Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO2 electroreduction

doi:10.1016/S1872-2067(24)60087-2

Abstract

Abstract:

Electrochemical CO₂ reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion. The development of efficient catalysts with high conductivity and readily accessible active sites for CO₂ electroreduction remains challenging yet indispensable. In this work, a reliable poly(ethyleneimine) (PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles (NPs) (denoted as Ni@NHCS), where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres, but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites. Benefiting from the unique structural properties of Ni@NHCS, the aggregation and exposure of Ni NPs can be effectively prevented, while the accessibility of abundant catalytically active Ni-Nx sites can be ensured. As a result, Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^-2 and a Faradaic efficiency of 93.0% at -1.0 V vs. RHE, outperforming those of its PEI-free analog. Apart from the excellent activity and selectivity, the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability. The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO₂ reduction. Furthermore, the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

Key words: Hollow carbon sphere, Ni nanoparticle, CO₂ reduction, Electrocatalysis, Single-atom catalyst

Kaining Li, Yasutaka Kuwahara, Hiromi Yamashita. Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2024, 64: 66-76.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60087-2

https://www.cjcatal.com/EN/Y2024/V64/I9/66

Figures/Tables 8

Fig. 1. Schematic illustration of the preparation process of Ni@NHCS.

Fig. 2. Morphological characterizations of Ni@NHCS. TEM images (a,b) selected area electron diffraction (SAED) pattern (c), HR-TEM image (d), partially enlarged regions in (d) (e,f). HAADF-STEM (g) and the corresponding STEM elemental maps of Ni (h), N (i), C (j), and overlap (k) of Ni@NHCS sample.

Fig. 3. (a) XRD patterns of Ni@NHCS, Ni/HCS, and NHCS. Ni K-edge XANES spectra (b) and Ni K-edge FT-EXAFS spectra (c) of Ni@NHCS, Ni/HCS, and references. (d) H2-TPR profiles of Ni2+-PEI@HCS (precursor of Ni@NHCS) and PEI@HCS (precursor of NHCS).

Fig. 4. (a) N 1s XPS spectra of NHCS and Ni@NHCS. (b) Ni 2p XPS spectrum of Ni@NHCS.

Fig. 5. Time-dependent current density curves of Ni@NHCS (a), NHCS (b), and Ni/HCS (c). FECO and FEH2 for Ni@NHCS (d), NHCS (e), and Ni/HCS (f).

Fig. 6. (a) CO partial current density (JCO) of Ni@NHCS, NHCS, and Ni/HCS at given potentials. (b) EIS spectra over Ni@NHCS, NHCS, and Ni/HCS. (c) Long-term CO2 reduction test of Ni@NHCS at -1.0 V vs. RHE. (d) Performance comparison of Ni@NHCS with reported electrocatalytic CO2-to-CO conversion catalysts.

Fig. 7. (a) Plots of charging current density differences vs scan rates. (b) N2-adsorption/desorption isotherms of as-prepared samples. (c) CO2 uptake amount of as-prepared samples in a flow of 10% CO2/N2 for 6 h at 25 °C. (d) CO-TPD profiles of Ni@NHCS and Ni/HCS.

Fig. 8. (a) XRD patterns of Ni@NHCS before and after acid treatment. TEM image (b), SAED pattern (c), HAADF-STEM image (d), and EDS elemental mapping images (e) of Ni@NHCS-acid. (f) FECO and CO partial current density of Ni@NHCS and Ni@NHCS-acid.

