Journal Home > Volume 15 , Issue 7
Nano Research 2022, 15(7): 5816-5823 https://doi.org/10.1007/s12274-022-4197-6
Research Article | Issue | Published: 18 April 2022

Ligand centered electrocatalytic efficient CO2 reduction reaction at low overpotential on single-atom Ni regulated molecular catalyst

Show Author's Information Jiazhi Wang1,2,  Qi Hao1,3,  Haixia Zhong4,  Kai Li1,  Xinbo Zhang1,2( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
University of Science and Technology of China, Hefei 230026, China
Key Laboratory of Automobile Materials, Ministry of Education, Jilin University, Changchun 130022, China
Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden 01062, Germany
Keywords:
iron phthalocyanine, carbon dioxide reduction reaction, single-atom Ni, molecular catalyst, ultra-low overpotential
Topics:
Catalytic
Cite this article:
Wang J, Hao Q, Zhong H, et al. Ligand centered electrocatalytic efficient CO2 reduction reaction at low overpotential on single-atom Ni regulated molecular catalyst. Nano Research, 2022, 15(7): 5816-5823. https://doi.org/10.1007/s12274-022-4197-6
Download citation
EndNote(RIS)
BibTeX

577

Views

24

Downloads

Citations

11

Crossref

10

WoS

11

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Electrochemical CO2 reduction reaction (CO2RR) into value-added chemicals/fuels is crucial for realizing the sustainable carbon cycle while mitigating the energy crisis. However, it is impeded by the relatively high overpotential and low energy efficiency due to the lack of efficient electrocatalysts. Herein, we develop an isolated single-atom Ni catalyst regulated strategy to activate and stabilize the iron phthalocyanine molecule (Ni SA@FePc) toward a highly efficient CO2RR process at low overpotential. The well-defined and homogenous catalytic centers with unique structures confer Ni SA@FePc with a significantly enhanced CO2RR performance compared to single-atom Ni catalyst and FePc molecule and afford the atomic understanding on active sites and catalytic mechanism. As expected, Ni SA@FePc exhibits a high selectivity of more significant Faraday efficiency (≥ 95%) over a wide potential range, a high current density of ~ 252 mA·cm−2 at low overpotential (390 mV), and excellent long-term stability for CO2RR to CO. X-ray absorption spectroscopy measurement and theoretical calculation indicate the formation of NiN4-O2-FePc heterogeneous structure for Ni SA@FePc. And CO2RR prefers to occur at the raised N centers of NiN4-O2-FePc heterogeneous structure for Ni SA@FePc, which enables facilitated adsorption of *COOH and desorption of CO, and thus accelerated overall reaction kinetics.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Ligand centered electrocatalytic efficient CO2 reduction reaction at low overpotential on single-atom Ni regulated molecular catalyst

Show Author's information Jiazhi Wang1,2, Qi Hao1,3, Haixia Zhong4, Kai Li1, Xinbo Zhang1,2( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
University of Science and Technology of China, Hefei 230026, China
Key Laboratory of Automobile Materials, Ministry of Education, Jilin University, Changchun 130022, China
Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden 01062, Germany

Abstract

Electrochemical CO2 reduction reaction (CO2RR) into value-added chemicals/fuels is crucial for realizing the sustainable carbon cycle while mitigating the energy crisis. However, it is impeded by the relatively high overpotential and low energy efficiency due to the lack of efficient electrocatalysts. Herein, we develop an isolated single-atom Ni catalyst regulated strategy to activate and stabilize the iron phthalocyanine molecule (Ni SA@FePc) toward a highly efficient CO2RR process at low overpotential. The well-defined and homogenous catalytic centers with unique structures confer Ni SA@FePc with a significantly enhanced CO2RR performance compared to single-atom Ni catalyst and FePc molecule and afford the atomic understanding on active sites and catalytic mechanism. As expected, Ni SA@FePc exhibits a high selectivity of more significant Faraday efficiency (≥ 95%) over a wide potential range, a high current density of ~ 252 mA·cm−2 at low overpotential (390 mV), and excellent long-term stability for CO2RR to CO. X-ray absorption spectroscopy measurement and theoretical calculation indicate the formation of NiN4-O2-FePc heterogeneous structure for Ni SA@FePc. And CO2RR prefers to occur at the raised N centers of NiN4-O2-FePc heterogeneous structure for Ni SA@FePc, which enables facilitated adsorption of *COOH and desorption of CO, and thus accelerated overall reaction kinetics.

