Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO2 reduction

doi:10.1016/S1872-2067(25)64759-0

Abstract

Abstract:

Electrocatalytic conversion of carbon dioxide (CO₂) offers an effective method of CO₂ fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni₁/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (N_pyri), achieved over 90% faradaic efficiency for CO at potentials from -0.7 to -1.0 V and a mass activity of 6.5 A/mg_Ni at -0.78 V along with high stability, outperforming other Ni SACs with lower CN and more N_pyri. Theoretical calculations of various three and four-coordinated Ni₁-N_xC_y structures revealed a linear correlation between the reaction Gibbs free energy for the potential-limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3d orbitals, therein the four-coordinated Ni₁-N₁C₃ with the highest HOMO position is identified as the active site for the electrocatalytic CO₂-to-CO process, in line with the experimental results.

Key words: Single-atom catalyst, Ni₁/NC, Coordination structure regulation, Active site structure, Electrochemical CO₂ reduction

Yuxing Xu, Leilei Wang, Qin Liu, Botao Teng, Chuanqiang Wu, Binghui Ge, Wentuan Bi, Minghui Gu, Mengkai Zhang, Huan Yan, Junling Lu. Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2025, 79: 68-77.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64759-0

https://www.cjcatal.com/EN/Y2025/V79/I12/68

Figures/Tables 7

Fig. 1. (a) Schematic illustration of tailoring of anchor sites on the NC support by calcining NC supports at 600, 800, 900, and 1000 °C, respectively. N: blue; C: grey. (b) XPS of various NC support in the N 1s region, along with deconvolutions. (c) Quantitive analysis of various of N species in different NCs.

Fig. 2. (a) Schematic illustration of synthesis of Ni1/NC SACs by Ni ALD where Ni atoms are selectively deposited on the defective anchor sites, but not on the regular surfaces. Representative aberration-corrected HAADF-STEM images of Ni1/NC-600 (b), Ni1/NC-900 (c), and Ni1/NC-1000-3h (d) at high-magnifications. Some Ni atoms are highlighted by red circles. (e) The contents of Npyri and Ni loadings in these Ni1/NC SACs based on the XPS and ICP-AES results, respectively.

Fig. 3. (a) Fourie-transformed EXAFS spectra of Ni1/NC SACs as well as the Ni foil, NiO and NiPC references at the Ni K edge. (b) WT-EXAFS contour plots of Ni foil, NiO, NiPC and Ni1/NC-1000-3h, respectively. (c) XANES spectra of Ni1/NC SACs, as well as the Ni foil, NiO and NiPC references, at the Ni K edge. The legends in (c) also apply to (a). (d) Corresponding XPS spectra of Ni1/NC SACs in the Ni 2p region.

Fig. 4. LSV curves (a), FEs (b) and CO partial current densities (c) at -0.78 V of Ni1/NC-600, Ni1/NC-800, Ni1/NC-900, Ni1/NC-1000-1h and Ni1/NC-1000-3h in CO2-saturated 0.5 mol L-1 KHCO3 with H-cell. (d) Durability test of Ni1/NC-1000-3h at a constant potential of -0.65 V in CO2-saturated 0.5 mol L-1 KHCO3 with H-cell.

Fig. 5. (a) Top view of the electron density isosurface maps of the NxCy (x = 1, 2, 3, 4; y = 1, 2, 3; x + y = 3 or 4). The balls in blue, grey and white represent N, C and H, respectively. The electron density isosurfaces are plotted at 0.001 e Bohr-3. (b) Top view of charge density differences of Ni atoms in various Ni1-NxCy. The yellow and cyan areas indicate the accumulation and depletion of electrons, respectively, with an isosurface value of 0.008 e Bohr-3.

Fig. 6. (a) The calculated Gibbs free energy diagrams on the Ni1-NxCy model surfaces. The insets show the optimized structures of *COOH and *CO intermediates adsorbed on Ni1-N1C3, respectively. Additional optimized structures of *COOH and *CO intermediates adsorbed on Ni1-NxCy are shown in Figs. S18-S21. (b) Side view of the charge density differences for adsorbed *COOH on Ni1-NxCy. The yellow and cyan areas indicate the accumulation and depletion of electrons, respectively, with an isosurface value of 0.008 e Bohr-3. Ni: green; N: blue; C: grey; O: red; H: white.

