Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst

doi:10.1016/S1872-2067(22)64136-6

Abstract

Abstract:

Electrocatalytic reduction of nitrogen into ammonia (NH₃) is a highly attractive but challenging route for NH₃ production. We propose to realize a synergetic work of multi reaction sites to overcome the limitation of sustainable NH₃ production. Herein, using ruthenium-sulfur-carbon (Ru-S-C) catalyst as a prototype, we show that the Ru/S dual-site cooperates to catalyse eletrocatalytic nitrogen reduction reaction (eNRR) at ambient conditions. With the combination of theoretical calculations, in situ Raman spectroscopy, and experimental observation, we demonstrate that such Ru/S dual-site cooperation greatly facilitates the activation and first protonation of N₂ in the rate-determining step of eNRR. As a result, Ru-S-C catalyst exhibits significantly enhanced eNRR performance compared with the routine Ru-N-C catalyst via a single-site catalytic mechanism. We anticipate that our specifically designed dual-site collaborative catalytic mechanism will open up a new way to offers new opportunities for advancing sustainable NH₃ production.

Key words: Ru/S dual-site mechanism, Electronic ‘push-push’, mechanism, Electrocatalytic nitrogen reduction, reaction

Liujing Yang, Chuanqi Cheng, Xun Zhang, Cheng Tang, Kun Du, Yuanyuan Yang, Shan-Cheng Shen, Shi-Long Xu, Peng-Fei Yin, Hai-Wei Liang, Tao Ling. Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst[J]. Chinese Journal of Catalysis, 2022, 43(12): 3177-3186.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64136-6

https://www.cjcatal.com/EN/Y2022/V43/I12/3177

Figures/Tables 4

Fig. 1. Theoretical investigation on activation and first protonation of N2 over Ru-S-C catalyst. (a,b) Schematic diagrams of N2 activation without and with S-H*, respectively. The grey, light red, light blue, yellow, and red coloured balls represent C, Ru, N, S, and H atoms, respectively. (c) Projected density of states of N 2s, 2p, and Ru 3d of N2 adsorbed Ru-S-C catalyst without and with S-H*. (d) Schematic diagram of the formation of NNH* on Ru-S-C catalyst with S-H*. (e) DFT calculated free energy diagram of the NNH* formation on Ru-S-C catalyst with the S-H* (upper) and without S-H* (lower).

Fig. 2. Structural characterisation of the Ru-S-C catalyst. (a) HAADF-STEM image and EDS elemental mappings of Ru, C, and S. (b) XRD patterns of Ru-S-C catalyst and S-C framework. (c) HAADF-STEM image of the Ru-S-C catalyst, showing atomically dispersed Ru atoms (marked by yellow circles) on the S-C matrix. (d) Normalized XANES spectra of Ru-S-C, Ru foil, RuCl3, and RuO2 at the Ru K-edge, with the inset showing the enlarged spectra in a range from 22113 to 22134 eV. (e) Corresponding EXAFS spectra of Ru-S-C, Ru foil, RuCl3, and RuO2 at R space. (f) EXAFS fitting for Ru-S-C catalyst, with the inset showing the schematic diagram of a Ru-S4 moiety embedded in Ru-S-C catalyst.

Fig. 3. Electrochemical eNRR performances of Ru-S-C and Ru-N-C catalysts. (a) 1H NMR spectra (500 MHz) of the collected electrolyte after the eNRR process using 14N2 and 15N2 as the feeding N2 source. The 1H NMR spectra of the standard solutions containing 14NH4+ and 15NH4+ are also shown as the references. Faradaic efficiencies (b), NH3 yields (c), and TOFs (d) measured by ammonia sensitive electrode. The error bars represent variations in the three experimental samples. The inset in (c) shows the partial current density of eNRR based on geometric area.

Fig. 4. Experimental verification of the Ru/S dual-site mechanism of Ru-S-C catalyst. In situ Raman spectra tested in N2- (a) and Ar- (b) saturated 0.10 mol L-1 KOH at various applied potentials. (c) KIE of H/D of the Ru-S-C catalyst tested in N2-saturated 0.10 mol L-1 KOH at -0.15 VRHE. (d) Schematic diagram of the Ru/S dual-site collaborative catalytic mechanism.

