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Nano Research 2024, 17(5): 3745-3751 https://doi.org/10.1007/s12274-023-6294-6
Research Article | Issue | Published: 17 November 2023

Low-coordination environment design of single Co atoms for efficient CO2 photoreduction

Show Author's Information Zhentao Ma1,§,  Qingyu Wang1,2,§,  Limin Liu1,§,  Rong-Ao Zhang1,  Qichen Liu1,  Peigen Liu1,  Lihui Wu1,  Chengyuan Liu1,  Yu Bai3,  Yida Zhang1,2( ),  Haibin Pan1( ),  Xusheng Zheng1( )
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
College of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
Experimental Center of Engineering and Material Science, University of Science and Technology of China, Hefei 230026, China

§ Zhentao Ma, Qingyu Wang, and Limin Liu contributed equally to this work.

Keywords:
photocatalytic CO2 reduction, electron transfer, CO2 adsorption, single atoms, low-coordination
Topics:
Photocatalysis
Cite this article:
Ma Z, Wang Q, Liu L, et al. Low-coordination environment design of single Co atoms for efficient CO2 photoreduction. Nano Research, 2024, 17(5): 3745-3751. https://doi.org/10.1007/s12274-023-6294-6
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Abstract Full text Electronic supplementary material About this article

Photocatalytic carbon dioxide (CO2) to carbon monoxide (CO) offers a promising way for both alleviating the greenhouse effect and meeting the industrial demand. Herein, we constructed a Co single-atom catalyst with intentional low-coordination environment design on porous ZnO (denoted as Co1/ZnO). Impressively, Co1/ZnO exhibited a remarkable activity with a CO yield rate of 22.25 mmol·g−1·h−1 and a selectivity of 80.2% for CO2 photoreduction reactions under visible light. The incorporation of single Co atoms provided an additional photo-generated electron transfer channel, which suppressed the carrier recombination of photocatalysts. Moreover, the unsaturated Co active sites were capable to adsorb CO2 molecule spontaneously, thus facilitating the activation of CO2 molecule during CO2 reduction course.


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Electronic supplementary material
About this article

Low-coordination environment design of single Co atoms for efficient CO2 photoreduction

Show Author's information Zhentao Ma1,§, Qingyu Wang1,2,§, Limin Liu1,§, Rong-Ao Zhang1, Qichen Liu1, Peigen Liu1, Lihui Wu1, Chengyuan Liu1, Yu Bai3, Yida Zhang1,2( ), Haibin Pan1( ), Xusheng Zheng1( )
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
College of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
Experimental Center of Engineering and Material Science, University of Science and Technology of China, Hefei 230026, China

§ Zhentao Ma, Qingyu Wang, and Limin Liu contributed equally to this work.

Abstract

Photocatalytic carbon dioxide (CO2) to carbon monoxide (CO) offers a promising way for both alleviating the greenhouse effect and meeting the industrial demand. Herein, we constructed a Co single-atom catalyst with intentional low-coordination environment design on porous ZnO (denoted as Co1/ZnO). Impressively, Co1/ZnO exhibited a remarkable activity with a CO yield rate of 22.25 mmol·g−1·h−1 and a selectivity of 80.2% for CO2 photoreduction reactions under visible light. The incorporation of single Co atoms provided an additional photo-generated electron transfer channel, which suppressed the carrier recombination of photocatalysts. Moreover, the unsaturated Co active sites were capable to adsorb CO2 molecule spontaneously, thus facilitating the activation of CO2 molecule during CO2 reduction course.

Keywords: photocatalytic CO2 reduction, electron transfer, CO2 adsorption, single atoms, low-coordination

References(55)

[1]

Ran, J. R.; Jaroniec, M.; Qiao, S. Z. Cocatalysts in semiconductor-based photocatalytic CO2 reduction: Achievements, challenges, and opportunities. Adv. Mater. 2018, 30, 1704649.
DOI Google Scholar
[2]

Sun, Z. Y.; Talreja, N.; Tao, H. C.; Texter, J.; Muhler, M.; Strunk, J.; Chen, J. F. Catalysis of carbon dioxide photoreduction on nanosheets: Fundamentals and challenges. Angew. Chem., Int. Ed. 2018, 57, 7610–7627.
DOI Google Scholar
[3]

Yang, P. J.; Zhuzhang, H. Y.; Wang, R. R.; Lin, W.; Wang, X. C. Carbon vacancies in a melon polymeric matrix promote photocatalytic carbon dioxide conversion. Angew. Chem., Int. Ed. 2019, 58, 1134–1137.
DOI Google Scholar
[4]

Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, 15, 7806–7839.
DOI Google Scholar
[5]
Wang, L. G.; Wu, J. B.; Wang, S. W.; Liu, H.; Wang, Y.; Wang, D. S. The reformation of catalyst: From a trial-and-error synthesis to rational design. Nano Res., in press, DOI: 10.1007/s12274-023-6037-8.
DOI
[6]

Shen, J.; Wang, D. S. How to select heterogeneous CO2 reduction electrocatalyst. Nano Res. Energy 2024, 3, e9120096.
DOI Google Scholar
[7]

Xiang, Y. Z.; Kruse, N. Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins. Nat. Commun. 2016, 7, 13058.
DOI Google Scholar
[8]

Ai, H. J.; Zhao, F. Q.; Geng, H. Q.; Wu, X. F. Palladium-catalyzed thiocarbonylation of alkenes toward linear thioesters. ACS Catal. 2021, 11, 3614–3619.
DOI Google Scholar
[9]

Peng, J. B.; Geng, H. Q.; Wu, X. F. The chemistry of CO: Carbonylation. Chem 2019, 5, 526–552.
DOI Google Scholar
[10]

Jahangiri, H.; Bennett, J.; Mahjoubi, P.; Wilson, K.; Gu, S. A review of advanced catalyst development for Fischer–Tropsch synthesis of hydrocarbons from biomass derived syn-gas. Catal. Sci. Technol. 2014, 4, 2210–2229.
DOI Google Scholar
[11]

Yang, H. L.; Zhang, D. D.; Luo, Y.; Yang, W. X.; Zhan, X. Q.; Yang, W. Y.; Hou, H. L. Highly efficient and selective visible-light driven photoreduction of CO2 to CO by metal–organic frameworks-derived Ni-Co-O porous microrods. Small 2022, 18, 2202939.
DOI Google Scholar
[12]

Zhong, W. F.; Sa, R. J.; Li, L. Y.; He, Y. J.; Li, L. Y.; Bi, J. H.; Zhuang, Z. Y.; Yu, Y.; Zou, Z. G. A covalent organic framework bearing single Ni sites as a synergistic photocatalyst for selective photoreduction of CO2 to CO. J. Am. Chem. Soc. 2019, 141, 7615–7621.
DOI Google Scholar
[13]

Huang, Y. H.; Wang, K.; Guo, T.; Li, J.; Wu, X. Y.; Zhang, G. K. Construction of 2D/2D Bi2Se3/g-C3N4 nanocomposite with high interfacial charge separation and photo-heat conversion efficiency for selective photocatalytic CO2 reduction. Appl. Catal. B: Environ. 2020, 277, 119232.
DOI Google Scholar
[14]

Xiong, Y.; Dong, J. C.; Huang, Z. Q.; Xin, P. Y.; Chen, W. X.; Wang, Y.; Li, Z.; Jin, Z.; Xing, W.; Zhuang, Z. B. et al. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 2020, 15, 390–397.
DOI Google Scholar
[15]
Gan, T.; Wang, D. S. Atomically dispersed materials: Ideal catalysts in atomic era. Nano Res., in press, DOI: 10.1007/s12274-023-5700-4.
DOI
[16]

Li, M. H.; Zhang, C. C.; Tang, Y.; Chen, Q. L.; Li, W.; Han, Z.; Chen, S. Y.; Lv, C. C.; Yan, Y. J.; Zhang, Y. et al. Environment molecules boost the chemoselective hydrogenation of nitroarenes on cobalt single-atom catalysts. ACS Catal. 2022, 12, 11960–11973.
DOI Google Scholar
[17]

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. 2021, 133, 23806–23810.
DOI Google Scholar
[18]

Song, Z. X.; Zhang, L.; Doyle-Davis, K.; Fu, X. Z.; Luo, J. L.; Sun, X. L. Recent advances in MOF-derived single atom catalysts for electrochemical applications. Adv. Energy Mater. 2020, 10, 2001561.
DOI Google Scholar
[19]

Wang, L. G.; Liu, H.; Zhuang, J. H.; Wang, D. S. Small-scale big science: From Nano- to atomically dispersed catalytic materials. Small Sci. 2022, 2, 2200036.
DOI Google Scholar
[20]

