Rational design of bismuth-based catalysts for electrochemical CO2 reduction

doi:10.1016/S1872-2067(22)64132-9

Abstract

Abstract:

Sustainable conversion of carbon dioxide (CO₂) to high value-added chemicals and fuels is a promising solution to solve the problem of excessive CO₂ emissions and alleviate the shortage of fossil fuels, maintaining the balance of the carbon cycle in nature. The development of catalytic system is of great significance to improve the efficiency and selectivity for electrochemical CO₂ conversion. In particular, bismuth (Bi) based catalysts are the most promising candidates, while confronting challenges. This review aims to elucidate the fundamental issues of efficient and stable Bi-based catalysts, constructing a bridge between the category, synthesis approach and electrochemical performance. In this review, the categories of Bi-based catalysts are firstly introduced, such as metals, alloys, single atoms, compounds and composites. Followed by the statement of the reliable and versatile synthetic approaches, the representative optimization strategies, such as morphology manipulation, defect engineering, component and heterostructure regulation, have been highlighted in the discussion, paving in-depth insight upon the design principles, reaction activity, selectivity and stability. Afterward, in situ characterization techniques will be discussed to illustrate the mechanisms of electrochemical CO₂ conversion. In the end, the challenges and perspectives are also provided, promoting a systematic understanding in terms of the bottleneck and opportunities in the field of electrochemical CO₂ conversion.

Key words: Bi-based catalysts, Electrochemical CO₂ conversion, Design principle, Reaction activity, In situ characterization technique

Bo Zhang, Yunzhen Wu, Panlong Zhai, Chen Wang, Licheng Sun, Jungang Hou. Rational design of bismuth-based catalysts for electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2022, 43(12): 3062-3088.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64132-9

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Figures/Tables 23

Fig. 1. Schematic illustration of Bi-based catalysts for electrochemical CO2 conversion.

Fig. 2. The reaction pathways of CPET.

Fig. 3. The reaction pathways of SPET.

Fig. 4. The reaction pathways of hydride.

Fig. 5. (a) The proposed formation mechanisms of Bi-SAs-NS/C catalyst. Reprinted with permission from Ref. [65]. Copyright 2021, Springer Nature. (b,c) Magnified HAADF-STEM images, (d) Energy dispersive X-ray spectroscopy (EDS) elemental mapping of Bi SACs/NC. Reprinted with permission from Ref. [66]. Copyright 2019, American Chemical Society. (e,f) Magnified HAADF-STEM images of Bi SAs/NC; (g) The corresponding intensity profiles along the line X-Y in (c). Reprinted with permission from Ref. [67]. Copyright 2020, Royal Society of Chemistry.

Fig. 6. (a) Schematic illustration of Bi nanoparticles with grain boundary. Reprinted with permission from Ref. [86]. Copyright 2020, Springer Nature. (b) STEM-EDS elemental mapping of bismuth nitrate nanosheet. (c) TEM of nanosheet. (d,e) TEM and high-resolution TEM images of in situ reduced metallic 2D-Bi nanosheets. Reprinted with permission from Ref. [87]. Copyright 2019, Springer Nature. (f-h) SEM and STEM-HAADF images of Bi2O3 nanotube. Reprinted with permission from Ref. [75]. Copyright 2019, Springer Nature.

Fig. 7. (a) The flow chart of the experimental procedures. (b,c) Bi-Sn nano-alloys for photocatalytic dye degradation and electrochemical CO2 reduction. (d) Bi-Sn binary alloy phase diagram. Reprinted with permission from Ref. [99]. Copyright 2019, Springer Nature. (e,f) Calculated reaction energy profiles for CO2RR to form CO (top) and HCOOH (bottom) on Sn (101) surface and Bi-Sn (101) surface. Reprinted with permission from Ref. [96]. Copyright 2018, Wiely-VCH.

Fig. 8. (a) Schematic of the preparation process. (b) Cross-sectional SEM image. (c-e) Top-view images at different magnifications for the Bi2O3 fractal films. Reprinted with permission from Ref. [112]. Copyright 2020, Wiely-VCH. SEM (f) and TEM (g) images and (h) Elemental maps of C, Bi, and O for Bi2O3@C/HB. Reprinted with permission from Ref. [113]. Copyright 2021, American Chemical Society.

Fig. 9. (a) Illustration the preparation of Bi NP@MWCNTs. (b,d) TEM images. (c) Histograms of particle-size distributions of Bi NP@MWCNTs. Reprinted with permission from Ref. [119]. Copyright 2020, American Chemical Society. (e) SEM image of Bi2O3 nanosheets. (f,g) SEM and TEM images of Bi2S3-Bi2O3 nanosheets. (h) Elemental mapping images of Bi2S3-Bi2O3 nanosheets. Reprinted with permission from Ref. [133]. Copyright 2020, Royal Society of Chemistry.

