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Title: Understanding trends in electrochemical carbon dioxide reduction rates

Abstract

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbon monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.

Authors:
 [1];  [1];  [2];  [3]; ORCiD logo [4];  [1]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); Tsinghua Univ., Beijing (China)
  3. Stanford Univ., Stanford, CA (United States); Zhejiang Univ., Hangzhou (China)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1368688
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; electrochemistry

Citation Formats

Liu, Xinyan, Xiao, Jianping, Peng, Hongjie, Hong, Xin, Chan, Karen, and Norskov, Jens K. Understanding trends in electrochemical carbon dioxide reduction rates. United States: N. p., 2017. Web. doi:10.1038/ncomms15438.
Liu, Xinyan, Xiao, Jianping, Peng, Hongjie, Hong, Xin, Chan, Karen, & Norskov, Jens K. Understanding trends in electrochemical carbon dioxide reduction rates. United States. https://doi.org/10.1038/ncomms15438
Liu, Xinyan, Xiao, Jianping, Peng, Hongjie, Hong, Xin, Chan, Karen, and Norskov, Jens K. 2017. "Understanding trends in electrochemical carbon dioxide reduction rates". United States. https://doi.org/10.1038/ncomms15438. https://www.osti.gov/servlets/purl/1368688.
@article{osti_1368688,
title = {Understanding trends in electrochemical carbon dioxide reduction rates},
author = {Liu, Xinyan and Xiao, Jianping and Peng, Hongjie and Hong, Xin and Chan, Karen and Norskov, Jens K.},
abstractNote = {Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbon monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.},
doi = {10.1038/ncomms15438},
url = {https://www.osti.gov/biblio/1368688}, journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 8,
place = {United States},
year = {Mon May 22 00:00:00 EDT 2017},
month = {Mon May 22 00:00:00 EDT 2017}
}

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Works referenced in this record:

The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction
journal, January 2012


Mesostructure-Induced Selectivity in CO 2 Reduction Catalysis
journal, November 2015


A Highly Selective Copper-Indium Bimetallic Electrocatalyst for the Electrochemical Reduction of Aqueous CO 2 to CO
journal, December 2014


Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid
journal, July 2016


Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media
journal, August 1994


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009


Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014


Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014


The Structure of the Hydrogen Ion (H aq + ) in Water
journal, February 2010


Operational constraints and strategies for systems to effect the sustainable, solar-driven reduction of atmospheric CO 2
journal, January 2015


Particle Size Effects in the Catalytic Electroreduction of CO 2 on Cu Nanoparticles
journal, May 2014


Modeling the electrified solid–liquid interface
journal, November 2008


Modeling and Experimental Validation of Electrochemical Reduction of CO 2 to CO in a Microfluidic Cell
journal, November 2014


Electrochemical reduction of bicarbonate ions at a bright palladium cathode
journal, January 1985

  • Spichiger-Ulmann, Martine; Augustynski, Jan
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 81, Issue 3
  • https://doi.org/10.1039/f19858100713

Electrochemical reduction of carbon dioxide at a series of platinum single crystal electrodes
journal, August 2000


Pd catalysts supported onto nanostructured carbon materials for CO2 valorization by electrochemical reduction
journal, February 2015


On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces
journal, November 2013


Active and Selective Conversion of CO 2 to CO on Ultrathin Au Nanowires
journal, November 2014


How Doped MoS 2 Breaks Transition-Metal Scaling Relations for CO 2 Electrochemical Reduction
journal, June 2016


A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2
journal, June 2016


Nickel–Gallium-Catalyzed Electrochemical Reduction of CO 2 to Highly Reduced Products at Low Overpotentials
journal, February 2016


Electrochemical Reduction of CO 2 at Copper Nanofoams
journal, August 2014


Synthesis of thin film AuPd alloys and their investigation for electrocatalytic CO 2 reduction
journal, January 2015


Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
journal, January 2014


Structural effect on the rate of CO2 reduction on single crystal electrodes of palladium
journal, January 1997


Assessing the reliability of calculated catalytic ammonia synthesis rates
journal, July 2014


Selective electrochemical reduction of CO 2 to different alcohol products by an organically doped alloy catalyst
journal, January 2016


Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
journal, May 2015


Temperature-Dependent Hydrogen Electrochemistry on Platinum Low-Index Single-Crystal Surfaces in Acid Solutions
journal, July 1997


Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts
journal, July 2015


Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016


Molybdenum Sulfides and Selenides as Possible Electrocatalysts for CO 2 Reduction
journal, July 2014


Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer
journal, June 2015


Special points for Brillouin-zone integrations
journal, June 1976


Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials
journal, September 2011