Tan, H. Y.; Wang, J. L.; Lin, S. C.; Kuo, T. R.; Chen, H. M. Dynamic coordination structure evolutions of atomically dispersed metal catalysts for electrocatalytic reactions. Adv. Mater. Interfaces 2023, 10, 2202050.
DOI Google Scholar
[21]

Xu, H. X.; Cheng, D. J.; Cao, D. P.; Zeng, X. C. A universal principle for a rational design of single-atom electrocatalysts. Nat. Catal. 2018, 1, 339–348.
DOI Google Scholar
[22]

Shan, J. Q.; Ye, C.; Jiang, Y. L.; Jaroniec, M.; Zheng, Y.; Qiao, S. Z. Metal–metal interactions in correlated single-atom catalysts. Sci. Adv. 2022, 8, eabo0762.
DOI Google Scholar
[23]
Li, R. Z.; Zhao, J.; Liu, B. Z.; Wang, D. S. Atomic distance engineering in metal catalysts to regulate catalytic performance. Adv. Mater., in press, DOI: 10.1002/adma.202308653.
DOI
[24]

Zhang, Y.; Jiao, L.; Yang, W. J.; Xie, C. F.; Jiang, H. L. Rational fabrication of low-coordinate single-atom Ni electrocatalysts by MOFs for highly selective CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 7607–7611.
DOI Google Scholar
[25]

Ding, R.; Chen, Y. W.; Li, X. K.; Rui, Z. Y.; Hua, K.; Wu, Y. K.; Duan, X.; Wang, X. B.; Li, J.; Liu, J. G. Atomically dispersed, low-coordinate Co–N sites on carbon nanotubes as inexpensive and efficient electrocatalysts for hydrogen evolution. Small 2022, 18, 2105335.
DOI Google Scholar
[26]

Jiang, M. P.; Huang, K. K.; Liu, J. H.; Wang, D.; Wang, Y.; Wang, X.; Li, Z. D.; Wang, X. Y.; Geng, Z. B.; Hou, X. Y. et al. Magnetic-field-regulated TiO2 {100} facets: A strategy for C–C coupling in CO2 photocatalytic conversion. Chem 2020, 6, 2335–2346.
DOI Google Scholar
[27]

Zheng, W. Z.; Yang, J.; Chen, H. Q.; Hou, Y.; Wang, Q.; Gu, M.; He, F.; Xia, Y.; Xia, Z.; Li, Z. J. et al. Atomically defined undercoordinated active sites for highly efficient CO2 electroreduction. Adv. Funct. Mater. 2020, 30, 1907658.
DOI Google Scholar
[28]

Zheng, K.; Wu, Y.; Zhu, J. C.; Wu, M. Y.; Jiao, X. C.; Li, L.; Wang, S. M.; Fan, M. H.; Hu, J.; Yan, W. S. et al. Room-temperature photooxidation of CH4 to CH3OH with nearly 100% selectivity over hetero-ZnO/Fe2O3 porous nanosheets. J. Am. Chem. Soc. 2022, 144, 12357–12366.
DOI Google Scholar
[29]

Hu, C. L.; Zhang, L.; Zhao, Z. J.; Luo, J.; Shi, J.; Huang, Z. Q.; Gong, J. L. Edge sites with unsaturated coordination on core–shell Mn3O4@Mn x Co3− x O4 nanostructures for electrocatalytic Water Oxidation. Adv. Mater. 2017, 29, 1701820.
DOI Google Scholar
[30]

Li, Y. H.; Kidkhunthod, P.; Zhou, Y. T.; Wang, X.; Lee, J. M. Dense heterointerfaces and unsaturated coordination synergistically accelerate electrocatalysis in Pt/Pt5P2 porous nanocages. Adv. Funct. Mater. 2022, 32, 2205985.
DOI Google Scholar
[31]

Han, B.; Ou, X. W.; Deng, Z. Q.; Song, Y.; Tian, C.; Deng, H.; Xu, Y. J.; Lin, Z. Nickel metal-organic framework monolayers for photoreduction of diluted CO2: Metal-node-dependent activity and selectivity. Angew. Chem., Int. Ed. 2018, 57, 16811–16815.
DOI Google Scholar
[32]

Wang, S. B.; Guan, B. Y.; Lou, X. W. Rationally designed hierarchical N-doped carbon@NiCo2O4 double-shelled nanoboxes for enhanced visible light CO2 reduction. Energy Environ. Sci. 2018, 11, 306–310.
DOI Google Scholar
[33]

