Precise design of nickel phthalocyanine molecular structure: Optimizing electronic and spatial effects for remarkable electrocatalytic CO2 reduction

doi:10.1016/S1872-2067(23)64412-2

Abstract

Abstract:

The atomic dispersion offered by transition metal-nitrogen-carbon electrocatalysts (M-N-C) represents a promising system for efficient catalysis of the CO₂ reduction reaction (CO₂RR) to a CO product. However, accurate elucidation of the catalytic mechanism of M-N-C catalysts synthesized by pyrolysis is impeded by the ambiguity of the coordination environment of the MN_x active site. Herein, by combining theoretical and experimental methods, the influence of the electronic and geometric effects of the NiN₄ site in a group of nickel phthalocyanine (NiPc)-based molecular catalysts on the performance of CO₂RR are investigated. Density functional theory calculations indicate that only electron-withdrawing and ortho-nitro-substituted NiPc-based molecularly dispersed electrocatalysts can significantly enhance the NiN₄ active site for CO₂ activation. The lowest activation energy is required for forming the *COOH intermediate compared to other reference catalysts. Our modeling is in complete accordance with our experimental results, proving that the position of the substituent groups and push-pull electron effects simultaneously play crucial roles in CO₂RR catalyst performance.

Key words: CO₂ reduction reaction, Precise design, Electrocatalyst, Nickel phthalocyanine

Jingjing Li, Fengwei Zhang, Xinyu Zhan, Hefang Guo, Han Zhang, Wen-Yan Zan, Zhenyu Sun, Xian-Ming Zhang. Precise design of nickel phthalocyanine molecular structure: Optimizing electronic and spatial effects for remarkable electrocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2023, 48: 117-126.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64412-2

https://www.cjcatal.com/EN/Y2023/V48/I5/117

Figures/Tables 5

Scheme 1. Schematic of the preparation route for NiPc-based molecularly dispersed electrocatalysts.

Fig. 1. TEM (a), HRTEM (b), HAADF-STEM (c) images, and EDS maps (d) of NiPc(α-NO2)4/CNTs. Ni K-edge XANES spectra (e) and Fourier transformed EXAFS spectra (f) of NiPc(α-NO2)4/CNTs, NiPc(α-NH2)4/CNTs, NiPc/CNTs, standard NiO, and Ni foil.

Fig. 2. High-resolution XPS spectra in N 1s region (a?c) and Ni 2p region (d?f) of NiPc/CNTs, NiPc(α-NO2)4/CNTs, and NiPc(α-NH2)4/CNTs MDEs.

Fig. 3. (a) Linear sweep voltammetry curves of NiPc(α-NO2)4/CNTs and reference catalysts. (b) FECO at different potentials on various catalysts. (c) Product selectivity comparison at ?1.0 V vs. RHE. (d) CO partial current density at various potentials. (e) Electrochemical impedance spectroscopy (EIS) curves with corresponding fitting profiles for NiPc-based MDEs. (f) TOF values of CO2 to CO over various NiPc-based MDEs at different potentials.

Fig. 4. (a) The reaction pathway and free energy diagrams of CO2RR to CO over NiPc-based MDEs. (b) The difference in CO2RR and HER limiting potentials. (c?e) Various DFT optimized intermediates along the CO2RR pathway by NiPc(α-NO2)4/CNTs.