References

[1]	T. Lei, D. Wang, X. Yu, S. Ma, W. Zhao, C. Cui, J. Meng, S. Tao, D. Guan, Nature, 2023, 622, 514-520.
[2]	P. Achakulwisut, P. Erickson, C. Guivarch, R. Schaeffer, E. Brutschin, S. Pye, Nat. Commun., 2023, 14, 5425.
[3]	D. J. Beerling, E. P. Kantzas, M. R. Lomas, P. Wade, R. M. Eufrasio, P. Renforth, B. Sarkar, M. G. Andrews, R. H. James, C. R. Pearce, J.-F. Mercure, H. Pollitt, P. B. Holden, N. R. Edwards, M. Khanna, L. Koh, S. Quegan, N. F. Pidgeon, I. A. Janssens, J. Hansen, S. A. Banwart, Nature, 2020, 583, 242-248.
[4]	Y.-S. Yu, X. Zhang, J.-W. Liu, Y. Lee, X.-S. Li, Energy Environ. Sci., 2021, 14, 5611-5668.
[5]	N. Zhu, X. Zhang, N. Chen, J. Zhu, X. Zheng, Z. Chen, T. Sheng, Z. Wu, Y. Xiong, J. Am. Chem. Soc., 2023, 145, 24852-24861.
[6]	Z. Wang, Y. Li, X. Zhao, S. Chen, Q. Nian, X. Luo, J. Fan, D. Ruan, B. Q. Xiong, X. Ren, J. Am. Chem. Soc., 2023, 145, 6339-6348.
[7]	S. Liang, J. Xiao, T. Zhang, Y. Zheng, Q. Wang, B. Liu, Angew. Chem. Int. Ed., 2023, 62, e202310740.
[8]	F. Wang, G. Wang, P. Deng, Y. Chen, J. Li, D. Wu, Z. Wang, C. Wang, Y. Hua, X. Tian, Small, 2023, 19, 2301128.
[9]	W. Ma, X. He, W. Wang, S. Xie, Q. Zhang, Y. Wang, Chem. Soc. Rev., 2021, 50, 12897-12914.
[10]	W. Ren, X. Tan, W. Yang, C. Jia, S. Xu, K. Wang, S. C. Smith, C. Zhao, Angew. Chem. Int. Ed., 2019, 58, 6972-6976.
[11]	H. Jiang, L. Wang, H. Kaneko, R. Gu, G. Su, L. Li, J. Zhang, H. Song, F. Zhu, A. Yamaguchi, J. Xu, F. Liu, M. Miyauchi, W. Ding, M. Zhong, Nat. Catal., 2023, 6, 519-530.
[12]	Y. Niu, C. Zhang, Y. Wang, D. Fang, L. Zhang, C. Wang, ChemSusChem, 2021, 14, 1140-1154.
[13]	Z. Liu, T. Yan, H. Shi, H. Pan, Y. Cheng, P. Kang, ACS Appl. Mater. Interfaces, 2022, 14, 7900-7908.
[14]	M. Liang, Y. Liu, J. Zhang, F. Wang, Z. Miao, L. Diao, J. Mu, J. Zhou, S. Zhuo, Appl. Catal. B, 2022, 306, 121115.
[15]	C. Z. Yuan, H. B. Li, Y. F. Jiang, K. Liang, S. J. Zhao, X. X. Fang, L. B. Ma, T. Zhao, C. Lin, A. W. Xu, J. Mater. Chem. A, 2019, 7, 6894-6900.
[16]	X. Wang, D. Wu, C. Dai, C. Xu, P. Sui, R. Feng, Y. Wei, X. Z. Fu, J. L. Luo, J. Mater. Chem. A, 2020, 8, 5105-5114.
[17]	M. Jia, C. Choi, T.-S. Wu, C. Ma, P. Kang, H. Tao, Q. Fan, S. Hong, S. Liu, Y.-L. Soo, Y. Jung, J. Qiu, Z. Sun, Chem. Sci., 2018, 9, 8775-8780.
[18]	W. Zheng, C. Guo, J. Yang, F. He, B. Yang, Z. Li, L. Lei, J. Xiao, G. Wu, Y. Hou, Carbon, 2019, 150, 52-59.