Zhong, H.; Sa, R. J.; Lv, H. W.; Yang, S. L.; Yuan, D. Q.; Wang, X. C.; Wang, R. H. Covalent organic framework hosting metalloporphyrin-based carbon dots for visible-light-driven selective CO2 reduction. Adv. Funct. Mater. 2020, 30, 2002654.
DOI Google Scholar
[34]

Gao, C.; Meng, Q. Q.; Zhao, K.; Yin, H. J.; Wang, D. W.; Guo, J.; Zhao, S. L.; Chang, L.; He, M.; Li, Q. X. et al. Co3O4 hexagonal platelets with controllable facets enabling highly efficient visible-light photocatalytic reduction of CO2. Adv. Mater. 2016, 28, 6485–6490.
DOI Google Scholar
[35]

Geng, Z. G.; Kong, X. D.; Chen, W. W.; Su, H. Y.; Liu, Y.; Cai, F.; Wang, G. X.; Zeng, J. Oxygen vacancies in ZnO nanosheets enhance CO2 electrochemical reduction to CO. Angew. Chem., Int. Ed. 2018, 57, 6054–6059.
DOI Google Scholar
[36]

Wang, Y. F.; Zheng, Z.; Wang, J. Q.; Liu, X. Y.; Ren, J. Z.; An, C. B.; Zhang, S. Q.; Hou, J. H. New method for preparing ZnO layer for efficient and stable organic solar cells. Adv. Mater. 2023, 35, 2208305.
DOI Google Scholar
[37]

Zhang, L. W.; Long, R.; Zhang, Y. M.; Duan, D. L.; Xiong, Y. J.; Zhang, Y. J.; Bi, Y. P. Direct observation of dynamic bond evolution in single-atom Pt/C3N4 catalysts. Angew. Chem. 2020, 132, 6283–6288.
DOI Google Scholar
[38]

Li, X. Y.; Zhuang, Z. C.; Chai, J.; Shao, R. W.; Wang, J. H.; Jiang, Z. L.; Zhu, S. W.; Gu, H. F.; Zhang, J.; Ma, Z. T. et al. Atomically strained metal sites for highly efficient and selective photooxidation. Nano Lett. 2023, 23, 2905–2914.
DOI Google Scholar
[39]

Wang, G.; Wu, Y.; Li, Z. J.; Lou, Z. Z.; Chen, Q. Q.; Li, Y. F.; Wang, D. S.; Mao, J. J. Engineering a copper single-atom electron bridge to achieve efficient photocatalytic CO2 conversion. Angew. Chem., Int. Ed. 2023, 62, e202218460.
DOI Google Scholar
[40]

Hirsch, O.; Kvashnina, K. O.; Luo, L.; Süess, M. J.; Glatzel, P.; Koziej, D. High-energy resolution X-ray absorption and emission spectroscopy reveals insight into unique selectivity of La-based nanoparticles for CO2. Proc. Natl. Acad. Sci. USA 2015, 112, 15803–15808.
DOI Google Scholar
[41]

Yu, S. W.; Tobin, J. G.; Crowhurst, J. C.; Sharma, S.; Dewhurst, J. K.; Olalde-Velasco, P.; Yang, W. L.; Siekhaus, W. J. f–f origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations. Phys. Rev. B 2011, 83, 165102.
DOI Google Scholar
[42]

Zhang, Y. D.; Hou, T. T.; Xu, Q.; Wang, Q. Y.; Bai, Y.; Yang, S. K.; Rao, D. W.; Wu, L. H.; Pan, H. B.; Chen, J. F. et al. Dual-metal sites boosting polarization of nitrogen molecules for efficient nitrogen photofixation. Adv. Sci. 2021, 8, 2100302.
DOI Google Scholar
[43]

Liras, M.; Barawi, M.; de la Pena O'Shea, V. A. Hybrid materials based on conjugated polymers and inorganic semiconductors as photocatalysts: From environmental to energy applications. Chem. Soc. Rev. 2019, 48, 5454–5487.
DOI Google Scholar
[44]

Zhao, D. M.; Dong, C. L.; Wang, B.; Chen, C.; Huang, Y. C.; Diao, Z. D.; Li, S. Z.; Guo, L. J.; Shen, S. H. Synergy of dopants and defects in graphitic carbon nitride with exceptionally modulated band structures for efficient photocatalytic oxygen evolution. Adv. Mater. 2019, 31, 1903545.
DOI Google Scholar
[45]