Fig. 10. (a) Atomic structure of BiOBr and BiOBr-templated Bi catalyst after electroreduction. (b) In situ grazing-incidence wide-angle X-ray scattering (GIWAXS) of BiOBr at open-circuit potential and reducing potential showcasing the catalyst reconfiguration. Reprinted with permission from Ref. [104]. Copyright 2018, Wiely-VCH. (c) SEM image; (d) AFM image of BiOI nanosheets. Reprinted with permission from Ref. [80]. Copyright 2018, Springer-Nature.

Fig. 11. (a) Schematic illustration for the preparation of Bi dendrite electrode. Reprinted with permission from Ref. [138]. Copyright 2017, American Chemical Society.Transient current curves and SEM images of electrodeposited Bi films formed by direct-current 60 s (b), pulse-current 6 cycles (c), and direct-current 120 s (d). Reprinted with permission from Ref. [82]. Copyright 2017, Elsevier Ltd.

Fig. 12. (a) Schematic illustration of the scalable preparation of ultrathin Bi nanosheets via a liquid-phase exfoliation process. TEM (b), HRTEM (c) and AFM (d) images of few-layer Bi nanosheets. Reprinted with permission from Ref. [142]. Copyright 2018, Elsevier Ltd. (e) Schematic illustration of the electrochemical exfoliation method used for the preparation of BOCNS; TEM (f) and HRTEM (g) images. (h) SEAD pattern of electrochemically exfoliated BOCNS. Reprinted with permission from Ref. [145]. Copyright 2018, Wiely-VCH.

Fig. 13. (a) Schematic illustration of the fabrication of Bi nanostructure. Reprinted with permission from Ref. [146]. Copyright 2019, Royal Society of Chemistry. (b) Schematic illustration of Bi NPs for CO2RR. Reprinted with permission from Ref. [54]. Copyright 2016, American Chemical Society. (c) Schematic illustration of the synthesis process for Bi2O3-NGQDs. Reprinted with permission from Ref. [148]. Copyright 2018, Wiely-VCH.

Fig. 14. An illustration of a generic MOF, composed of tetrametallic SBUs (cyan polyhedra) linked together by terephthalate (gray). Reprinted with permission from Ref. [149]. Copyright 2019, Royal Society of Chemistry.

Fig. 15. (a) Schematic illustration of the preparation of Bi@C and Bi2O3@C catalysts. (b-d) TEM images of Bi2O3@C catalysts. Reprinted with permission from Ref. [124]. Copyright 2020, Wiely-VCH. (e) Schematic illustration for the preparation of Bi-ene. (f) AFM image; TEM (g) and HRTEM (h) images of Bi-ene. Reprinted with permission from Ref. [153]. Copyright 2020, Wiely-VCH.

Fig. 16. (a) Schematic illustration for the preparation process of the Bi2O3NSs@MCCM. Reprinted with permission from Ref. [156]. Copyright 2019, Wiely-VCH. (b) Schematic illustration for molten salts assisted synthesis of Bi nanosheets. Reprinted with permission from Ref. [157]. Copyright 2020, Wiely-VCH.

Table 1 The performance of Bi-based catalysts for CO2RR.