Fig. 7. (a) The PDOS projected onto the Ni-3d in Ni1-NxCy. The insets show the charge density differences for adsorbed *COOH on Ni1-N1C3 and Ni1-N4, respectively, with an isosurface value of 0.008 e Bohr-3. (b) Linear scaling relationship between calculated ΔG for CO2 to *COOH and the HOMO position of Ni-3d on proposed model surfaces. The averaged COHP (c) and ICOHP (d) between Ni-C and between Ni-N in Ni1-NxCy model. Pink represents bonding contributions, while cyan represents antibonding contributions.

References

[1]	C. W. Li, J. Ciston, M. W. Kanan, Nature, 2014, 508, 504-507.
[2]	J. Qiao, Y. Liu, F. Hong, J. Zhang, Chem. Soc. Rev., 2014, 43, 631-675.
[3]	B. Obama, Science, 2017, 355, 126-129.
[4]	Y. Xue, Y. Guo, H. Cui, Z. Zhou, Small Methods, 2021, 5, 2100736.
[5]	H. B. Gray, Nat. Chem., 2009, 1, 7-8.
[6]	A. Vasileff, Y. Zheng, S. Z. Qiao, Adv. Energy Mater., 2017, 7, 1700759.
[7]	D.-D. Zhu, J.-L. Liu, S.-Z. Qiao, Adv. Mater., 2016, 28, 3423-3452.
[8]	S. Lin, C. S. Diercks, Y.-B. Zhang, N. Kornienko, E. M. Nichols, Y. Zhao, A. R. Paris, D. Kim, P. Yang, O. M. Yaghi, C. J. Chang, Science, 2015, 349, 1208-1213.
[9]	D. U. Nielsen, X.-M. Hu, K. Daasbjerg, T. Skrydstrup, Nat. Catal., 2018, 1, 244-254.
[10]	A. S. Varela, N. Ranjbar Sahraie, J. Steinberg, W. Ju, H.-S. Oh, P. Strasser, Angew. Chem. Int. Ed., 2015, 54, 10758-10762.
[11]	T. Zheng, K. Jiang, H. Wang, Adv. Mater., 2018, 30, 1802066.
[12]	S. Jin, Z. Hao, K. Zhang, Z. Yan, J. Chen, Angew. Chem. Int. Ed., 2021, 60, 20627-20648.
[13]	Y. Imada, M. Osaki, M. Noguchi, T. Maeda, M. Fujiki, S. Kawamorita, N. Komiya, T. Naota, ChemCatChem, 2015, 7, 99-106.
[14]	H. Mistry, Y.-W. Choi, A. Bagger, F. Scholten, C. S. Bonifacio, I. Sinev, N. J. Divins, I. Zegkinoglou, H. S. Jeon, K. Kisslinger, E. A. Stach, J. C. Yang, J. Rossmeisl, B. Roldan Cuenya, Angew. Chem. Int. Ed., 2017, 56, 11394-11398.
[15]	Y. Chen, C. W. Li, M. W. Kanan, J. Am. Chem. Soc., 2012, 134, 19969-19972.
[16]	W. Zhu, R. Michalsky, Ö. Metin, H. Lv, S. Guo, C. J. Wright, X. Sun, A. A. Peterson, S. Sun, J. Am. Chem. Soc., 2013, 135, 16833-16836.
[17]	A. Bagger, W. Ju, A. S. Varela, P. Strasser, J. Rossmeisl, Catal. Today, 2017, 288, 74-78.
[18]	J. Zhang, W. Cai, F.-X. Hu, H. Yang, B. Liu, Chem. Sci., 2021, 12, 6800-6819.
[19]	M. Li, H.Wang, W. Luo, P. C. Sherrell, J. Chen, J. Yang, Adv. Mater., 2020, 32, 2001848.
[20]	W. Ju, A. Bagger, G.-P. Hao, A. S. Varela, I. Sinev, V. Bon, B. Roldan Cuenya, S. Kaskel, J. Rossmeisl, P. Strasser, Nat. Commun., 2017, 8, 944.
