In situ reconstruction of vegetable sponge-like Bi2O3 for efficient CO2 electroreduction to formate

Shi, Ying-Li; Wen, Chun Fang; Wu, Xinsheng; Zhao, Jian; Mao, Feng; Liu, Peng Fei; Yang, Hua Gui

doi:10.1039/d1qm01557e

Cited by 11 publications

(10 citation statements)

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“…Unless otherwise stated, electrolysis was carried out for a duration of 1 h with the application of a freshly prepared ap-Bi 2 O 3 @GDE in each case. The catalyst testing results are presented in Figure and confirm the superior selectivity of the dendritic Bi 2 O 3 catalyst (precursor) toward formate production that has already been reported for H-type cell experiments. , Representative current (density) versus time traces are provided in Figure S11. In 1 mol dm –3 KOH solution, the formate efficiency (FE formate ) increases from an initial value of 72.2% to a maximum of 97.4% as the applied potential was changed from −0.3 to −0.8 V vs RHE.…”

Section: Resultsmentioning

confidence: 99%

“…For a CO 2 -saturated 0.5 mol dm –3 KHCO 3 electrolyte solution, a combination of electrochemical analysis and operando Raman spectroscopy during CO 2 RR revealed the coupling of two potential-dependent CO 2 RR pathways as the origin of this superior catalytic performance . At low applied overpotentials (−0.3 to −0.6 V vs the reversible hydrogen electrode (RHE)), the CO 2 RR was shown to proceed predominantly via the so-called subcarbonate pathway (see Figure ), where a pristine Bi 2 O 3 precursor undergoes a rapid transformation into a bulk bismuth subcarbonate phase. ,− The term “bismuth subcarbonate” refers to a mixed oxide/carbonate compound in which bismuth has an oxidation state of +3. (BiO) 2 CO 3 is formed (formally) through partial exchange of O 2– by CO 3 2– anions through the reaction of the oxidic precursor with gaseous or dissolved CO 2 .…”

Section: Introductionmentioning

confidence: 99%

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CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions

et al. 2022

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Herein, we demonstrate the superior performance of bismuth subcarbonate ((BiO) 2 CO 3 ) layer catalysts for formate production using a fluidic CO 2 -fed electrolyzer device. The subcarbonate catalyst readily forms in situ from a CO 2 -absorbing Bi 2 O 3 precursor material during the CO 2 reduction reaction (CO 2 RR). In 1 mol dm −3 KOH electrolyte solution, a maximum Faradaic efficiency of FE formate = 97.4% (corresponding partial current density of formate formation: PCD formate = −111.6 mA cm −2 ) was achieved at a comparably low applied electrolysis potential of −0.8 V vs the reversible hydrogen electrode (RHE). Even higher values of PCD formate = −441.2 mA cm −2 (FE formate = 62%) were observed at a more cathodic potential, −2.5 V vs RHE. As the alkalinity of the liquid electrolyte is further increased (e.g., by using 5 mol dm −3 KOH solution), the performance of formate production is boosted beyond PCD formate values of −1 A cm −2 . Combined X-ray diffraction and Raman spectroscopic investigations demonstrate an extraordinarily high stability of Bi(III) cations in the catalytically active subcarbonate catalyst phase down to cathode potentials of −1.5 V vs RHE. This stabilization effect can clearly be attributed to the high abundance of gaseous CO 2 under the operating conditions of the gas-fed electrolyzer. In the absence of any CO 2 supply, the reductive Bi(III) → Bi(0) transition already occurs under much milder conditions of −0.3 V vs RHE, as evidenced by in situ Raman spectroscopy in CO 2 -free 1 mol dm −3 KOH electrolyte solution. An advanced X-ray diffraction computed tomography technique was applied to gain deeper insights into the spatial distribution of the metallic and subcarbonate phases comprising the active composite catalyst layer during the CO 2 RR.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions

et al. 2022

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“…[ 204 ] An edible sponge‐like Bi 2 O 3 with unique porous morphology and low crystallinity was synthesized, which was in situ reconstructed into 2D NSs containing metallic Bi and Bi 2 O 2 CO 3 , and served as the active species for eCO 2 RR to formate. [ 205 ] Wang et al examined the reaction performance and intrinsic properties of functionalized Bi nanosheets (Bi‐NHS) electrocatalysts by adding 3‐aminopropyltriethoxysilane ( Figure a). [ 206 ] Experimental results and DFT calculations show that eCO 2 RR to formate on Bi(001)‐NHS surfaces are more energetically favorable than on bare Bi(001) surfaces, and 3‐aminopropyltriethoxysilane are excellent ligands to stabilize the catalytic activities of metallic Bi.…”