References

[1]	I. Coric, B. Q. Mercado, E. Bill, D. J. Vinyard, P. L. Holland, Nature, 2015, 526, 96-99.
[2]	W. Qiu, X. Y. Xie, J. Qiu, W. H. Fang, R. Liang, X. Ren, X. Ji, G. Cui, A. M. Asiri, G. Cui, B. Tang, X. Sun, Nat. Commun., 2018, 9, 3485.
[3]	A. Good, Science, 2018, 359, 869-870.
[4]	A. J. Medford, M. C. Hatzell, ACS Catal., 2017, 7, 2624-2643.
[5]	X. Li, T. Li, Y. Ma, Q. Wei, W. Qiu, H. Guo, X. Shi, P. Zhang, A. M. Asiri, L. Chen, B. Tang, X. Sun, Adv. Energy Mater., 2018, 8, 1801357.
[6]	C. Lv, C. Yan, G. Chen, Y. Ding, J. Sun, Y. Zhou, G. Yu, Angew. Chem. Int. Ed., 2018, 57, 6073-6076.
[7]	Y.-C. Hao, Y. Guo, L.-W. Chen, M. Shu, X.-Y. Wang, T.-A. Bu, W.-Y. Gao, N. Zhang, X. Su, X. Feng, J.-W. Zhou, B. Wang, C.-W. Hu, A.-X. Yin, R. Si, Y.-W. Zhang, C.-H. Yan, Nat. Catal., 2019, 2, 448-456.
[8]	X. Cui, C. Tang, Q. Zhang, Adv. Energy Mater., 2018, 8, 1800369.
[9]	G. F. Chen, X. Cao, S. Wu, X. Zeng, L. X. Ding, M. Zhu, H. Wang, J. Am. Chem. Soc., 2017, 139, 9771-9774.
[10]	X. Zhao, G. Hu, G. F. Chen, H. Zhang, S. Zhang, H. Wang, Adv. Mater., 2021, 33, 2007650.
[11]	C. Tang, S. Z. Qiao, Chem. Soc. Rev., 2019, 48, 3166-3180.
[12]	M. M. Shi, D. Bao, S.-J. Li, B.-R. Wulan, J.-M. Yan, Q. Jiang, Adv. Energy Mater., 2018, 8, 1800124.
[13]	Y. Yang, L. Zhang, Z. Hu, Y. Zheng, C. Tang, P. Chen, R. Wang, K. Qiu, J. Mao, T. Ling, S. Z. Qiao, Angew. Chem. Int. Ed., 2020, 59, 4525-4531.
[14]	H. Jin, L. Li, X. Liu, C. Tang, W. Xu, S. Chen, L. Song, Y. Zheng, S. Z. Qiao, Adv. Mater., 2019, 31, 1902709.
[15]	C. Tang, Y. Zheng, M. Jaroniec, S. Z. Qiao, Angew. Chem. Int. Ed., 2021, 60, 19572-19590.
[16]	M. Kitano, Y. Inoue, Y. Yamazaki, F. Hayashi, S. Kanbara, S. Matsuishi, T. Yokoyama, S. W. Kim, M. Hara, H. Hosono, Nat. Chem., 2012, 4, 934-940.
[17]	S. Wang, X. Hai, X. Ding, K. Chang, Y. Xiang, X. Meng, Z. Yang, H. Chen, J. Ye, Adv. Mater., 2017, 29, 1701774.
[18]	M. M. Shi, D. Bao, B. R. Wulan, Y. H. Li, Y. F. Zhang, J. M. Yan, Q. Jiang, Adv. Mater., 2017, 29, 1606550.
[19]	R. Hao, W. Sun, Q. Liu, X. Liu, J. Chen, X. Lv, W. Li, Y. p. Liu, Z. Shen, Small, 2020, 16, 2000015.
[20]	J. Zhao, Z. Chen, J. Am. Chem. Soc., 2017, 139, 12480-12487.
[21]	L. Zhang, X. Ji, X. Ren, Y. Ma, X. Shi, Z. Tian, A. M. Asiri, L. Chen, B. Tang, X. Sun, Adv. Mater., 2018, 30, 1800191.
[22]	S. Zhao, X. Lu, L. Wang, J. Gale, R. Amal, Adv. Mater., 2019, 31, 1805367.
[23]	Z. Han, C. Choi, S. Hong, T.-S. Wu, Y.-L. Soo, Y. Jung, J. Qiu, Z. Sun, Appl. Catal. B, 2019, 257, 117896.
[24]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Norskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[25]	H. Shen, C. Choi, J. Masa, X. Li, J. Qiu, Y. Jung, Z. Sun, Chem, 2021, 7, 1708-1754.