[21]	D. Karapinar, N. T. Huan, N. Ranjbar Sahraie, J. Li, D. Wakerley, N. Touati, S. Zanna, D. Taverna, L. H. Galvão Tizei, A. Zitolo, F. Jaouen, V. Mougel, M. Fontecave, Angew. Chem. Int. Ed., 2019, 58, 15098-15103.
[22]	X. Li, S. Xi, L. Sun, S. Dou, Z. Huang, T. Su, X. Wang, Adv. Sci., 2020, 7, 2001545.
[23]	M. Jia, S. Hong, T.-S. Wu, X. Li, Y.-L. Soo, Z. Sun, Chem. Commun., 2019, 55, 12024-12027.
[24]	X. Wang, Z. Chen, X. Zhao, T. Yao, W. Chen, R. You, C. Zhao, G. Wu, J. Wang, W. Huang, J. Yang, X. Hong, S. Wei, Y. Wu, Y. Li, Angew. Chem. Int. Ed., 2018, 57, 1944-1948.
[25]	Y.-N. Gong, L. Jiao, Y. Qian, C.-Y. Pan, L. Zheng, X. Cai, B. Liu, S.-H. Yu, H.-L. Jiang, Angew. Chem. Int. Ed., 2020, 59, 2705-2709.
[26]	S. Liang, L. Huang, Y. Gao, Q. Wang, B. Liu, Adv. Sci., 2021, 8, 2102886.
[27]	Y. Li, Y. Xu, S. Chen, X. Shi, Q. Gu, L. Wang, M. Gu, B. Teng, B. Yang, J. Lu, Angew. Chem. Int. Ed., 2024, 63, e202413043.
[28]	L. Lin, H. Li, Y. Wang, H. Li, P. Wei, B. Nan, R. Si, G. Wang, X. Bao, Angew. Chem. Int. Ed., 2021, 60, 26582-26586.
[29]	M. Wen, N. Sun, L. Jiao, S.-Q. Zang, H.-L. Jiang, Angew. Chem. Int. Ed., 2024, 63, e202318338.
[30]	Y. Guo, S. Yao, Y. Xue, X. Hu, H. Cui, Z. Zhou, Appl. Catal. B, 2022, 304, 120997.
[31]	C. Li, W. Ju, S. Vijay, J. Timoshenko, K. Mou, D. A. Cullen, J. Yang, X. Wang, P. Pachfule, S. Brückner, H. S. Jeon, F. T. Haase, S.-C. Tsang, C. Rettenmaier, K. Chan, B. R. Cuenya, A. Thomas, P. Strasser, Angew. Chem. Int. Ed., 2022, 61, e202114707.
[32]	Z. Chen, X. Zhang, W. Liu, M. Jiao, K. Mou, X. Zhang, L. Liu, Energy Environ. Sci., 2021, 14, 2349-2356.
[33]	X. Li, W. Bi, M. Chen, Y. Sun, H. Ju, W. Yan, J. Zhu, X. Wu, W. Chu, C. Wu, Y. Xie, J. Am. Chem. Soc., 2017, 139, 14889-14892.
[34]	X. Hu, S. Yao, L. Chen, X. Zhang, M. Jiao, Z. Lu, Z. Zhou, J. Mater. Chem. A, 2021, 9, 23515-23521.
[35]	C. Yan, H. Li, Y. Ye, H. Wu, F. Cai, R. Si, J. Xiao, S. Miao, S. Xie, F. Yang, Y. Li, G. Wang, X. Bao, Energy Environ. Sci., 2018, 11, 1204-1210.
[36]	H. Kim, D. Shin, W. Yang, D. H. Won, H.-S. Oh, M. W. Chung, D. Jeong, S. H. Kim, K. H. Chae, J. Y. Ryu, J. Lee, S. J. Cho, J. Seo, H. Kim, C. H. Choi, J. Am. Chem. Soc., 2021, 143, 925-933.
[37]	Y. Zhang, L. Jiao, W. Yang, C. Xie, H.-L. Jiang, Angew. Chem. Int. Ed., 2021, 60, 7607-7611.
[38]	L. Yuan, S. Zeng, G. Li, Y. Wang, K. Peng, J. Feng, X. Zhang, S. Zhang, Adv. Funct. Mater., 2023, 33, 2306994.
[39]	Z.-L. Wang, J. Choi, M. Xu, X. Hao, H. Zhang, Z. Jiang, M. Zuo, J. Kim, W. Zhou, X. Meng, Q. Yu, Z. Sun, S. Wei, J. Ye, G. G. Wallace, D. L. Officer, Y. Yamauchi, ChemSusChem, 2020, 13, 929-937.
