Electrocatalytic Reduction of CO2 to Widely Proportionally Syngas Enabled by Cu x In y Alloy Synergistic Polyoxometalates

doi:10.19894/j.issn.1000-0518.240135

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (12): 1751-1759.DOI: 10.19894/j.issn.1000-0518.240135

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Electrocatalytic Reduction of CO₂ to Widely Proportionally Syngas Enabled by Cu _x In _y Alloy Synergistic Polyoxometalates

Yue-Hua TAI, Wen-Cong SUN, Lin-Kui HE, Li ZHOU, Shu-Miao LI, Wen-Xue TIAN, Chun-Xiang LI()

School of Chemistry and Chemical Engineering，Harbin Institute of Technology，Harbin 150001，China

Received:2024-04-24 Accepted:2024-10-21 Published:2024-12-01 Online:2025-01-02
Contact: Chun-Xiang LI
About author:lichx@hit.edu.cn
Supported by:
the Education Science Planning Project of Heilongjiang Province(GJB1423127)

Abstract

Abstract:

Utilizing non grid connected electricity for CO₂ conversion and reuse is one of the promising approaches in the context of “dual carbon”. In order to achieve a wide and adjustable proportion of syngas via CO₂ reduction， synergistic catalytic system of Cu _x In _y alloy and PV₂MoW₉ were designed and constructed. Among alloy series of Cu _x In _y， Cu₁In₃ exhibits the optimal CO₂ electrocatalytic activity， achieving a high CO Faraday efficiency of 95.3% under an applied voltage of -0.6 V and a stable duration of up to 53 h. Further experimental analysis and theoretical studies indicated that copper-indium alloy weakens the binding between the intermediate ^*CO and the catalyst， accelerates the process of ^*CO desorption into CO， and thus improves the selectivity of CO. In this system， the CO₂ reduction process is as follows： CO₂ → ${}^{*} C O_{2}^{-}$ → ^*COOH→ ^*CO →CO.

Key words: Electrocatalytic CO₂ reduction reaction, Copper-indium alloy, Synthetic gas, Polyoxometalates

CLC Number:

O643.3

Yue-Hua TAI, Wen-Cong SUN, Lin-Kui HE, Li ZHOU, Shu-Miao LI, Wen-Xue TIAN, Chun-Xiang LI. Electrocatalytic Reduction of CO₂ to Widely Proportionally Syngas Enabled by Cu _x In _y Alloy Synergistic Polyoxometalates[J]. Chinese Journal of Applied Chemistry, 2024, 41(12): 1751-1759.

Figures/Tables 9

Fig.1 XRD pattern of （A） Cu，（B） In，（C） Cu2In3 and （D） Cu x In y

Table 1 ICP test results of Cu x In y

Catalysts	10⁶ Cu	10⁶ In	Nominal （n（Cu）∶n（In））	x（Cu）/%	x（In）/%	Actual （n（Cu）∶n（In））
Cu₁In₃	9.37	46.12	0.33	26.85	73.15	0.36
Cu₂In₃	14.44	34.06	0.67	43.38	56.62	0.76
CuIn	17.83	30.07	1.00	51.63	48.36	1.06

Fig.2 SEM and mapping images of （A， B） CuIn，（C， D） Cu1In3 and （E， F） Cu2In3

Fig.3 TEM （A， B） and HRTEM （C） for Cu1In3

Fig.4 FE （CO and H2） of Cu1In3 （A）， Cu2In3 （B） and CuIn （C） in PV2MoW9 medium after electrolysis for 1 h at different voltage；（D） The current density for CO of Cu x In y in PV2MoW9 medium after electrolysis for 1 h

Fig.5 Tafel slopes for （A） Cu， In， CuxIny in CO2-saturaed 0.1 mol/L Na2SO4 and （B） CuxIny-PV2MoW9 system for ECO2RR

Fig.6 Stability test of Cu1In3 in PV2MoW9-Na2SO4 medium electrolysis at -0.6 V

Fig.7 XPS spectra of In3d （A）， O1s （B）， W4f （C） and Cu2p （D） for Cu1In3 before and after ECO2RR

Fig.8 In-situ FT-IR spectra of Cu1In3 in PV2MoW9 medium at -0.6 V in the range of 2800~1200 cm-1 （A） and 1200~500 cm-1 （B）

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Electrocatalytic Reduction of CO₂ to Widely Proportionally Syngas Enabled by Cu _x In _y Alloy Synergistic Polyoxometalates

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