References

[1]	D. M. Koshy, S. C. Chen, D. U. Lee, M. B. Stevens, A. M. Abdellah, S. M. Dull, G. Chen, D. Nordlund, A. Gallo, C. Hahn, D. C. Higgins, Z. N. Bao, T. F. Jaramillo, Angew. Chem. Int. Ed., 2020, 59, 4043-4050.
[2]	J.-P. Cao, Y.-S. Xue, N.-F. Li, J.-J. Gong, R.-K. Kang, Y. Xu, J. Am. Chem. Soc., 2019, 141, 19487-19497.
[3]	A. D. Riccardis, M. Lee, R. V. Kazantsev, A. J. Garza, G. S. Zeng, D. M. Larson, E. L. Clark, P. Lobaccaro, P. W. W. Burroughs, E. Bloise, J. W. Ager, A. T. Bell, M. Head-Gordon, G. Mele, F. M. Toma, ACS Appl. Mater. Interfaces, 2020, 12, 5251-5258.
[4]	B. P. Yang, K. Liu, H. J. W. Li, C. X. Liu, J. W. Fu, H. M. Li, J. E. Huang, P. F. Ou, T. Alkayyali, C. Cai, Y. X. Duan, H. Liu, P. D. An, N. Zhang, W. Z. Li, X. Q. Qiu, C. K. Jia, J. H. Hu, L. Y. Chai, Z. Lin, Y. L. Gao, M. Miyauchi, E. Cortes, S. A. Maier, M. Liu, J. Am. Chem. Soc., 2022, 144, 3039-3049.
[5]	C. He, Y. Zhang, Y. F. Zhang, L. Zhao, L.-P. Yuan, J. N. Zhang, J. M. Ma, J.-S. Hu, Angew. Chem. Int. Ed., 2020, 59, 4914-4919.
[6]	Y. C. Wang, Y. Liu, W. Liu, J. Wu, Q. Li, Q. G. Feng, Z. Y. Chen, X. Xiong, D. S. Wang, Y. P. Lei, Energy Environ. Sci., 2020, 13, 4609-4624.
[7]	X. Wang, P. F. Ou, J. Wicks, Y. Xie, Y. Wang, J. Li, J. Tam, D. Ren, J. Y. Howe, Z. Y. Wang, A. Ozden, Y. Z. Finfrock, Y. Xu, Y. H. Li, A. S. Rasouli, K. Bertens, A. H. Ip, M. Graetzel, D. Sinton, E. H. Sargent, Nat. Commun., 2021, 12, 3387.
[8]	A. J. Gottle, M. T. M. Koper, J. Am. Chem. Soc., 2018, 140, 4826-4834.
[9]	J. E. Huang, F. W. Li, A. Ozden, A. S. Rasouli, F. P. G. d. Arquer, S. J. Liu, S. Z. Zhang, M. C. Luo, X. Wang, Y. W. Lum, Y. Xu, K. Bertens, R. K. Miao, C.-T. Dinh, D. Sinton, E. H. Sargent, Science, 2021, 372, 1074-1078.
[10]	C. P. O’Brien, R. K. Miao, S. J. Liu, Y. Xu, G. Lee, A. Robb, J. E. Huang, K. Xie, K. Bertens, C. M. Gabardo, J. P. Edwards, C.-T. Dinh, E. H. Sargent, D. Sinton, ACS Energy Lett., 2021, 6, 2952-2959.
[11]	P. S. Li, J. H. Bi, J. Y. Liu, Q. G. Zhu, C. J. Chen, X. F. Sun, J. L. Zhang, B. X. Han, Nat. Commun., 2022, 13, 1965.
[12]	Z. D. Li, D. He, X. X. Yan, S. Dai, S. Younan, Z. J. Ke, X. Q. Pan, X. H. Xiao, H. J. Wu, J. Gu, Angew. Chem. Int. Ed., 2020, 59, 18572-18577.
[13]	Y. J. Sa, H. Jung, D. Shin, H. Y. Jeong, S. Ringe, H. Kim, Y. J. Hwang, S. H. Joo, ACS Catal., 2020, 10, 10920-10931.
[14]	J. C. Zhang, W. Z. Cai, F. X. Hu, H. B. Yang, B. Liu, Chem. Sci., 2021, 12, 6800-6819.
[15]	X. Y. Cao, L. L. Zhao, B. R. Wulan, D. X. Tan, Q. W. Chen, J. Z. Ma, J. T. Zhang, Angew. Chem. Int. Ed., 2021, 61, e202113918.
[16]	S. H. Gong, W. B. Wang, C. N. Zhang, M. H. Zhu, R. Q. Lu, J. J. Ye, H. Yang, C. D. Wu, J. Liu, D. W. Rao, S. Y. Shao, X. M. Lv, Adv. Funct. Mater., 2022, 32, 2110649.