[19]	Z. Li, D. He, X. Yan, S. Dai, S. Younan, Z. Ke, X. Pan, X. Xiao, H. Wu, J. Gu, Angew. Chem. Int. Ed., 2020, 59, 18572-18577.
[20]	J. W. Sun, X. Wu, P. F. Liu, J. Chen, Y. Liu, Z. X. Lou, J. Y. Zhao, H. Y. Yuan, A. Chen, X. L. Wang, M. Zhu, S. Dai, H. G. Yang, Nat. Commun., 2023, 14, 1599.
[21]	S. Liang, Q. Jiang, Q. Wang, Y. Liu, Adv. Energy Mater., 2021, 11, 2101477.
[22]	H. Bin Yang, S. F. Hung, S. Liu, K. Yuan, S. Miao, L. Zhang, X. Huang, H. Y. Wang, W. Cai, R. Chen, J. Gao, X. Yang, W. Chen, Y. Huang, H. M. Chen, C. M. Li, T. Zhang, B. Liu, Nat. Energy, 2018, 3, 140-147.
[23]	K. Li, Y. Kuwahara, H. Yamashita, Chem. Sci., 2024, 15, 854-878.
[24]	P. Zhang, H. Chen, L. Chen, Y. Xiong, Z. Sun, H. Yang, Y. Fu, Y. Zhang, T. Liao, F. Li, Chin. J. Catal., 2023, 45, 152-161.
[25]	H. Nishihara, T. Hirota, K. Matsuura, M. Ohwada, N. Hoshino, T. Akutagawa, T. Higuchi, H. Jinnai, Y. Koseki, H. Kasai, Y. Matsuo, J. Maruyama, Y. Hayasaka, H. Konaka, Y. Yamada, S. Yamaguchi, K. Kamiya, T. Kamimura, H. Nobukuni, F. Tani, Nat. Commun., 2017, 8, 109-117.
[26]	W. Chaikittisilp, R. Khunsupat, T. T. Chen, C. W. Jones, Ind. Eng. Chem. Res., 2011, 50, 14203-14210.
[27]	H. J. Moon, J. M. Carrillo, J. Leisen, B. G. Sumpter, N. C. Osti, M. Tyagi, C. W. Jones, J. Am. Chem. Soc., 2022, 144, 11664-11675.
[28]	Y. Kuwahara, D.-Y. Kang,J. R. Copeland, N. A. Brunelli, S. A. Didas, P. Bollini, C. Sievers, T. Kamegawa, H. Yamashita, C. W. Jones, J. Am. Chem. Soc., 2012, 134, 10757-10760.
[29]	Y. Kuwahara, H. Kango, H. Yamashita, ACS Catal., 2019, 9, 1993-2006.
[30]	Y. Kuwahara, Y. Fujie, T. Mihogi, H. Yamashita, ACS Catal., 2020, 10, 6356-6366.
[31]	G. Yang, Y. Kuwahara, K. Mori, C. Louis, H. Yamashita, J. Phys. Chem. C, 2021, 125, 3961-3971.
[32]	Z. A. Qiao, P. Zhang, S. H. Chai, M. Chi, G. M. Veith, N. C. Gallego, M. Kidder, S. Dai, J. Am. Chem. Soc., 2014, 136, 11260-11263.
[33]	H. Zhang, O. Noonan, X. Huang, Y. Yang, C. Xu, L. Zhou, C. Yu, ACS Nano, 2016, 10, 4579-4586.
[34]	G. Yang, Y. Kuwahara, S. Masuda, K. Mori, C. Louis, H. Yamashita, J. Mater. Chem. A, 2020, 8, 4437-4446.
[35]	Q. Lu, C. Chen, Q. Di, W. Liu, X. Sun, Y. Tuo, Y. Zhou, Y. Pan, X. Feng, L. Li, D. Chen, J. Zhang, ACS Catal., 2022, 12, 1364-1374.
[36]	H. Chen, C. Yuan, X. Yang, X. Cheng, A. A. Elzatahry, A. Alghamdi, J. Su, X. He, Y. Deng, ACS Appl. Nano Mater., 2020, 3, 4586-4598.