Keywords: iron phthalocyanine, carbon dioxide reduction reaction, single-atom Ni, molecular catalyst, ultra-low overpotential

References(41)

1

Chu, S.; Cui, Y.; Liu, N. The path towards sustainable energy. Nat. Mater. 2017, 16, 16–22.
DOI Google Scholar
2

Mitchell, S.; Pérez-Ramírez, J. Single atom catalysis: A decade of stunning progress and the promise for a bright future. Nat. Commun. 2020, 11, 4302.
DOI Google Scholar
3

Obama, B. The irreversible momentum of clean energy. Science 2017, 355, 126–129.
DOI Google Scholar
4

Gu, J.; Hsu, C. S.; Bai, L. C.; Chen, H. M.; Hu, X. L. Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO. Science 2019, 364, 1091–1094.
DOI Google Scholar
5

Zheng, T. T.; Jiang, K.; Ta, N.; Hu, Y. F.; Zeng, J.; Liu, J. Y.; Wang, H. T. Large-scale and highly selective CO2 electrocatalytic reduction on nickel single-atom catalyst. Joule 2019, 3, 265–278.
DOI Google Scholar
6

Wu, Y. S.; Jiang, Z.; Lu, X.; Liang, Y. Y.; Wang, H. L. Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 2019, 575, 639–642.
DOI Google Scholar
7

Wang, Y. C.; Xu, L.; Zhan, L. S.; Yang, P. Y.; Tang, S. H.; Liu, M. J.; Zhao, X.; Xiong, Y.; Chen, Z. Y.; Lei, Y. H. Electron accumulation enables Bi efficient CO2 reduction for formate production to boost clean Zn-CO2 batteries. Nano Energy 2022, 92, 106780.
DOI Google Scholar
8

Zhang, X.; Wu, Z. S.; Zhang, X.; Li, L. W.; Li, Y. Y.; Xu, H. M.; Li, X. X.; Yu, X. L.; Zhang, Z. S.; Liang, Y. Y. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 2017, 8, 14675.
DOI Google Scholar
9

Zhong, M.; Tran, K.; Min, Y. M.; Wang, C. H.; Wang, Z. Y.; Dinh, C. T.; De Luna, P.; Yu, Z. Q.; Rasouli, A. S.; Brodersen, P. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 2020, 581, 178–183.
DOI Google Scholar
10

Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Roldan Cuenya, B.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. Nat. Commun. 2017, 8, 944.
DOI Google Scholar
11

Zhang, T. Y.; Han, X.; Yang, H. B.; Han, A. J.; Hu, E. Y.; Li, Y. P.; Yang, X. Q.; Wang, L.; Liu, J. F.; Liu, B. Atomically dispersed nickel(I) on an alloy-encapsulated nitrogen-doped carbon nanotube array for high-performance electrochemical CO2 reduction reaction. Angew. Chem., Int. Ed. 2020, 59, 12055–12061.
DOI Google Scholar
12

Chen, K. J.; Liu, K.; An, P. D.; Li, H. J. W.; Lin, Y. Y.; Hu, J. H.; Jia, C. K.; Fu, J. W.; Li, H. M.; Liu, H. et al. Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction. Nat. Commun. 2020, 11, 4173.
DOI Google Scholar
13

Zhang, X.; Wang, Y.; Gu, M.; Wang, M. Y.; Zhang, Z. S.; Pan, W. Y.; Jiang, Z.; Zheng, H. Z.; Lucero, M.; Wang, H. L. et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction. Nat. Energy 2020, 5, 684–692.
DOI Google Scholar
14

Hou, Y.; Qiu, M.; Kim, M. G.; Liu, P.; Nam, G.; Zhang, T.; Zhuang, X. D.; Yang, B.; Cho, J.; Chen, M. W. et al. Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation. Nat. Commun. 2019, 10, 1392.
DOI Google Scholar
15

Sun, X. H.; Tuo, Y. X.; Ye, C. L.; Chen, C.; Lu, Q.; Li, G. N.; Jiang, P.; Chen, S. H.; Zhu, P.; Ma, M. et al. Phosphorus induced electron localization of single iron sites for boosted CO2 electroreduction reaction. Angew. Chem., Int. Ed. 2021, 60, 23614–23618.
DOI Google Scholar
16