[26]	C. Tang, L. Chen, H. Li, L. Li, Y. Jiao, Y. Zheng, H. Xu, K. Davey, S. Z. Qiao, J. Am. Chem. Soc., 2021, 143, 7819-7827.
[27]	D. F. Harris, D. A. Lukoyanov, H. Kallas, C. Trncik, Z. Y. Yang, P. Compton, N. Kelleher, O. Einsle, D. R. Dean, B. M. Hoffman, L. C. Seefeldt, Biochemistry, 2019, 58, 3293-3301.
[28]	D. F. Harris, D. A. Lukoyanov, S. Shaw, P. Compton, M. Tokmina-Lukaszewska, B. Bothner, N. Kelleher, D. R. Dean, B. M. Hoffman, L. C. Seefeldt, Biochemistry, 2018, 57, 701-710.
[29]	B. M. Hoffman, D. Lukoyanov, Z. Y. Yang, D. R. Dean, L. C. Seefeldt, Chem. Rev., 2014, 114, 4041-4062.
[30]	Q. Q. Yan, D. X. Wu, S. Q. Chu, Z. Q. Chen, Y. Lin, M. X. Chen, J. Zhang, X. J. Wu, H. W. Liang, Nat. Commun., 2019, 10, 4977.
[31]	L. Ma, Y. Cheng, G. Cavataio, R. W. McCabe, L. Fu, J. Li, Appl. Catal. B, 2014, 156- 157, 428-437.
[32]	G. W. Watt, J. D. Chrisp, Anal. Chem., 1952, 24, 2006-2008.
[33]	G. Lin, Q. Ju, X. Guo, W. Zhao, S. Adimi, J. Ye, Q. Bi, J. Wang, M. Yang, F. Huang, Adv. Mater., 2021, 33, 2007509.
[34]	W. Ma, S. Xie, X. G. Zhang, F. Sun, J. Kang, Z. Jiang, Q. Zhang, D. Y. Wu, Y. Wang, Nat. Commun., 2019, 10, 892.
[35]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186
[36]	P. E. Blochl, Phy. Rev. B, 1994, 50, 17953-17979.
[37]	P. P. John, B. Kieron, E. Matthias, Phys. Rev. Lett., 1996, 77, 3865-3868.
[38]	K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys., 2014, 140, 084106.
[39]	P. Xiao, D. Sheppard, J. Rogal, G. Henkelman, J. Chem. Phys., 2014, 140, 174104.
[40]	A. L. Speelman, I. Coric, C. Van Stappen, S. DeBeer, B. Q. Mercado, P. L. Holland, J. Am. Chem. Soc., 2019, 141, 13148-13157.
[41]	L. C. Seefeldt, Z. Y. Yang, D. A. Lukoyanov, D. F. Harris, D. R. Dean, S. Raugei, B. M. Hoffman, Chem. Rev., 2020, 120, 5082-5106.
[42]	J. Staszak-Jirkovsky, C. D. Malliakas, P. P. Lopes, N. Danilovic, S. S. Kota, K. C. Chang, B. Genorio, D. Strmcnik, V. R. Stamenkovic, M. G. Kanatzidis, N. M. Markovic, Nat. Mater., 2016, 15, 197-203.
[43]	C. Hu, Q. Ma, S.-F. Hung, Z.-N. Chen, D. Ou, B. Ren, H. M. Chen, G. Fu, N. Zheng, Chem, 2017, 3, 122-133.
[44]	L. Wang, M. X. Chen, Q. Q. Yan, S. L. Xu, S. Q. Chu, P. Chen, Y. Lin, H. W. Liang, Sci. Adv., 2019, 5, eaax6322.
[45]	C. He, Z.-Y. Wu, L. Zhao, M. Ming, Y. Zhang, Y. Yi, J.-S. Hu, ACS Catal., 2019, 9, 7311-7317.
[46]	W. Zhao, L. Zhang, Q. Luo, Z. Hu, W. Zhang, S. Smith, J. Yang, ACS Catal., 2019, 9, 3419-3425.
[47]	M. Wang, S. Liu, T. Qian, J. Liu, J. Zhou, H. Ji, J. Xiong, J. Zhong, C. Yan, Nat. Commun., 2019, 10, 341.
[48]	L. Han, X. Liu, J. Chen, R. Lin, H. Liu, F. Lu, S. Bak, Z. Liang, S. Zhao, E. Stavitski, J. Luo, R. R. Adzic, H. L. Xin, Angew. Chem. Int. Ed., 2019, 58, 2321-2325.
