A Perovskite Electronic Structure Descriptor for Electrochemical CO2 Reduction and the Competing H2 Evolution Reaction

2019 ◽  
Vol 123 (40) ◽  
pp. 24469-24476
Author(s):  
Jonathan Hwang ◽  
Karthik Akkiraju ◽  
Juan Corchado-García ◽  
Yang Shao-Horn
Keyword(s):  
Electronic Structure ◽  
Co2 Reduction ◽  
H2 Evolution ◽  
Electrochemical Co2 Reduction ◽  
Structure Descriptor

Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H2 Evolution Rates during Electrochemical CO2 Reduction

2021 ◽  
Vol 143 (36) ◽  
pp. 14712-14725
Author(s):  
David M. Koshy ◽  
Sneha A. Akhade ◽  
Adam Shugar ◽  
Kabir Abiose ◽  
Jingwei Shi ◽  
...  
Keyword(s):  
Co2 Reduction ◽  
H2 Evolution ◽  
Chemical Modifications ◽  
Electrochemical Co2 Reduction ◽  
Ag Catalyst ◽  
Catalyst Surfaces

scholarly journals Metal–Ligand Exchange Coupling Promotes Iron-Catalyzed Electrochemical CO2 Reduction at Low Overpotentials

2020 ◽  
Author(s):  
Jeffrey Derrick ◽  
Matthias Loipersberger ◽  
Diana Iovan ◽  
Peter T. Smith ◽  
Khetpakorn Chakarawet ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Ligand Exchange ◽  
Exchange Coupling ◽  
Co2 Reduction ◽  
Open Shell ◽  
Electronic Delocalization ◽  
Electrochemical Co2 Reduction ◽  
Reduction Of Co2 ◽  
High Degree ◽  
Metal Ligand

Biological and heterogenous catalysts for electrochemical CO2 reduction often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over hydrogen evolution. Here, we report a molecular iron(II) complex that achieves a similar feat as a result of strong metal–ligand exchange coupling. This interaction promotes an open-shell singlet electronic structure that drives the electrochemical reduction of CO2 to CO with over 90% selectivity and turnover frequencies of 100,000 s−1 at low overpotentials, with no degradation over 20 hours. The decrease in the thermodynamic barrier engendered by this strong metal–ligand exchange coupling enables homogeneous CO2 reduction catalysis in water without compromising reaction selectivity.

scholarly journals A Short Perspective on Electrochemical CO2 Reduction to CO

2020 ◽  
Vol 74 (6) ◽  
pp. 478-482
Author(s):  
Maxime Tarrago ◽  
Shengfa Ye
Keyword(s):  
Electronic Structure ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Co2 Reduction ◽  
Short Review ◽  
Product Selectivity ◽  
Electrochemical Co2 Reduction ◽  
Co Reduction

This short review summarizes examples of many homogeneous non-noble catalysts for CO2-to-CO reduction and compares their feasible mechanisms. The focus is to show that elucidating the electronic structure of the catalytic system likely provides better understanding of the reaction mechanism and product selectivity.

Facile synthesis of Cu catalysts with multiple high-index facets for the suppression of competing H2 evolution during the electrocatalytic CO2 reduction

Nanoscale ◽  
2021 ◽  
Author(s):  
Monday Philip ◽  
Abebe Reda Woldu ◽  
Muhammad Bilal Akbar ◽  
Hitler Louis ◽  
Huang Cong
Keyword(s):  
Co2 Reduction ◽  
Reduction Reaction ◽  
High Index ◽  
Cu Nanoparticles ◽  
H2 Evolution ◽  
Facile Synthesis ◽  
Electrochemical Co2 Reduction ◽  
Cu Catalysts ◽  
Co2 Reduction Reaction

Electrochemical CO2 reduction reaction (CO2RR) over high-index facets of Cu nanoparticles (NPs) is favourable toward the formation of multi-carbon products, such as hydrocarbons and oxygenates. However, the facile synthesis of...

scholarly journals Metal–Ligand Exchange Coupling Promotes Iron-Catalyzed Electrochemical CO2 Reduction at Low Overpotentials

2020 ◽  
Author(s):  
Jeffrey Derrick ◽  
Matthias Loipersberger ◽  
Diana Iovan ◽  
Peter T. Smith ◽  
Khetpakorn Chakarawet ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Ligand Exchange ◽  
Exchange Coupling ◽  
Co2 Reduction ◽  
Open Shell ◽  
Electronic Delocalization ◽  
Electrochemical Co2 Reduction ◽  
Reduction Of Co2 ◽  
High Degree ◽  
Metal Ligand

Biological and heterogenous catalysts for electrochemical CO2 reduction often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over hydrogen evolution. Here, we report a molecular iron(II) complex that achieves a similar feat as a result of strong metal–ligand exchange coupling. This interaction promotes an open-shell singlet electronic structure that drives the electrochemical reduction of CO2 to CO with over 90% selectivity and turnover frequencies of 100,000 s−1 at low overpotentials, with no degradation over 20 hours. The decrease in the thermodynamic barrier engendered by this strong metal–ligand exchange coupling enables homogeneous CO2 reduction catalysis in water without compromising reaction selectivity.

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

2020 ◽  
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 CO<sub>2</sub> to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO<sub>2</sub> 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 CO<sub>2</sub> reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

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