Yang, H. B.; Hung, S. F.; Liu, S.; Yuan, K. D.; Miao, S.; Zhang, L. P.; Huang, X.; Wang, H. Y.; Cai, W. Z.; Chen, R. et al. Atomically dispersed Ni(I) as the active site for electrochemical CO2 reduction. Nat. Energy 2018, 3, 140–147.
DOI Google Scholar
17

Jiang, K.; Siahrostami, S.; Zheng, T. T.; Hu, Y. F.; Hwang, S.; Stavitski, E.; Peng, Y. D.; Dynes, J.; Gangisetty, M.; Su, D. et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction. Energy Environ. Sci. 2018, 11, 893–903.
DOI Google Scholar
18

Jiang, Z. L.; Wang, T.; Pei, J. J.; Shang, H. S.; Zhou, D. N.; Li, H. J.; Dong, J. C.; Wang, Y.; Cao, R.; Zhuang, Z. B. et al. Discovery of main group single Sb–N4 active sites for CO2 electroreduction to formate with high efficiency. Energy Environ. Sci. 2020, 13, 2856–2863.
DOI Google Scholar
19

Lin, L.; Li, H. B.; Yan, C. C.; Li, H. F.; Si, R.; Li, M. R.; Xiao, J. P.; Wang, G. X.; Bao, X. H. Synergistic catalysis over iron-nitrogen sites anchored with cobalt phthalocyanine for efficient CO2 electroreduction. Adv. Mater. 2019, 31, 1903470.
DOI Google Scholar
20

Ren, S. X.; Joulié, D.; Salvatore, D.; Torbensen, K.; Wang, M.; Robert, M.; Berlinguette, C. P. Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell. Science 2019, 365, 367–369.
DOI Google Scholar
21

Ren, W. H.; Tan, X.; Yang, W. F.; Jia, C.; Xu, S. M.; Wang, K. X.; Smith, S. C.; Zhao, C. Isolated diatomic Ni-Fe metal-nitrogen sites for synergistic electroreduction of CO2. Angew. Chem., Int. Ed. 2019, 58, 6972–6976.
DOI Google Scholar
22

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
23

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
24

Wang, V.; Xu, N.; Liu, J. C.; Tang, G.; Geng, W. T. VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput. Phys. Commun. 2021, 267, 108033.
DOI Google Scholar
25

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2021, 100013.
DOI Google Scholar
26

Zhou, H.; Yang, T.; Kou, Z. K.; Shen, L.; Zhao, Y. F.; Wang, Z. Y.; Wang, X. Q.; Yang, Z. K.; Du, J. Y.; Xu, J. et al. Negative pressure pyrolysis induced highly accessible single sites dispersed on 3D graphene frameworks for enhanced oxygen reduction. Angew. Chem., Int. Ed. 2020, 59, 20465–20469.
DOI Google Scholar
27

Zhu, Z. J.; Yin, H. J.; Wang, Y.; Chuang, C. H.; Xing, L.; Dong, M. Y.; Lu, Y. R.; Casillas-Garcia, G.; Zheng, Y. L.; Chen, S. et al. Coexisting single-atomic Fe and Ni sites on hierarchically ordered porous carbon as a highly efficient ORR electrocatalyst. Adv. Mater. 2020, 32, 2004670.
DOI Google Scholar
28

Yang, H. P.; Lin, Q.; Zhang, C.; Yu, X. Y.; Cheng, Z.; Li, G. D.; Hu, Q.; Ren, X. Z.; Zhang, Q. L.; Liu, J. H. et al. Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities. Nat. Commun. 2020, 11, 593.
DOI Google Scholar
29

Chen, Y. J.; Gao, R.; Ji, S. F.; Li, H. J.; Tang, K.; Jiang, P.; Hu, H. B.; Zhang, Z. D.; Hao, H. G.; Qu, Q. Y. et al. Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal–organic frameworks: Enhanced oxygen reduction performance. Angew. Chem., Int. Ed. 2021, 60, 3212–3221.
DOI Google Scholar
30

Yang, Q. H.; Yang, C. C.; Lin, C. H.; Jiang, H. L. Metal–organic framework-derived hollow N-doped porous carbon with ultrahigh concentrations of single Zn atoms for efficient carbon dioxide conversion. Angew. Chem., Int. Ed. 2019, 58, 3511–3515.
DOI Google Scholar
31

