Decreasing the Overpotential for Formate Production in Electrochemical CO2 Reduction Achieved by Anodized Sn Electrode

Electrochemical CO2 reduction to produce formate ions has studied for the sustainable carbon cycle. Mercury in the liquid state is known to be an active metallic component to selectively convert CO2 to formate ions, but it is not scalable to use as an electrode in electrochemical CO2 reduction. Therefore, scalable amalgam electrodes with different base metals are tested to produce formate by an electrochemical CO2 reduction. The amalgam electrodes are prepared by the electrodeposition of Hg on the pre-electrodeposited Pd, Au, Pt and Cu nanoparticles on the glassy carbon. The formate faradaic efficiency with the Pd, Au, Pt and Cu is lower than 25%, while the one with the respective metal amalgams is higher than 50%. Pd amalgam among the tested samples shows the highest formate faradic efficiency and current density. The formate faradaic efficiency is recorded 85% at −2.1 V vs SCE and the formate current density is −6.9 mA cm−2. It is concluded that Pd2Hg5 alloy on the Pd amalgam electrode is an active phase for formate production in the electrochemical CO2 reduction.

Download Full-text

Copper–Gold Interactions Enhancing Formate Production from Electrochemical CO2 Reduction

ACS Catalysis ◽

10.1021/acscatal.9b03158 ◽

2019 ◽

Vol 9 (12) ◽

pp. 10894-10898 ◽

Cited By ~ 8

Author(s):

Zixu Tao ◽

Zishan Wu ◽

Xiaolei Yuan ◽

Yueshen Wu ◽

Hailiang Wang

Keyword(s):

Co2 Reduction ◽

Electrochemical Co2 Reduction ◽

Copper Gold ◽

Formate Production

Download Full-text

Sn-doped Bi2O3 Nanosheets for Highly Efficient Electrochemical CO2 Reduction toward Formate Production

Nanoscale ◽

10.1039/d1nr06038d ◽

2021 ◽

Author(s):

Xiao Li ◽

Xingqiao Wu ◽

Junjie Li ◽

Jingbo Huang ◽

Liang Ji ◽

...

Keyword(s):

Greenhouse Gas ◽

Co2 Reduction ◽

Value Added ◽

Efficient Conversion ◽

Highly Efficient ◽

Electrochemical Co2 Reduction ◽

Huge Challenge ◽

Formate Production

Electrocatalytic CO2 reduction into formate is considered as a perfect route to efficient conversion of greenhouse gas CO2 to value-added chemicals. However, it still remains a huge challenge to design...

Download Full-text

Orbital Interactions in Bi-Sn Bimetallic Electrocatalysts for Highly Selective Electrochemical CO2 Reduction toward Formate Production

Advanced Energy Materials ◽

10.1002/aenm.201802427 ◽

2018 ◽

Vol 8 (31) ◽

pp. 1802427 ◽

Cited By ~ 68

Author(s):

Guobin Wen ◽

Dong Un Lee ◽

Bohua Ren ◽

Fathy M. Hassan ◽

Gaopeng Jiang ◽

...

Keyword(s):

Co2 Reduction ◽

Orbital Interactions ◽

Electrochemical Co2 Reduction ◽

Formate Production

Download Full-text

Molecular Inhibition for Selective CO2 Conversion

10.26434/chemrxiv-2022-63b91 ◽

2022 ◽

Author(s):

Charles Creissen ◽

José Guillermo Rivera de la Cruz ◽

Dilan Karapinar ◽

Dario Taverna ◽

Moritz Schreiber ◽

...

Keyword(s):

Heterogeneous Catalysts ◽

Co2 Reduction ◽

Copper Catalysts ◽

Reaction Rates ◽

Product Distribution ◽

Flow Cell ◽

Novel Approach ◽

Electrochemical Co2 Reduction ◽

Conventional Material ◽

Formate Production

Electrochemical CO2 reduction presents a sustainable route to the production of chemicals and fuels. Achieving a narrow product distribution with copper catalysts is challenging and conventional material modifications offer limited control over selectivity. Here, we show that the mild cathodic potentials required to reach high currents in an alkaline gas-fed flow cell permits retention of a surface-bound thiol (4-mercaptopyridine), enabling molecule-directed selective formate generation at high reaction rates. Combined experimental and computational results showed that formate production is favoured due to the inhibition of a CO producing pathway caused by destabilising interactions with the anchored molecule. The immobilisation of molecules to inhibit specific carbon-based products therefore offers a novel approach to rationally tune the selectivity of heterogeneous catalysts.

Download Full-text

An NADH-Inspired Redox Mediator Strategy to Promote Second-Sphere Electron and Proton Transfer for Cooperative Electrochemical CO2 Reduction Catalyzed by Iron Porphyrin

10.26434/chemrxiv.12159207.v1 ◽

2020 ◽

Cited By ~ 1

Author(s):

Peter T. Smith ◽

Sophia Weng ◽

Christopher Chang

Keyword(s):

Proton Transfer ◽

Co2 Reduction ◽

Iron Porphyrin ◽

Redox Mediators ◽

Reservoir Properties ◽

Proton Reduction ◽

Electrochemical Co2 Reduction ◽

Starting Point ◽

Rate Improvement ◽

Molecular Catalysts

We present a bioinspired strategy for enhancing electrochemical carbon dioxide reduction catalysis by cooperative use of base-metal molecular catalysts with intermolecular second-sphere redox mediators that facilitate both electron and proton transfer. Functional synthetic mimics of the biological redox cofactor NADH, which are electrochemically stable and are capable of mediating both electron and proton transfer, can enhance the activity of an iron porphyrin catalyst for electrochemical reduction of CO2 to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO2 versus proton reduction. Evaluation of a systematic series of NADH analogs and redox-inactive control additives with varying proton and electron reservoir properties reveals that both electron and proton transfer contribute to the observed catalytic enhancements. This work establishes that second-sphere dual control of electron and proton inventories is a viable design strategy for developing more effective electrocatalysts for CO2 reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

Download Full-text