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Progress in Chemistry 2022, Vol. 34 Issue (4): 983-991 DOI: 10.7536/PC210122 Previous Articles   Next Articles

• Review •

The progress on Electrochemical CO2-to-Formate Conversion by p-Block Metal Based Catalysts

Fengshou Yu(), Jiayu Zhan, Lu-Hua Zhang   

  1. National Local Joint Engineering Laboratory for Energy Conservation of Chemical Process Integration and Resources Utilization, School of Chemical Engineering and Technology, Hebei University of Technology,Tianjin 300131, China
  • Received: Revised: Online: Published:
  • Contact: Fengshou Yu
  • Supported by:
    National Natural Science Foundation of China(21905073); National Natural Science Foundation of China(22008048); Hundred Talents Project of Hebei Province(E2019050015)
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Electrochemical CO2 reduction to value added chemical feedstocks and fuels driven by renewable electricity gives a promising and appealing approach to address the global challenges in energy and sustainability and eventually close the anthropogenic carbon cycle. The most crucial step for this conversion is to develop robust electrocatalysts promoting adsorption of CO2 molecule and subsequent activation with low energy barriers. Due to the different overpotentials and electron transfer amount needed for various reduction products, there is huge gap of producing price among a variety of products. Based on recent research, formic acid (or formate) is one of the most economically viable and useful reduction product in a couple of chemical processes. In this paper, starting with fundamental understanding of reaction mechanism, we review the main progress of p-block post-transition metal (e.g., Sn, Bi, and In) based electrocatalysts for electrochemical CO2 reduction to produce formic acid. In addition, strategies to facilitate the catalytic performance of CO2 to formic acid) conversion including reduction conversion of metal oxides, morphology control, doping and alloying to modulate the electronic structure are also be briefly reviewed. Finally, we summarize the existing challenges and present perspectives for the future development of this exciting field.

Contents

1 Introduction

2 The mechanism of CO2-to-formate conversion

3 p-block metal-based catalysts

3. 1 Sn-based catalysts

3. 2 Bi-based catalysts

3.3 In-based catalysts

4 Conclusion and outlook

Key words: carbon dioxide, electrochemical, reduction, catalysis, formic acid, p-block metals
Fig. 1 Market price of select CO2 recycling products as a function of energy content. Lines represent minimum energy and CO2 costs[10]. Copyright 2020, Wiley-VCH
Table 1 The performance of various p-block metal-based electrocatalysts for CO2-to-HCOOH conversion
Electrocatalysts Electrolyte Formate FEmax j at FEmax (mA·cm-2) ref
Sn 0.1 M KHCO3 88.4%@-1.48 V vs NHE 5.0 23
Sn/SnO2 0.1 M KHCO3 82.1%@-1.6 V vs SCE 22.9 25
np-Sn/SnO2 0.5 M NaHCO3 80%@-1.1 V vs RHE 16 26
Sn/CP-UPED 0.1 M KHCO3 88.8%@-1.7 V vs Ag/AgCl 6.5 27
OE-Sn 0.1 M KHCO3 85%@-1.8 V vs Ag/AgCl 5.4 28
SnO2/CC 3 M KCl 87%@-1.6 V vs Ag/AgCl 45 34
Sn-pNWs 0.1 M KHCO3 80.1%@-1.0 V vs RHE 4.806 35
Sn(S)/Au 0.1 M KHCO3 93.3%@-0.75 V vs RHE 55 36
SnO2/CC 0.1 M NaHCO3 93%@-1.8 V vs SCE 55 41
SnO2/CP 0.1 M NaHCO3 90%@-1.8 V vs SCE - 42
Bi-SnO/Cu foam 0.1 M KHCO3 93%@-1.7 V vs Ag/AgCl 12 48
CuSn3 0.1 M KHCO3 95%@-0.5 V vs RHE 33 53
PdSn/C 0.5 M KHCO3 99%@-0.43 V vs RHE - 19
Ag76Sn24 - 87.2%@-0.9 V versus RHE - 55
Bi dendrite 0.5 M KHCO3 89%@-0.74 V vs RHE 2.7 65
Bi flake 0.1 M KHCO3 99%@-0.6 V vs RHE - 66
Bi Nanosheets 0.1 M KHCO3 86%@-1.1 V vs RHE 16.5 67
Commercial Bi 0.5 M NaHCO3 90%@-1.74 V vs SCE 24 68
BiBrO templated 2 M KHCO3 90% 200 69
BiOBr 0.1 M KHCO3 99%@-0.95 V vs RHE - 70
Bi2O3NSs@MCCM 0.1 M KHCO3 93.8%@-1.256 V vs RHE - 71
Cu-Bi 0.1 M KHCO3 90%@-0.8 V vs RHE - 73
In NPS 0.5 M K2SO4 100% - 76
In 0.5 M KHCO3 86%@-0.86 V vs RHE 5.8 80
Fig. 2 Possible reaction pathways for electrochemical CO2 reduction to formate, CO, and other products
Fig. 3 SEM images of porous SnO2 nanosheets on carbon cloth (a), and the current density (b) and corresponding FE (c) for reduction products at various potentials[34]. Copyright 2017, Wiley-VCH. The HRTEM image of the Sn quantum sheets confined in graphene (d) and Linear sweep voltammetric curves (e) and Faradaic efficiencies (f) for formate formation[42]. Copyright 2016, Nature. The structure of Ag-Sn with ultrathin partially oxidized SnO2 shell (g), and the corresponding HAADF-STEM image (h) and electron energy loss spectroscopy (EELS) mappings (i)[55]. Copyright 2017, American Chemical Society
Fig. 4 (a) SEM image of BiOI. (b) potential-dependent Faradaic efficiencies of HCOO-, CO, and H2 on Bi nanosheet in comparison with the Faradaic efficiency of HCOO- on commercial Bi nanopowder[68]. Copyright 2018, Nature. (c) STEM image and schematic representation of BiOx/C. (d) Faradic efficiencies of BiOx/C for the formation of HCOO-, H2, and CO[72]. Copyright 2018, American Chemical Society
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