[40]	X. Zhao, Y. Liu, J. Am. Chem. Soc., 2020, 142, 5773-5777.
[41]	L. Wang, C. Zhu, M. Xu, C. Zhao, J. Gu, L. Cao, X. Zhang, Z. Sun, S. Wei, W. Zhou, W.-X. Li, J. Lu, J. Am. Chem. Soc., 2021, 143, 18854-18858.
[42]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[43]	B. Hammer, L. B. Hansen, J. K. Nørskov, Phys. Rev. B, 1999, 59, 7413-7421.
[44]	Y. Zhang, W. Yang, Phys. Rev. Lett., 1998, 80, 890.
[45]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[46]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[47]	S. Grimme, J. Comput. Chem., 2006, 27, 1787-1799.
[48]	W. Tang, E. Sanville, G. Henkelman, J. Phys. Condens. Matter, 2009, 21, 084204.
[49]	K. Momma, F. Izumi, J. Appl. Crystallogr., 2011, 44, 1272-1276.
[50]	V. Wang, N. Xu, J.-C. Liu, G. Tang, W.-T. Geng, Comput. Phys. Commun., 2021, 267, 108033.
[51]	B. Delley, J. Chem. Phys., 2000, 113, 7756-7764.
[52]	V. L. Deringer, A. L. Tchougréeff, R. Dronskowski, J. Phys. Chem. A, 2011, 115, 5461-5466.
[53]	R. Dronskowski, P. E. Bloechl, J. Phys. Chem., 1993, 97, 8617-8624.
[54]	S. Maintz, V. L. Deringer, A. L. Tchougréeff, R. Dronskowski, J. Comput. Chem., 2013, 34, 2557-2567.
[55]	S. Maintz, V. L. Deringer, A. L. Tchougréeff, R. Dronskowski, J. Comput. Chem., 2016, 37, 1030-1035.
[56]	J. Gu, M. Jian, L. Huang, Z. Sun, A. Li, Y. Pan, J. Yang, W. Wen, W. Zhou, Y. Lin, H.-J. Wang, X. Liu, L. Wang, X. Shi, X. Huang, L. Cao, S. Chen, X. Zheng, H. Pan, J. Zhu, S. Wei, W.-X. Li, J. Lu, Nat. Nanotechnol., 2021, 16, 1141-1149.
[57]	J. Lu, J. W. Elam, P. C. Stair, Acc. Chem. Res., 2013, 46, 1806-1815.
[58]	L. Jiao, J. Zhu, Y. Zhang, W. Yang, S. Zhou, A. Li, C. Xie, X. Zheng, W. Zhou, S.-H. Yu, H.-L. Jiang, J. Am. Chem. Soc., 2021, 143, 19417-19424.
[59]	J. Yin, J. Jin, Z. Yin, L. Zhu, X. Du, Y. Peng, P. Xi, C.-H. Yan, S. Sun, Nat. Commun., 2023, 14, 1724.
[60]	Q. Li, J. Fu, W. Zhu, Z. Chen, B. Shen, L. Wu, Z. Xi, T. Wang, G. Lu, J.-J. Zhu, S. Sun, J. Am. Chem. Soc., 2017, 139, 4290-4293.
[61]	Z. Fu, B. Yang, R. Wu, Phys. Rev. Lett., 2020, 125, 156001.
[62]	X. Shi, Z. Wen, Q. Gu, L. Jiao, H.-L. Jiang, H. Lv, H. Wang, J. Ding, M. P. Lyons, A. Chang, Z. Feng, S. Chen, Y. Lin, X. Xu, P. Du, W. Xu, M. Sun, Y. Li, B. Yang, T. Zhang, X. Wu, J. Lu, Nature, 2025, 640, 668-675.
[63]	J.-J. Velasco-Vélez, C.-H. Chuang, D. Gao, Q. Zhu, D. Ivanov, H. S. Jeon, R. Arrigo, R. V. Mom, E. Stotz, H.-L. Wu, T. E. Jones, B. Roldan Cuenya, A. Knop-Gericke, R. Schlögl, ACS Catal., 2020, 10, 11510-11518.

Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO₂ reduction

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Gang Wang, Imran Muhammad, Hui-Min Yan, Jun Li, Yang-Gang Wang. Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO₂ electroreduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 120-129.
[2]	Eryu Wang, Yi-Chun Chu, Wenjun Zhang, Yanping Wei, Chuanling Si, Regina Palkovits, Xin-Ping Wu, Zupeng Chen. Sustainable co-production of H₂ and lactic acid from lignocellulose photoreforming using Pt-C₃N₄ single-atom catalyst [J]. Chinese Journal of Catalysis, 2025, 74(7): 308-318.
[3]	Xiaochun Hu, Longgang Tao, Kun Lei, Zhiqiang Sun, Mingwu Tan. Unraveling TiO₂ phase effects on Pt single-atom catalysts for efficient CO₂ conversion [J]. Chinese Journal of Catalysis, 2025, 73(6): 186-195.
[4]	Lei Xiong, Xianbiao Fu. Recent advances and challenges in electrochemical CO₂ reduction to CH₄ [J]. Chinese Journal of Catalysis, 2025, 73(6): 39-61.
[5]	Chenghong Hu, Yue Zhang, Yi Zhang, Qintong Huang, Kui Shen, Liyu Chen, Yingwei Li. Single-atomic Fe sites modulated by Sn regulator for enhanced electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 72(5): 222-229.
[6]	Fenli Liu, Man Yang, Jianglin Duan, Zhiyu Yin, Mingyang Shi, Fuqing Chen, Huifeng Xiong, Xin Liu, Wengang Liu, Qixing Xia, Shaodong Sun, Dan Feng, Haifeng Qi, Yong Qin, Yujing Ren. Peripheral N_V-induced electron transfer to Fe₁ single atoms for highly efficient O₂ activation [J]. Chinese Journal of Catalysis, 2025, 72(5): 187-198.
[7]	Fanrong Chen, Jiaju Fu, Liang Ding, Xiaoying Lu, Zhe Jiang, Xiaoling Zhang, Jin-Song Hu. Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate [J]. Chinese Journal of Catalysis, 2025, 71(4): 138-145.
[8]	Tao Ban, Jian-Wei Wang, Xi-Yang Yu, Hai-Kuo Tian, Xin Gao, Zheng-Qing Huang, Chun-Ran Chang. Machine learning-assisted screening of SA-FLP dual-active-site catalysts for the production of methanol from methane and water [J]. Chinese Journal of Catalysis, 2025, 70(3): 311-321.
[9]	Jiayi Cui, Xintao Yu, Xueyao Li, Jianmin Yu, Lishan Peng, Zidong Wei. Advances in spin regulation of M-N-C single-atom catalysts and their applications in electrocatalysis [J]. Chinese Journal of Catalysis, 2025, 69(2): 17-34.
[10]	Mingzhi Wang, Wensheng Fang, Deyu Zhu, Chenfeng Xia, Wei Guo, BaoYu Xia. Tandem design on electrocatalysts and reactors for electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 69(2): 1-16.
[11]	Yangyang Li, Jingyi Yang, Botao Qiao, Tao Zhang. Size-dependent strong metal-support interaction modulation of Pt/CoFe₂O₄ catalysts [J]. Chinese Journal of Catalysis, 2025, 69(2): 292-302.
[12]	Tianyou Zhao, Fengming Hu, Meiqi Zhu, Chang-Jie Yang, Xin-Yu Wang, Yong-Zhou Pan, Jiarui Yang, Xia Zhang, Wen-Hao Li, Dingsheng Wang. Future development of single-atom catalysts in portable energy and sensor technologies [J]. Chinese Journal of Catalysis, 2025, 78(11): 100-137.
[13]	Hao Dai, Tao Song, Xian Yue, Shuting Wei, Fuzhi Li, Yanchao Xu, Siyan Shu, Ziang Cui, Cheng Wang, Jun Gu, Lele Duan. Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO₂ electroreduction to CH₄ [J]. Chinese Journal of Catalysis, 2024, 64(9): 123-132.
[14]	Jialin Wang, Kaini Zhang, Ta Thi Thuy Nga, Yiqing Wang, Yuchuan Shi, Daixing Wei, Chung-Li Dong, Shaohua Shen. Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2024, 64(9): 54-65.
[15]	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(9): 66-76.