[37]	H. Tan, X. Wang, D. Jia, P. Hao, Y. Sang, H. Liu, J. Mater. Chem. A, 2017, 5, 2580-2591.
[38]	R. Li, P. Kuang, S. Wageh, A. A. Al-Ghamdi, H. Tang, J. Yu, Chem. Eng. J., 2023, 453, 139797.
[39]	P. Geng, Y. Lin, M. Du, C. Wu, T. Luo, Y. Peng, L. Wang, X. Jiang, S. Wang, X. Zhang, L. Ni, S. Chen, M. Shakouri, H. Pang, Adv. Sci., 2023, 10, 2302215.
[40]	B. Ming, T. Jia, Y. Zhang, J. Li, C. Chen, W. Song, J. Zhao, Appl. Catal. B, 2024, 344, 123653.
[41]	S. Büchele, A. J. Martín, S. Mitchell, F. Krumeich, S. M. Collins, S. Xi, A. Borgna, J. Pérez-Ramírez, ACS Catal., 2020, 10, 3444-3454.
[42]	W. Ren, X. Tan, C. Jia, A. Krammer, Q. Sun, J. Qu, S. C. Smith, A. Schueler, X. Hu, C. Zhao, Angew. Chem. Int. Ed., 2022, 61, e202203335.
[43]	Q. Hao, H. Zhong, J. Wang, K. Liu, J. Yan, Z. Ren, N. Zhou, X. Zhao, H. Zhang, D. Liu, X. Liu, L. Chen, J. Luo, X. Zhang, Nat. Synth., 2022, 1, 719-728.
[44]	K. Li, Y. Kuwahara, K. Chida, T. Yoshii, H. Nishihara, H. Yamashita, Chem. Eng. J., 2024, 488, 150952.
[45]	M. Fan, Q. Yuan, Y. Zhao, Z. Wang, A. Wang, Y. Liu, K. Sun, J. Wu, L. Wang, J. Jiang, Adv. Mater., 2022, 34, 2107040.
[46]	D. Guo, R. Shibuya, C. Akiba, S. Saji, T. Kondo, J. Nakamura, Science, 2016, 351, 361-365.
[47]	Y. Li, X. F. Lu, S. Xi, D. Luan, X. Wang, X. W. (David) Lou, Angew. Chem. Int. Ed., 2022, 61, e202201491.
[48]	Y. Li, S. L. Zhang, W. Cheng, Y. Chen, D. Luan, S. Gao, X. W. (David) Lou, Adv. Mater., 2022, 34, 2105204.
[49]	K. Gan, H. Li, R. Li, J. Niu, J. He, D. Jia, X. He, Inorg. Chem. Front., 2023, 10, 2414-2422.
[50]	W. Zhang, S. Yang, M. Jiang, Y. Hu, C. Hu, X. Zhang, Z. Jin, Nano Lett., 2021, 21, 2650-2657.
[51]	K. Li, Y. Kuwahara, H. Yamashita, Appl. Catal. B, 2023, 331, 122713.
[52]	J. Yuan, S. Chen, Y. Zhang, R. Li, J. Zhang, T. Peng, Adv. Mater., 2022, 34, 2203139.
[53]	Q. Wang, K. Liu, J. Fu, C. Cai, H. Li, Y. Long, S. Chen, B. Liu, H. Li, W. Li, X. Qiu, N. Zhang, J. Hu, H. Pan, M. Liu, Angew. Chem. Int. Ed., 2021, 60, 25241-25245.
[54]	Q. Wang, M. Dai, H. Li, Y. Lu, T. Chan, C. Ma, K. Liu, J. Fu, W. Liao, S. Chen, E. Pensa, Y. Wang, S. Zhang, Y. Sun, E. Cortés, M. Liu, Adv. Mater., 2023, 35, 2300695.

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO₂ electroreduction

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