Zhang, B. X.; Zhang, J. L.; Shi, J. B.; Tan, D. X.; Liu, L. F.; Zhang, F. Y.; Lu, C.; Su, Z. Z.; Tan, X. N.; Cheng, X. Y. et al. Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction. Nat. Commun. 2019, 10, 2980.
DOI Google Scholar
32

Luo, F.; Roy, A.; Silvioli, L.; Cullen, D. A.; Zitolo, A.; Sougrati, M. T.; Oguz, I. C.; Mineva, T.; Teschner, D.; Wagner, S. et al. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nat. Mater. 2020, 19, 1215–1223.
DOI Google Scholar
33

Zang, W. J.; Sun, T.; Yang, T.; Xi, S. B.; Waqar, M.; Kou, Z. K.; Lyu, Z.; Feng, Y. P.; Wang, J.; Pennycook, S. J. Efficient hydrogen evolution of oxidized Ni–N3 defective sites for alkaline freshwater and seawater electrolysis. Adv. Mater. 2021, 33, 2003846.
DOI Google Scholar
34

Yan, C. C.; Li, H. B.; Ye, Y. F.; Wu, H. H.; Cai, F.; Si, R.; Xiao, J. P.; Miao, S.; Xie, S. H.; Yang, F. et al. Coordinatively unsaturated nickel-nitrogen sites towards selective and high-rate CO2 electroreduction. Energy Environ. Sci. 2018, 11, 1204–1210.
DOI Google Scholar
35

Voiry, D.; Shin, H. S.; Loh, K. P.; Chhowalla, M. Low-dimensional catalysts for hydrogen evolution and CO2 reduction. Nat. Rev. Chem. 2018, 2, 0105.
DOI Google Scholar
36

Kong, X. D.; Ke, J. W.; Wang, Z. Q.; Liu, Y.; Wang, Y. B.; Zhou, W. R.; Yang, Z. W.; Yan, W. S.; Geng, Z. G.; Zeng, J. Co-based molecular catalysts for efficient CO2 reduction via regulating spin states. Appl. Catal. B:Environ. 2021, 290, 120067.
DOI Google Scholar
37

Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts. J. Am. Chem. Soc. 2019, 141, 9664–9672.
DOI Google Scholar
38

Bénisvy, L.; Halut, S.; Donnadieu, B.; Tuchagues, J. P.; Chottard, J. C.; Li, Y. Monomeric iron(II) hydroxo and iron(III) dihydroxo complexes stabilized by intermolecular hydrogen bonding. Inorg. Chem. 2006, 45, 2403–2405.
DOI Google Scholar
39

Hikichi, S.; Ogihara, T.; Fujisawa, K.; Kitajima, N.; Akita, M.; Moro-Oka, Y. Synthesis and characterization of the benzoylformato ferrous complexes with the hindered tris(pyrazolyl)borate ligand as a structural model for mononuclear non-heme iron enzymes. Inorg. Chem. 1997, 36, 4539–4547.
DOI Google Scholar
40

Chen, S. H.; Li, W. H.; Jiang, W. J.; Yang, J. R.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhuang, Z. C.; Chen, M. Z.; Sun, X. H. et al. MOF encapsulating N-heterocyclic carbene-ligated copper single-atom site catalyst towards efficient methane electrosynthesis. Angew. Chem., Int. Ed. 2022, 61, e202114450.
DOI Google Scholar
41

Wang, Y. N.; Zheng, Y.; Han, C.; Chen, W. Surface charge transfer doping for two-dimensional semiconductor-based electronic and optoelectronic devices. Nano Res. 2021, 14, 1682–1697.
DOI Google Scholar
File
12274_2022_4197_MOESM1_ESM.pdf (2.1 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 09 January 2022
Revised: 24 January 2022
Accepted: 25 January 2022
Published: 18 April 2022
Issue date: July 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

H. X. Z. acknowledges funding from the Alexander von Humboldt Foundation. This work was supported by the National Natural Science Foundation of China (No. 21725103), National Key R&D Program of China (No. 2019YFA0705704), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDA21010210), Jilin Province Science and Technology Development Plan Funding Project (No. 20200201079JC), Changchun Science and Technology Development Plan Funding Project (No. 19SS010), Jilin Province Capital Construction Funds Project (No. 2020C026-1), and the K. C. Wong Education Foundation (No. GJTD-2018-09).

Return