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Cobalt-Based Cocatalysts for Photocatalytic CO2 Reduction

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Abstract

Conversion of carbon dioxide (CO2) into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization. Although various types of semiconductor materials have been intensively explored, some severe issues, such as rapid charge recombination and sluggish redox reaction kinetics, remain. In this regard, cocatalyst modification by trapping charges and boosting surface reactions is one of the most efficient strategies to improve the efficiency of semiconductor photocatalysts. This review focuses on recent advances in CO2 photoreduction over cost-effective and earth-abundant cobalt (Co)-based cocatalysts, which are competitive candidates of noble metals for practical applications. First, the functions of Co-based cocatalysts for promoting photocatalytic CO2 reduction are briefly discussed. Then, different kinds of Co-based cocatalysts, including cobalt oxides and hydroxides, cobalt nitrides and phosphides, cobalt sulfides and selenides, Co single-atom, and Co-based metal–organic frameworks (MOFs), are summarized. The underlying mechanisms of these Co-based cocatalysts for facilitating CO2 adsorption–activation, boosting charge separation, and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations. In addition, the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO2 reduction is highlighted in some selected examples. Finally, the challenges and future perspectives on constructing more efficient Co-based cocatalysts for practical applications are proposed.

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Fig. 1
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Fig. 3

Reproduced with permission from Ref. [85]. Copyright © 2016 Royal Society of Chemistry. d Density functional theory (DFT) calculation of the adsorption and reduction of CO2 on Co3O4 surfaces, and free energy diagram describing the COOH* intermediate from CO2 reduction to CO on the {111} and {112} surfaces of Co3O4 hexagonal platelets. Reproduced with permission from Ref. [82]. Copyright © 2016 Wiley–VCH. e Electron paramagnetic resonance (EPR) spectra, f photocatalytic activities (λ ≥ 420 nm, 1 h), g TOF values, and h reaction mechanism of the CO2 reduction over OV–Co3O4. Reproduced with permission from Ref. [94]. Copyright © 2022 Elsevier

Fig. 4

Reproduced with permission from Ref. [76]. Copyright © 2021 American Chemical Society. d Photocatalytic CO and O2 production rates of CdS, 0.2-Co(OH)2/CdS, 0.5-Co(OH)2/CdS, and 1-Co(OH)2/CdS within 4 h. e CO, O2, H2, and CH4 production rates of CdS and 0.5-Co(OH)2/CdS. Reproduced with permission from Ref. [97]. Copyright © 2021 Royal Society of Chemistry

Fig. 5
Fig. 6

Reproduced with permission from Ref. [107]. Copyright © 2021 Royal Society of Chemistry. d Illustration of the synthetic process of hierarchical FeCoS2–CoS2 DSNTs, e scanning electron microscopy image of FeCoS2–CoS2 DSNTs, f CO2 photoreduction performance of different samples, and g CO2 adsorption isotherms of FeCoS2–CoS2 DSNTs at 0 ℃. Reproduced with permission from Ref. [109]. Copyright © 2020 Wiley–VCH

Fig. 7

Reproduced with permission from Ref. [111]. Copyright © 2020 Royal Society of Chemistry. d Photocatalytic CO2RR activity under various conditions, and e atomic force microscopy image of Co0.85Se nanosheets. Reproduced with permission from Ref. [110]. Copyright © 2018 Elsevier

Fig. 8

Reproduced with permission from Ref. [180]. Copyright © 2016 Royal Society of Chemistry. Crystal structure of c CoP. Reproduced with permission from Ref. [185]. Copyright © 2016 Royal Society of Chemistry

Fig. 9

Reproduced with permission from Ref. [102]. Copyright © 2021 Elsevier. e CO2 photoreduction activity over Co2N/BiOBr, f free energy diagrams of the CO2‒CO conversion over Co2N and BiOBr. Reproduced with permission from Ref. [74]. Copyright © 2021 Elsevier

Fig. 10

Reproduced with permission from Ref. [105]. Copyright © 2021 Wiley–VCH. e Diagram of the CoP@NC synthetic process, f in situ room-temperature PL spectra, and g time-resolved PL spectra of the Ru solution in the absence/presence of CoP or CoP@NC. Reproduced with permission from Ref. [106]. Copyright © 2021 Wiley–VCH. h Relative energy change diagram for the CO2 reduction to CO catalyzed by CoP in the system containing a proton donor and i yields of CO and H2. Reproduced with permission from Ref. [103]. Copyright © 2018 Wiley–VCH

Fig. 11

Reproduced with permission from Ref. [75]. Copyright © 2019 Nature Publishing Group. c Comparison of the catalytic performances between W18O49 and W18O49@Co, and Mott − Schottky plots of d W18O49 and e W18O49@Co. Reproduced with permission from Ref. [118]. Copyright © 2021 American Chemical Society

Fig. 12

Reproduced with permission from Ref. [117]. Copyright © 2021 Elsevier. d PL spectra of [Ru(bpy)3]Cl2·6H2O and [Ru(bpy)3]Cl2·6H2O + Co-SA@SP-800, e CO and H2 yields of the M-SA@SP-800 (M = Fe, Ni, and Cu), and f CO and H2 yield rates from the CO2 photoreduction under various reaction conditions. Reproduced with permission from Ref. [116]. Copyright © 2021 Royal Society of Chemistry

Fig. 13

Reproduced with permission from Ref. [208]. Copyright © 2021 Springer. b Chemical structure of Co-ZIF-9. Ball-and-stick representation of the second building units showing the coordination environment around cobalt (left) and packing diagram of Co-ZIF-9 (right). Reproduced with permission from Ref. [123]. Copyright © 2014 Wiley–VCH

Fig. 14

Reproduced with permission from Ref. [130]. Copyright © 2018 Royal Society of Chemistry. f Comparison of the photocurrent–potential curves of different samples. Reproduced with permission from Ref. [126]. Copyright © 2016 Royal Society of Chemistry. g Photocatalytic production of CO and H2 catalyzed by MOF-Cu, MOF-Co, and MOF-Ni. Reproduced with permission from Ref. [132]. Copyright © 2019 American Chemical Society

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Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (Nos. 21905049 and 22178057), the Natural Science Foundation of Fujian Province (Nos. 2020J01201 and 2021J01197), the Research Foundation of the Academy of Carbon Neutrality of Fujian Normal University (TZH2022-07), and the Award Program for Minjiang Scholar Professorship.

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  1. College of Environmental and Resource Sciences, College of Carbon Neutral Modern Industry, Fujian Key Laboratory of Pollution Control and Resource Reuse, Fujian Normal University, Fuzhou, 350007, China

    Mengqing Li, Lijuan Shen & Min-Quan Yang

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Li, M., Shen, L. & Yang, MQ. Cobalt-Based Cocatalysts for Photocatalytic CO2 Reduction. Trans. Tianjin Univ. 28, 506–532 (2022). https://doi.org/10.1007/s12209-022-00350-x

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