[17]	A. Thevenon, A. Rosas-Hernandez, A. M. F. Herreros, T. Agapie, J. C. Peters, ACS Catal., 2021, 11, 4530-4537.
[18]	J. Wordsworth, T. M. Benedetti, S. V. Somerville, W. Schuhmann, R. D. Tilley, J. J. Gooding, Angew. Chem. Int. Ed., 2022, 61, e202200755.
[19]	D. Karapinar, N. T. Huan, N. R. Sahraie, J. Li, D. Wakerley, N. Touati, S. Zanna, D. Taverna, L. H. GalvaoTizei, A. Zitolo, F. Jaouen, V. Mougel, M. Fontecave, Angew. Chem. Int. Ed., 2019, 58, 15098-15103.
[20]	Z. Zhang, L. Yu, Y. C. Tu, R. X. Chen, L. H. Wu, J. F. Zhu, D. H. Deng, Cell Rep. Phys. Science, 2020, 1, 100145.
[21]	T.-T. Zhuang, Z.-Q. Liang, A. Seifitokaldani, Y. Li, P. D. Luna, T. Burdyny, F. L. Che, F. Meng, Y. M. Min, R. Quintero-Bermudez, C. T. Dinh, Y. J. Pang, M. Zhong, B. Zhang, J. Li, P.-N. Chen, X.-L. Zheng, H. Y. Liang, W.-N. Ge, B.-J. Ye, D. Sinton, S.-H. Yu, E. H. Sargent, Nat. Catal., 2018, 1, 421-428.
[22]	Z. Zhang, J. P. Xiao, X. J. Chen, S. Yu, L. Yu, R. Si, Y. Wang, S. H. Wang, X. G. Meng, Y. Wang, Z. Q. Tian, D. H. Deng, Angew. Chem. Int. Ed., 2018, 57, 16339-16342.
[23]	L. Lin, H. B. Li, C. C. Yan, H. F. Li, R. Si, M. G. Li, J. P. Xiao, G. X. Wang, X. H. Bao, Adv. Mater., 2019, 31, 1903470.
[24]	W. Q. Liu, J. W. Qi, P. Y. Bai, W. D. Zhang, L. Xu, Appl. Catal. B, 2020, 272, 118974.
[25]	A. S. Varela, W. Ju, A. Bagger, P. Franco, J. Rossmeisl, P. Strasser, ACS Catal., 2019, 9, 7270-7284.
[26]	H. P. Yang, Y. Wu, Q. Lin, L. D. Fan, X. Y. Chai, Q. L. Zhang, J. H. Liu, C. X. He, Z. Q. Lin, Angew. Chem. Int. Ed., 2018, 57, 15476-15480.
[27]	Y. Wang, M. Y. Wang, Z. S. Zhang, Q. Wang, Z. Jiang, M. Lucero, X. Zhang, X. X. Li, M. Gu, Z. X. Feng, Y. Y. Liang, ACS Catal., 2019, 9, 6252-6261.
[28]	S. Jin, Y. X. Ni, Z. M. Hao, K. Zhang, Y. Lu, Z. H. Yan, Y. J. Wei, Y. R. Lu, T. S. Chan, J. Chen, Angew. Chem. Int. Ed., 2020, 59, 21885-21889.
[29]	Y. Li, W. T. Shan, M. J. Zachman, M. Y. Wang, S. Hwang, H. Tabassum, J. Yang, X. X. Yang, S. Karakalos, Z. X. Feng, G. F. Wang, G. Wu, Angew. Chem. Int. Ed., 2022, 61, e202205632.
[30]	B. T. Chen, B. R. Li, Z. Q. Tian, W. B. Liu, W. P. Liu, W. W. Sun, K. Wang, L. Chen, J. Z. Jiang, Adv. Energy Mater., 2021, 11, 2102152.
[31]	T. T. Zheng, K. Jiang, H. T. Wang, Adv. Mater., 2018, 30, 1802066.
[32]	B. Han, X. Ding, B. Q. Yu, H. Wu, W. Zhou, W. P. Liu, C. Y. Wei, B. T. Chen, D. D. Qi, H. L. Wang, K. Wang, Y. L. Chen, B. L. Chen, J. Z. Jiang, J. Am. Chem. Soc., 2021, 143, 7104-7113.
[33]	Y. S. Wu, Y. Y. Liang, H. L. Wang, Acc. Chem. Res. 2021, 54, 3149-3159.
[34]	Y. S. Wu, Z. Jiang, X. Lu, Y. Y. Liang, H. L. Wang, Nature, 2019, 575, 639-642.
[35]	X. Zhang, Z. S. Wu, X. Zhang, L. W. Li, Y. Y. Li, H. M. Xu, X. X. Li, X. L. Yu, Z. S. Zhang, Y. Y. Liang, H. L. Wang, Nat. Commun., 2017, 8, 14675.