Inhibited proton transfer enhances Au-catalyzed CO 2 -to-fuels selectivity
journal, July 2016


Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011


Global warming footprint of the electrochemical reduction of carbon dioxide to formate
journal, October 2015


Insights into the electrocatalytic reduction of CO 2 on metallic silver surfaces
journal, January 2014


Electrochemical reduction of CO2 on single crystal electrodes of silver Ag(111), Ag(100) and Ag(110)
journal, December 1997


Electrochemical Reduction of Carbon Dioxide on an Indium Wire in a KOH/Methanol-Based Electrolyte at Ambient Temperature and Pressure
journal, March 1999


Robust carbon dioxide reduction on molybdenum disulphide edges
journal, July 2014


Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007


Electrochemical reduction of carbon dioxide atTi and hydrogen-storing Ti electrodes inKOH–methanol
journal, January 1998


Universal transition state scaling relations for (de)hydrogenation over transition metals
journal, January 2011


BEP relations for N2 dissociation over stepped transition metal and alloy surfaces
journal, January 2008


Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide
journal, January 2015


Controlling Catalytic Selectivities during CO 2 Electroreduction on Thin Cu Metal Overlayers
journal, July 2013


Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012


CO 2 Reduction on Cu at Low Overpotentials with Surface-Enhanced in Situ Spectroscopy
journal, July 2016


Electrocatalytic Carbon Dioxide Activation: The Rate-Determining Step of Pyridinium-Catalyzed CO2 Reduction
journal, February 2011


Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)
journal, January 2016


Barriers of Electrochemical CO 2 Reduction on Transition Metals
journal, July 2016


Towards the computational design of solid catalysts
journal, April 2009


Reconstruction of Cu(100) Electrode Surfaces during Hydrogen Evolution
journal, August 2009


Electroreduction of Carbon Monoxide Over a Copper Nanocube Catalyst: Surface Structure and pH Dependence on Selectivity
journal, February 2016


Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C 2+ Oxygenate Production
journal, March 2016


Role of Steps in N 2 Activation on Ru(0001)
journal, August 1999


Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013


Electrochemical behavior of Pd–Rh alloys
journal, March 2006


A Highly Selective Copper-Indium Bimetallic Electrocatalyst for the Electrochemical Reduction of Aqueous CO 2 to CO
journal, December 2014


Electrocatalytic Carbon Dioxide Activation: The Rate-Determining Step of Pyridinium-Catalyzed CO2 Reduction
journal, February 2011


A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2
journal, June 2016


Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
journal, May 2015


Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016


Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013


Active and Selective Conversion of CO 2 to CO on Ultrathin Au Nanowires
journal, November 2014


Reconstruction of Cu(100) Electrode Surfaces during Hydrogen Evolution
journal, August 2009


Mesostructure-Induced Selectivity in CO 2 Reduction Catalysis
journal, November 2015


Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C 2+ Oxygenate Production
journal, March 2016


Towards the computational design of solid catalysts
journal, April 2009


Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014


Robust carbon dioxide reduction on molybdenum disulphide edges
journal, July 2014


BEP relations for N2 dissociation over stepped transition metal and alloy surfaces
journal, January 2008


Universal transition state scaling relations for (de)hydrogenation over transition metals
journal, January 2011


Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
journal, January 2014


Electrochemical reduction of CO 2 to ethylene glycol on imidazolium ion-terminated self-assembly monolayer-modified Au electrodes in an aqueous solution
journal, January 2015


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009


Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid
journal, July 2016


Works referencing / citing this record:

Identifying Active Sites of Nitrogen-Doped Carbon Materials for the CO 2 Reduction Reaction
journal, April 2018


2D Metal Oxyhalide-Derived Catalysts for Efficient CO 2 Electroreduction
journal, August 2018


Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO 2
journal, April 2018


Toward Computational Design of Catalysts for CO 2 Selective Reduction via Reaction Phase Diagram Analysis
journal, January 2019


A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
journal, November 2019


Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction
journal, August 2018


Competition between H and CO for Active Sites Governs Copper-Mediated Electrosynthesis of Hydrocarbon Fuels
journal, July 2018


Reaction Mechanisms of Well-Defined Metal-N 4 Sites in Electrocatalytic CO 2 Reduction
journal, November 2018


Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction
journal, December 2019


Dynamic Changes in the Structure, Chemical State and Catalytic Selectivity of Cu Nanocubes during CO 2 Electroreduction: Size and Support Effects
journal, April 2018


Reaction Mechanisms of Well-Defined Metal-N 4 Sites in Electrocatalytic CO 2 Reduction
journal, November 2018


Nanocrystal/Metal–Organic Framework Hybrids as Electrocatalytic Platforms for CO 2 Conversion
journal, September 2019