Li, S.; Liu, Y. X.; Feng, K.; Li, C. Y.; Xu, J. B.; Lu, C.; Lin, H. P.; Feng, Y.; Ma, D.; Zhong, J. High valence state sites as favorable reductive centers for high-current-density water splitting. Angew. Chem., Int. Ed. 2023, 62, e202308670.
DOI Google Scholar
[46]

Zhang, Y. D.; Wang, Q. Y.; Yang, S. K.; Wang, H. W.; Rao, D. W.; Chen, T.; Wang, G. M.; Lu, J. L.; Zhu, J. F.; Wei, S. Q. et al. Tuning the interaction between ruthenium single atoms and the second coordination sphere for efficient nitrogen photofixation. Adv. Funct. Mater. 2022, 32, 2112452.
DOI Google Scholar
[47]

Wang, Q. Y.; Xiao, Y.; Yang, S. K.; Zhang, Y. D.; Wu, L. H.; Pan, H. B.; Rao, D. W.; Chen, T.; Sun, Z. H.; Wang, G. M. et al. Monitoring electron flow in nickel single-atom catalysts during nitrogen photofixation. Nano Lett. 2022, 22, 10216–10223.
DOI Google Scholar
[48]
Wang, Q. Y.; Zhang, Y. D.; Lin, M. X.; Wang, H. W.; Bai, Y.; Liu, C. Y.; Lu, J. L.; Luo, Q. Q.; Wang, G. M.; Jiang, H. L. et al. Photoinduced metastable asymmetric Cu single atoms for photoreduction of CO2 to ethylene. Adv. Energy Mater., in press, DOI: 10.1002/aenm.202302692.
DOI
[49]

Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans, J.; Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.; Sanz, J. F. et al. Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2. Science 2014, 345, 546–550.
DOI Google Scholar
[50]

Deng, X. Y.; Verdaguer, A.; Herranz, T.; Weis, C.; Bluhm, H.; Salmeron, M. Surface chemistry of Cu in the presence of CO2 and H2O. Langmuir 2008, 24, 9474–9478.
DOI Google Scholar
[51]

Jiao, X. C.; Li, X. D.; Jin, X. Y.; Sun, Y. F.; Xu, J. Q.; Liang, L.; Ju, H. X.; Zhu, J. F.; Pan, Y.; Yan, W. S. et al. Partially oxidized SnS2 atomic layers achieving efficient visible-light-driven CO2 reduction. J. Am. Chem. Soc. 2017, 139, 18044–18051.
DOI Google Scholar
[52]

Liu, P. G.; Huang, Z. X.; Gao, X. P.; Hong, X.; Zhu, J. F.; Wang, G. M.; Wu, Y. E.; Zeng, J.; Zheng, X. S. Synergy between palladium single atoms and nanoparticles via hydrogen spillover for enhancing CO2 photoreduction to CH4. Adv. Mater. 2022, 34, 2200057.
DOI Google Scholar
[53]

Li, X. Y.; Ding, Q.; Liu, J.; Dong, L. H.; Qin, X. Z.; Zhou, L. Q.; Zhao, Z. X.; Ji, H. B.; Zhang, S.; Chai, K. G. One-step ethylene purification from ternary mixtures by an ultramicroporous material with synergistic binding centers. Mater. Horiz. 2023, 10, 4463–4469.
DOI Google Scholar
[54]

Yi, J. D.; Xie, R. K.; Xie, Z. L.; Chai, G. L.; Liu, T. F.; Chen, R. P.; Huang, Y. B.; Cao, R. Highly selective CO2 electroreduction to CH4 by in situ generated Cu2O single-type sites on a conductive MOF: Stabilizing key intermediates with hydrogen bonding. Angew. Chem., Int. Ed. 2020, 59, 23641–23648.
DOI Google Scholar
[55]

Ning, S. B.; Ou, H. H.; Li, Y. G.; Lv, C. C.; Wang, S. F.; Wang, D. S.; Ye, J. H. Co0–Co δ + interface double-site-mediated C–C coupling for the photothermal conversion of CO2 into light olefins. Angew. Chem., Int. Ed. 2023, 62, e202302253.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 07 October 2023
Revised: 26 October 2023
Accepted: 27 October 2023
Published: 17 November 2023
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 1222508 and U1932213), the Fundamental Research Funds for the Central Universities (No. WK2060000016), the USTC Research Funds of the Double First-Class Initiative (No. YD2310002005), and the Youth Innovation Promotion Association CAS (No. 2020454). The authors thank the beamline BL11B in SSRF, BL10B, BL04B, and BL01B in NSRL for synchrotron radiation measurements.

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