z. Zhao, M. Jin, W. Li, Y. Ye, K. Li, G. Wang, Y. Zhang, H. Yin, H. Zhang, H. Zhao, EES Catal., 2023, 1, 45-53.
[27]	X. Yu, R. B. Araujo, Z. Qiu, E. Campos dos Santos, A. Anil, A. Cornell, L. G. M. Pettersson, M. Johnsson, Adv. Energy Mater., 2022, 12, 2103750.
[28]	W. Hong, C. Shang, J. Wang, E. Wang, Energy Environ. Sci., 2015, 8, 2910-2915.
[29]	L. Pan, J. Wang, F. Lu, Q. Liu, Y. Gao, Y. Wang, J. Jiang, C. Sun, J. Wang, X. Wang, Angew. Chem. Int. Ed., 2023, 62, e202216835.
[30]	Y. Wang, S. Xia, J. Zhang, Z. Li, R. Cai, C. Yu, Y. Zhang, J. Wu, Y. Wu, ACS Energy Lett., 2023, 8, 3373-3380.
[31]	S. Shin, S. Sultan, Z.-X. Chen, H. Lee, H. Choi, T.-U. Wi, C. Park, T. Kim, C. Lee, J. Jeong, H. Shin, T.-H. Kim, H. Ju, H. C. Yoon, H.-K. Song, H.-W. Lee, M.-J. Cheng, Y. Kwon, Energy Environ. Sci., 2023, 16, 2003-2013.
[32]	X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Nat. Commun., 2022, 13, 5471.
[33]	A. Zalineeva, A. Serov, M. Padilla, U. Martinez, K. Artyushkova, S. Baranton, C. Coutanceau, P. B. Atanassov, J. Am. Chem. Soc., 2014, 136, 3937-3945.
[34]	S. Li, J. Lai, R. Luque, G. Xu, Energy Environ. Sci., 2016, 9, 3097-3102.
[35]	H. Sheng, A. N. Janes, R. D. Ross, H. Hofstetter, K. Lee, J. R. Schmidt, S. Jin, Nat. Catal., 2022, 5, 716-725.
[36]	D. Liu, J. C. Liu, W. Cai, J. Ma, H. B. Yang, H. Xiao, J. Li, Y. Xiong, Y. Huang, B. Liu, Nat. Commun., 2019, 10, 1779.
[37]	L. S. Oh, M. Park, Y. S. Park, Y. Kim, W. Yoon, J. Hwang, E. Lim, J. H. Park, S. M. Choi, M. H. Seo, W. B. Kim, H. J. Kim, Adv. Mater., 2022, 35, 2203285.
[38]	J. Lai, F. Lin, Y. Tang, P. Zhou, Y. Chao, Y. Zhang, S. Guo, Adv. Energy Mater., 2019, 9, 1800684.
[39]	Y. Liu, X. Tu, X. Wei, D. Wang, X. Zhang, W. Chen, C. Chen, S. Wang, Angew. Chem. Int. Ed., 2023, 62, e202300387.
[40]	N. Meng, X. Ma, C. Wang, Y. Wang, R. Yang, J. Shao, Y. Huang, Y. Xu, B. Zhang, Y. Yu, ACS Nano, 2022, 16, 9095-9104.
[41]	C. Lv, J. Liu, C. Lee, Q. Zhu, J. Xu, H. Pan, C. Xue, Q. Yan, ACS Nano, 2022, 16, 15512-15527.
[42]	X. Wei, Y. Liu, X. Zhu, S. Bo, L. Xiao, C. Chen, T. T. T. Nga, Y. He, M. Qiu, C. Xie, D. Wang, Q. Liu, F. Dong, C. L. Dong, X. Z. Fu, S. Wang, Adv. Mater., 2023, 35, 2300020.

Continuous-flow electrosynthesis of urea and oxalic acid by CO₂-nitrate reduction and glycerol oxidation

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