Structure‐Sensitivity and Electrolyte Effects in CO 2 Electroreduction: From Model Studies to Applications
journal, June 2019


Electrochemical Carbon Dioxide Splitting
journal, February 2019


Sharp‐Tipped Zinc Nanowires as an Efficient Electrocatalyst for Carbon Dioxide Reduction
journal, September 2018


Electrocatalytic Metal-Organic Frameworks for Energy Applications
journal, November 2017


Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO 2 Reduction
journal, November 2019


Electrochemical Scanning Probe Microscopies in Electrocatalysis
journal, November 2018


MOFs for Electrocatalysis: From Serendipity to Design Strategies
journal, December 2018


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane
journal, July 2019


Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen
journal, December 2019


Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface
journal, January 2020


High-rate electroreduction of carbon monoxide to multi-carbon products
journal, August 2018


Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst
journal, October 2018


Designing materials for electrochemical carbon dioxide recycling
journal, July 2019


Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis
journal, December 2019


A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis
journal, January 2018


Electrochemical processes on solid shaped nanoparticles with defined facets
journal, January 2018


Coordinatively unsaturated nickel–nitrogen sites towards selective and high-rate CO 2 electroreduction
journal, January 2018


CO 2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions
journal, January 2019


Bio-inspired design: bulk iron–nickel sulfide allows for efficient solvent-dependent CO 2 reduction
journal, January 2019


Stannate derived bimetallic nanoparticles for electrocatalytic CO 2 reduction
journal, January 2018


Stepped surface-rich copper fiber felt as an efficient electrocatalyst for the CO 2 RR to formate
journal, January 2018


Copper-modulated bismuth nanocrystals alter the formate formation pathway to achieve highly selective CO 2 electroreduction
journal, January 2018


Establishing new scaling relations on two-dimensional MXenes for CO 2 electroreduction
journal, January 2018


Accessing the C–C transition state energy on transition metals
journal, January 2019


Silicon-doped graphene edges: an efficient metal-free catalyst for the reduction of CO 2 into methanol and ethanol
journal, January 2019


Design of doped cesium lead halide perovskite as a photo-catalytic CO 2 reduction catalyst
journal, January 2019


Single metal atoms regulated flexibly by a 2D InSe substrate for CO 2 reduction electrocatalysts
journal, January 2019


Theoretical search for novel Au or Ag bimetallic alloys capable of transforming CO 2 into hydrocarbons
journal, January 2019


Atomically dispersed asymmetric Cu–B pair on 2D carbon nitride synergistically boosts the conversion of CO into C 2 products
journal, January 2020


The identification of optimal active boron sites for N 2 reduction
journal, January 2020


On the origin of the elusive first intermediate of CO 2 electroreduction
journal, September 2018


Selective reduction of CO to acetaldehyde with CuAg electrocatalysts
journal, January 2020


High-performance functional nanocomposites using 3D ordered and continuous nanostructures generated from proximity-field nanopatterning
journal, August 2019


Atomic Ni Anchored Covalent Triazine Framework as High Efficient Electrocatalyst for Carbon Dioxide Conversion
journal, March 2019


A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction
journal, October 2018


A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials
journal, December 2018


Nanocrystal/Metal–Organic Framework Hybrids as Electrocatalytic Platforms for CO 2 Conversion
journal, July 2019


Structure Sensitivity in the Electrocatalytic Reduction of CO 2 with Gold Catalysts
journal, February 2019


Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction
journal, January 2020


Engineering Metal–Organic Frameworks for the Electrochemical Reduction of CO 2 : A Minireview
journal, July 2019


Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials
journal, December 2018


Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area
journal, June 2019


Molecular tunability of surface-functionalized metal nanocrystals for selective electrochemical CO 2 reduction
journal, January 2019


Machine learning for renewable energy materials
journal, January 2019


Chemical storage of renewable energy
journal, May 2018


Structure Sensitivity in the Electrocatalytic Reduction of CO 2 with Gold Catalysts
journal, February 2019


Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction
journal, August 2018


Nano-designed semiconductors for electro- and photoelectro-catalytic conversion of carbon dioxide
journal, January 2018


Effects of Anion Identity and Concentration on Electrochemical Reduction of CO 2
journal, February 2018


Cu atomic chains supported on β-borophene sheets for effective CO 2 electroreduction
journal, January 2018


Competition between H and CO for Active Sites Governs Copper-Mediated Electrosynthesis of Hydrocarbon Fuels
journal, July 2018


Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO 2 Reduction
journal, December 2019


Copper adparticle enabled selective electrosynthesis of n-propanol
journal, November 2018


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane
journal, July 2019


Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen
journal, December 2019


Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks
journal, March 2020