Section: Advanced Electrocatalysts For Cathodic Reactionsmentioning

confidence: 99%

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

et al. 2022

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Electro-organic synthesis has attracted a lot of attention in pharmaceutical science, medicinal chemistry, and future industrial applications in energy storage and conversion. To date, there has not been a detailed review on electro-organic synthesis with the strategy of heterogeneous catalysis. In this review, the most recent advances in synthesizing value-added chemicals by heterogeneous catalysis are summarized. An overview of electrocatalytic oxidation and reduction processes as well as paired electrocatalysis is provided, and the anodic oxidation of alcohols (monohydric and polyhydric), aldehydes, and amines are discussed. This review also provides in-depth insight into the cathodic reduction of carboxylates, carbon dioxide, C=C, C≡C, and reductive coupling reactions. Moreover, the electrocatalytic paired electro-synthesis methods, including parallel paired, sequential divergent paired, and convergent paired electrolysis, are summarized. Additionally, the strategies developed to achieve high electrosynthesis efficiency and the associated challenges are also addressed. It is believed that electro-organic synthesis is a promising direction of organic electrochemistry, offering numerous opportunities to develop new organic reaction methods.

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“…The catalyst testing results are presented in Figure 5 and confirm the superior selectivity of the dendritic Bi 2 O 3 catalyst (precursor) toward formate production that has already been reported for H-type cell experiments. 38,56 In 1 mol dm -3 KOH solution, the formate efficiency (FE formate ) increases from an initial value of 72.2% to a maximum of 97.4% as the applied potential was changed from -0.3 V to -0.8 V vs.…”

Section: Electrochemical Performance Testingmentioning

confidence: 99%

CO2 Conversion at High Current Densities: Stabilization of Bi(III) Containing Electrocatalysts under CO2 Gas Flow Conditions

Montiel

Dutta

Kiran

et al. 2022

Preprint

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Herein, we demonstrate the superior performance of novel bismuth subcarbonate ((BiO)2CO3) film catalysts for formate production using a fluidic CO2-fed electrolyzer device. The subcarbonate catalyst readily forms in situ from a CO2-absorbing Bi2O3 precursor material during the CO2 reduction reaction (CO2RR). In 1 mol dm–3 KOH electrolyte solution, a maximum Faradaic efficiency of FEformate = 97.4% (corresponding partial current density of formate formation: PCDformate = –111.6 mA cm–2) was achieved at a comparably low applied electrolysis potential of –0.8 V versus the reversible hydrogen electrode (RHE). Even higher values of PCDformate = –441.2 mA cm–2 (FEformate = 62%) were observed at more cathodic potential, –2.5 V vs. RHE. As the alkalinity of the liquid electrolyte is further increased (e.g., by using 5 mol dm–3 KOH solution), the performance of formate production is boosted beyond PCDformate values of –1 A cm–2. Combined X-ray diffraction and Raman spectroscopic investigations demonstrate an extraordinarily high stability of Bi(III) cations in the catalytically active subcarbonate catalyst phase down to cathode potentials of –1.5 V vs. RHE. This stabilization effect can clearly be attributed to the high abundance of gaseous CO2 under the operating conditions of the gas-fed electrolyzer. In the absence of any CO2 supply, however, the reductive Bi(III)-to-Bi(0) transition already occurs at much milder conditions of –0.3 V vs. RHE, as evidenced by in situ Raman spectroscopy in CO2-free 1 mol dm–3 KOH electrolyte solution. Advanced X-ray diffraction computed tomography (XRD-CT) technique was applied to gain deeper insights into the spatial distribution of the metallic and subcarbonate phases comprising the active composite catalyst layer (CL) during the CO2RR.

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In situ reconstruction of vegetable sponge-like Bi₂O₃ for efficient CO₂ electroreduction to formate

Abstract: The electrochemical reduction reaction of CO2 provides a renewable method to close the carbon cycle and alleviate the global energy issue. Bi-based electrocatalysts present huge prospect of catalyzing formate-selective CO2...

Cited by 11 publications

References 43 publications

CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions

CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

CO2 Conversion at High Current Densities: Stabilization of Bi(III) Containing Electrocatalysts under CO2 Gas Flow Conditions

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In situ reconstruction of vegetable sponge-like Bi2O3 for efficient CO2 electroreduction to formate

Abstract: The electrochemical reduction reaction of CO2 provides a renewable method to close the carbon cycle and alleviate the global energy issue. Bi-based electrocatalysts present huge prospect of catalyzing formate-selective CO2...

Cited by 11 publications

References 43 publications

CO2 Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO2 Gas Flow Conditions

CO2 Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO2 Gas Flow Conditions

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

CO2 Conversion at High Current Densities: Stabilization of Bi(III) Containing Electrocatalysts under CO2 Gas Flow Conditions

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Product

Resources

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In situ reconstruction of vegetable sponge-like Bi₂O₃ for efficient CO₂ electroreduction to formate

CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions

CO₂ Conversion at High Current Densities: Stabilization of Bi(III)-Containing Electrocatalysts under CO₂ Gas Flow Conditions