Catalyst	Electrolyte	Product	Potential	FE (%)	j_partial (mA cm^-2)	Ref.
Bi-CMEC	[BMIM]BF₄	CO	-1.95 V vs. RHE	95	5.51	[55]
POD-Bi	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.16 V vs. RHE	95	57	[78]
Ultrathin BiNS	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1 V vs. RHE	100	12.5	[80]
BiNS	0.05 mol L^‒1 H₂SO₄ + 3 mol L^‒1 KCl	HCOO^-	-1.23 V vs. RHE	92.2	237.1	[81]
Bi nanosheets	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.1 V vs. RHE	86	14.2	[142]
Bi@NPC	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.5 V vs. SCE	92	14.4	[127]
Cu foam@BiNW	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.69 V vs. RHE	95	15	[71]
BNTs	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1 V vs. RHE	97	NA	[76]
NTD-Bi	1 mol L^‒1 KOH	HCOO^-	-0.58 V vs. RHE	98	205.8	[75]
ED-Bi dendrites/BP	0.5 mol L^‒1 KHCO₃	HCOOH	-1 V vs. RHE	92	35	[134]
BiO_x/C	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1.13 V vs. RHE	93.4	16.1	[45]
Bi₂O₃-5h	0.5 mol L^‒1 KHCO₃	HCOOH	-0.9 V vs. RHE	91	8	[110]
f-Bi₂O₃	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.2 V vs. RHE	87	NA	[112]
Bi₂O₃NSs@MCCM	0.1 mol L^‒1 KHCO₃	HCOOH	-1.256 V vs. RHE	93.8	15	[156]
AgBi-500	0.1 mol L^‒1 KHCO₃	HCOO^-	-0.7 V vs. RHE	94.3	12.52	[195]
CuBi	0.5 mol L^‒1 KHCO₃	HCOOH	-1.2 V vs. RHE	90.86	35	[91]
BiSn-CF	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.14 V vs. RHE	96	43.2	[94]
Bi NP@MWCNTs	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.5 V vs. SCE	95.2	10.18	[119]
Bi/rGO	0.1 mol L^‒1 KHCO₃	HCOOH	-0.8 V vs. RHE	98	NA	[121]
Bi₂O₃@C-800	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.28 V vs. RHE	93	200	[125]
Bi SAs/NC	0.1 mol L^‒1 KHCO₃	CO	-0.5 V vs. RHE	97	3.9	[66]
Mp-Bi	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.9 V vs. RHE	100	15	[160]
SD-Bi	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.75 V vs. RHE	84	5	[106]
Bi-MoP nanosheets	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.86 V vs. RHE	93	30	[137]
Bi dendrite	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.74 V vs. RHE	89	2.7	[138]
Bi nanoflake	0.1 mol L^‒1 KHCO₃	HCOO^-	-0.6 V vs. RHE	100	NA	[82]
Bi-B	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1.8 V vs. SCE	96.4	15.2	[140]
BOCNS	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.7 V vs. RHE	85	9.35	[145]
Bi₄₅/GDE	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.45 V vs. SCE	90	1.5	[147]
Bi₂O₃-NGQDS	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.9 V vs. RHE	98.1	18.1	[148]

Table 1 The performance of Bi-based catalysts for CO2RR.

Catalyst	Electrolyte	Product	Potential	FE (%)	j_partial (mA cm^-2)	Ref.
Bi-CMEC	[BMIM]BF₄	CO	-1.95 V vs. RHE	95	5.51	[55]
POD-Bi	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.16 V vs. RHE	95	57	[78]
Ultrathin BiNS	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1 V vs. RHE	100	12.5	[80]
BiNS	0.05 mol L^‒1 H₂SO₄ + 3 mol L^‒1 KCl	HCOO^-	-1.23 V vs. RHE	92.2	237.1	[81]
Bi nanosheets	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.1 V vs. RHE	86	14.2	[142]
Bi@NPC	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.5 V vs. SCE	92	14.4	[127]
Cu foam@BiNW	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.69 V vs. RHE	95	15	[71]
BNTs	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1 V vs. RHE	97	NA	[76]
NTD-Bi	1 mol L^‒1 KOH	HCOO^-	-0.58 V vs. RHE	98	205.8	[75]
ED-Bi dendrites/BP	0.5 mol L^‒1 KHCO₃	HCOOH	-1 V vs. RHE	92	35	[134]
BiO_x/C	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1.13 V vs. RHE	93.4	16.1	[45]
Bi₂O₃-5h	0.5 mol L^‒1 KHCO₃	HCOOH	-0.9 V vs. RHE	91	8	[110]
f-Bi₂O₃	0.1 mol L^‒1 KHCO₃	HCOO^-	-1.2 V vs. RHE	87	NA	[112]
Bi₂O₃NSs@MCCM	0.1 mol L^‒1 KHCO₃	HCOOH	-1.256 V vs. RHE	93.8	15	[156]
AgBi-500	0.1 mol L^‒1 KHCO₃	HCOO^-	-0.7 V vs. RHE	94.3	12.52	[195]
CuBi	0.5 mol L^‒1 KHCO₃	HCOOH	-1.2 V vs. RHE	90.86	35	[91]
BiSn-CF	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.14 V vs. RHE	96	43.2	[94]
Bi NP@MWCNTs	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.5 V vs. SCE	95.2	10.18	[119]
Bi/rGO	0.1 mol L^‒1 KHCO₃	HCOOH	-0.8 V vs. RHE	98	NA	[121]
Bi₂O₃@C-800	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.28 V vs. RHE	93	200	[125]
Bi SAs/NC	0.1 mol L^‒1 KHCO₃	CO	-0.5 V vs. RHE	97	3.9	[66]
Mp-Bi	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.9 V vs. RHE	100	15	[160]
SD-Bi	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.75 V vs. RHE	84	5	[106]
Bi-MoP nanosheets	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.86 V vs. RHE	93	30	[137]
Bi dendrite	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.74 V vs. RHE	89	2.7	[138]
Bi nanoflake	0.1 mol L^‒1 KHCO₃	HCOO^-	-0.6 V vs. RHE	100	NA	[82]
Bi-B	0.5 mol L^‒1 NaHCO₃	HCOO^-	-1.8 V vs. SCE	96.4	15.2	[140]
BOCNS	0.5 mol L^‒1 NaHCO₃	HCOO^-	-0.7 V vs. RHE	85	9.35	[145]
Bi₄₅/GDE	0.5 mol L^‒1 KHCO₃	HCOO^-	-1.45 V vs. SCE	90	1.5	[147]
Bi₂O₃-NGQDS	0.5 mol L^‒1 KHCO₃	HCOO^-	-0.9 V vs. RHE	98.1	18.1	[148]