[36]	S. Liu, H. B. Yang, S. F. Hung, J. Ding, W. Z. Cai, L. H. Liu, J. J. Gao, X. N. Li, X. Y. Ren, Z. C. Kuang, Y. Q. Huang, T. Zhang, B. Liu, Angew. Chem. Int. Ed., 2020, 59, 798-803.
[37]	M. Huang, B. W. Deng, X. L. Zhao, Z. Y. Zhang, F. Li, K. L. Li, Z. H. Cui, L. X. Kong, J. M. Lu, F. Dong, L. L. Zhang, P. Chen, ACS Nano, 2022, 16, 2110-2119.
[38]	Z. C. Lin, Z. Jiang, Y. B. Yuan, H. Li, H. X. Wang, Y. R. Tang, C. C. Liu, Y. Y. Liang, Chin. J. Catal., 2022, 43, 104-109.
[39]	X. Zhang, Y. Wang, M. Gu, M. Y. Wang, Z. S. Zhang, W. Y. Pan, Z. Jiang, H. Z. Zheng, M. Lucero, H. L. Wang, G. E. Sterbinsky, Q. Ma, Y.-G. Wang, Z. X. Feng, J. Li, H. J. Dai, Y. Y. Liang, Nat. Energy, 2020, 5, 684-692.
[40]	X. S. Ding, B. H. Han, Angew. Chem. Int. Ed., 2015, 54, 6536-6539.
[41]	S. X. Xu, Y. X. Ding, J. Du, Y. Zhu, G. Q. Liu, Z. B. Wen, X. Liu, Y. B. Shi, H. Gao, L. C. Sun, F. Li, ACS Catal., 2022, 12, 5502-5509.
[42]	W. Q. Liu, P. Y. Bai, S. L. Wei, C. C. Yang, L. Xu, Angew. Chem. Int. Ed., 2022, 61, e202201166.
[43]	W. H. Ren, X. Tan, W. F. Yang, C. Jia, S. M. Xu, K. X. Wang, S. C. Smith, C. Zhao, Angew. Chem. Int. Ed., 2019, 58, 6972-6976.
[44]	Z. P. Chen, X. X. Zhang, W. Liu, X. Zhang, L. Liu, M. Y. Jiao, K. W. Mou, X. P. Zhang, L. C. Liu, Energy Environ. Sci., 2021, 14, 2349-2356.
[45]	A. A. Peterson, F. Ablid-Pedersen, F. Studt, J. Rossmeisl, J. K. Nørskov, Energy Environ. Sci., 2010, 3, 1311-1315.
[46]	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.
[47]	S. Liu, H. B. Yang, X. Huang, L. H. Liu, W. Z. Cai, J. J. Gao, X. N. Li, T. Zhang, Y. Q. Huang, B. Liu, Adv. Funct. Mater., 2018, 28, 1800499.
[48]	J. J. Li, W-Y. Zan, H. X. Kang, Z. P. Dong, X. M. Zhang, Y. X. Lin, Y-W, Mu, F. W. Zhang, X-M. Zhang, J. Gu, Appl. Catal. B., 2021, 298, 120510.
[49]	Y. Li, W. Shan, M. J. Zachman, M. Wang, S. Hwang, H. Tabassum, J. Yang, X. Yang, S. Karakalos, Z. Feng, G. Wang, G. Wu, Angew. Chem. Int. Ed., 2022, 61, e202205632.
[50]	Y. Wu, C. Chen, X. Yan, X. Sun, Q. Zhu, P. Li, Y. Li, S. Liu, J. Ma, Y. Huang, B. Han, Angew. Chem. Int. Ed., 2021, 60, 20803-20810.
[51]	J. Zhu, M. Xiao, D. Ren, R. Gao, X. Liu, Z. Zhang, D. Luo, W. Xing, D. Su, A. Yu, Z. Chen, J. Am. Chem. Soc., 2022, 144, 9661-9671.
[52]	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.
[53]	F. Pan, B. Li, E. Sarnello, Y. Fei, X. Feng, Y. Gang, X. Xiang, L. Fang, T. Li, Y. H. Hu, G. Wang, Y. Li, ACS Catal., 2020, 10, 10803-10811.
[54]	J. Pei, T. Wang, R. Sui, X. Zhang, D. Zhou, F. Qin, X. Zhao, Q. Liu, W. Yan, J. Dong, L. Zheng, A. Li, J. Mao, W. Zhu, W. Chen, Z. Zhuang, Energy Environ. Sci., 2021, 14, 3019-3028.

Precise design of nickel phthalocyanine molecular structure: Optimizing electronic and spatial effects for remarkable electrocatalytic CO₂ reduction

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