[49]	X. Wang, W. Wang, M. Qiao, G. Wu, W. Chen, T. Yuan, Q. Xu, M. Chen, Y. Zhang, X. Wang, J. Wang, J. Ge, X. Hong, Y. Li, Y. Wu, Y. Li, Sci. Bull., 2018, 63, 1246-1253.
[50]	Y. Wang, X. Cui, J. Zhao, G. Jia, L. Gu, Q. Zhang, L. Meng, Z. Shi, L. Zheng, C. Wang, Z. Zhang, W. Zheng, ACS Catal., 2018, 9, 336-344.
[51]	X. Liu, Y. Jiao, Y. Zheng, S.-Z. Qiao, ACS Catal., 2020, 10, 1847-1854.
[52]	Y. X. Lin, S. N. Zhang, Z. H. Xue, J. J. Zhang, H. Su, T. J. Zhao, G. Y. Zhai, X. H. Li, M. Antonietti, J. S. Chen, Nat. Commun., 2019, 10, 4380.
[53]	Y. Luo, G.-F. Chen, L. Ding, X. Chen, L.-X. Ding, H. Wang, Joule, 2019, 3, 279-289.
[54]	W. Zang, T. Yang, H. Zou, S. Xi, H. Zhang, X. Liu, Z. Kou, Y. Du, Y. P. Feng, L. Shen, L. Duan, J. Wang, S. J. Pennycook, ACS Catal., 2019, 9, 10166-10173.
[55]	Z. Geng, Y. Liu, X. Kong, P. Li, K. Li, Z. Liu, J. Du, M. Shu, R. Si, J. Zeng, Adv. Mater., 2018, 30, e1803498.
[56]	Q. Li, W. Chen, H. Xiao, Y. Gong, Z. Li, L. Zheng, X. Zheng, W. Yan, W. C. Cheong, R. Shen, N. Fu, L. Gu, Z. Zhuang, C. Chen, D. Wang, Q. Peng, J. Li, Y. Li, Adv. Mater., 2018, 30, 1800588.
[57]	S. Z. Andersen, V. Colic, S. Yang, J. A. Schwalbe, A. C. Nielander, J. M. McEnaney, K. Enemark-Rasmussen, J. G. Baker, A. R. Singh, B. A. Rohr, M. J. Statt, S. J. Blair, S. Mezzavilla, J. Kibsgaard, P. C. K. Vesborg, M. Cargnello, S. F. Bent, T. F. Jaramillo, I. E. L. Stephens, J. K. Norskov, I. Chorkendorff, Nature, 2019, 570, 504-508.
[58]	C. Paolucci, I. Khurana, A. A. Parekh, S. C. Li, A. J. Shih, H. Li, J. R. Di Iorio, J. D. Albarracin-Caballero, A. Yezerets, J. T. Miller, W. N. Delgass, F. H. Ribeiro, W. F. Schneider, R. Gounder, Science, 2017, 357, 898-903.
[59]	J. X. Feng, J. Q. Wu, Y. X. Tong, G. R. Li, J. Am. Chem. Soc., 2018, 140, 610-617.
[60]	J. Chen, G. Liu, Y. Z. Zhu, M. Su, P. Yin, X. J. Wu, Q. Lu, C. Tan, M. Zhao, Z. Liu, W. Yang, H. Li, G. H. Nam, L. Zhang, Z. Chen, X. Huang, P. M. Radjenovic, W. Huang, Z. Q. Tian, J. F. Li, H. Zhang, J. Am. Chem. Soc., 2020, 142, 7161-7167.
[61]	F. H. Westheimer, Chem. Rev., 2002, 61, 265-273.
[62]	P. Liu, Y. Zhao, R. Qin, S. Mo, G. Chen, L. Gu, D. M. Chevrier, P. Zhang, Q. Guo, D. Zang, B. Wu, G. Fu, N. Zheng, Science, 2016, 352, 797-800.
[63]	D. Malko, A. Kucernak, Electrochem. Commun., 2017, 83, 67-71.
[64]	E. D. German, M. Sheintuch, J Phys. Chem. C, 2010, 114, 3089-3097.
[65]	C. Pasquini, I. Zaharieva, D. Gonzalez-Flores, P. Chernev, M. R. Mohammadi, L. Guidoni, R. D. L. Smith, H. Dau, J. Am. Chem. Soc., 2019, 141, 2938-2948.
[66]	Q. Wang, L. Shang, D. Sun-Waterhouse, T. Zhang, G. Waterhouse, Smart Mat., 2021, 2, 154-175.