Fig. 17. TEM images (a,b), AFM image (c), LSV curves (d), FEformate (e) and jformate (f) for Bi-ene-NW. Reprinted with permission from Ref. [163]. Copyright 2021, Royal Society of Chemistry. LSV curves (g), FEformate (h) and the calculation (i) of ECSA for BiNSs with different thickness. Reprinted with permission from Ref. [164]. Copyright 2020, Springer Nature.

Fig. 18. (a) Chronoamperometric tests at different potentials in 1 mol L?1 KHCO3 and 1 mol L?1 KOH. (b) Polarization curves of nanotube-derived Bi (NTD-Bi) in 1 mol L?1 KHCO3 and 1 mol L?1 KOH. (c) Free-energy for formate production on ideal and defective surfaces. (d) The corresponding calculated polarization curves of CO2RR. Reprinted with permission from Ref. [75]. Copyright 2019, Springer Nature. (e) Free-energy for *OCHO and *COOH intermediate generation on defective Bi (001) facet. (f) Free-energy for *OCHO intermediate generation on ideal and defective Bi (001) facet. Reprinted with permission from Ref. [175]. Copyright 2020, Elsevier Ltd.

Fig. 19. (a) LSV curves in Ar-saturated or CO2-saturated 0.1 mol L?1 KHCO3. (b) FEs of various products at different applied potentials on Bi(B). Reprinted with permission from Ref. [181]. Copyright 2021, Wiley-VCH. FE of formate (c) and partial current density (d) of formate for S-BiOC. (e) Schematic illustration for the role of S-doping to promote the reduction of CO2 to formate. Reprinted with permission from Ref. [182]. Copyright 2021, Elsevier Ltd.

Fig. 20. (a) Current densities and FEformate at different potentials. (b) Tafel Slope over Bi-C/723 and bulk Bi for CO2RR. Reprinted with permission from Ref. [200]. Copyright 2021, Royal Society of Chemistry. jformate (c) and FEformate (d) at different potentials for Bi2S3-Bi2O3 NSs. Reprinted with permission from Ref. [196]. Copyright 2022, Wiely-VCH. LSV curves (e) and FEs (f) of products for Bi/Bi(Sn)Ox NWs. Reprinted with permission from Ref. [203]. Copyright 2021, American Chemical Society.

Fig. 21. (a) Potential-dependent operando Raman spectra of the CeO2/BiOCl. (b,c) Potential-dependent operando Raman spectra of the CeO2/BiOCl at different wavenumber region. Reprinted with permission from Ref. [132]. Copyright 2021, Oxford University Press. (d) In situ ATR-IR spectra collected under different applied potentials. Reprinted with permission from Ref. [153]. Copyright 2020, Wiely-VCH. (e,f) Operando XANES spectra of Bi L3-edge and corresponding Fourier transform of EXAFS spectrum as a function of electrochemical bias and with electroreduction time under electrochemical CO2 reduction conditions. Reprinted with permission from Ref. [152]. Copyright 2020, Elsevier Ltd. (g) STS map at + 283 mV of 1 BL=Bi2Te3 island showing the step edge. Reprinted with permission from Ref. [206]. Copyright 2012, American Physical Society. (h) DFT band-structure calculation and ARPES band dispersionthrough the Brillouin zon. (i) Differential conductivity of fully-planar bismuthene at different distances to the edge. Reprinted with permission from Ref. [207]. Copyright 2017, Science.

Fig. 22. (a) Sketch of the modules used in technical photosynthesis of 1-butanol and 1-hexanol from CO2 and H2O. Reprinted with permission from Ref. [208]. Copyright 2018, Springer-Nature. (b) Schematic illustration of the CO2 reduction cell with solid electrolyte. Reprinted with permission from Ref. [87]. Copyright 2019, Springer-Nature. (c) Schematic illustration of the flow cell configuration. Reprinted with permission from Ref. [75]. Copyright 2019, Springer-Nature. (d) Schematic illustration of the membrane electrode assembly. Reprinted with permission from Ref. [209]. Copyright 2021, American Chemical Society.

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Rational design of bismuth-based catalysts for electrochemical CO₂ reduction

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