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Title: pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper

Journal Article · · Nature Communications
 [1];  [1];  [2];  [3];  [1];  [1];  [1];  [1];  [1];  [1];  [4];  [1];  [5];  [6]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); Westlake Univ., Hangzhou (China)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Guangzhou Univ., Guangzhou (China)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
+ Show Author Affiliations

Here, we present a microkinetic model for CO(2) reduction (CO(2)R) on Cu(211) towards C2 products, based on energetics estimated from an explicit solvent model. We show that the differences in both Tafel slopes and pH dependence for C1 vs C2 activity arise from differences in their multi-step mechanisms. We find the depletion in C2 products observed at high overpotential and high pH to arise from the 2nd order dependence of C-C coupling on CO coverage, which decreases due to competition from the C1 pathway. We further demonstrate that CO(2) reduction at a fixed pH yield similar activities, due to the facile kinetics for CO2 reduction to CO on Cu, which suggests C2 products to be favored for CO2R under alkaline conditions. The mechanistic insights of this work elucidate how reaction conditions can lead to significant enhancements in selectivity and activity towards higher value C2 products.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1487380
Alternate ID(s):
OSTI ID: 1529394
Journal Information:
Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 362 works
Citation information provided by
Web of Science

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Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111) journal January 2016
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Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes journal February 2017
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Theoretical insight on reactivity trends in CO 2 electroreduction across transition metals journal January 2016
Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0 journal November 2015
Understanding trends in electrochemical carbon dioxide reduction rates journal May 2017
Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper journal December 2015
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes journal February 2017
The absolute electrode potential: an explanatory note (Recommendations 1986) journal September 1986
Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes journal June 2013
Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps journal January 2013
Acetaldehyde As an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper journal April 2016
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces text January 2003
Structure and Vibrations of the Vicinal Copper (211) Surface text January 1997
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide journal March 2016
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes journal February 2017
Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps journal January 2013
A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2 journal June 2016
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends journal February 2015
Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media journal August 1994
Modeling the electrified solid–liquid interface journal November 2008
Avoiding pitfalls in the modeling of electrochemical interfaces journal January 2013
On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces journal November 2013
Reaction mechanisms of CO2 electrochemical reduction on Cu(111) determined with density functional theory journal April 2014
CO adsorption energies on metals with correction for high coordination adsorption sites – A density functional study journal April 2007
Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO 2 Reduction journal May 2017
Theoretical Investigations of Transition Metal Surface Energies under Lattice Strain and CO Environment journal May 2018
Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction journal May 2015
Electrochemical Barriers Made Simple journal June 2015
Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0 journal November 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
Potential Dependence of Electrochemical Barriers from ab Initio Calculations journal April 2016
Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media journal May 2017
Mechanistic Insights into the Reduction of CO 2 on Tin Electrodes using in Situ ATR-IR Spectroscopy journal March 2015
Facet Dependence of CO 2 Reduction Paths on Cu Electrodes journal December 2015
In Situ Spectroscopic Study of CO 2 Electroreduction at Copper Electrodes in Acetonitrile journal March 2016
Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products journal January 2018
Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products journal July 2018
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation journal June 2013
Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes journal June 2012
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces journal August 2014
Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111) journal January 2016
Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C 2+ Oxygenate Production journal March 2016
Unifying Kinetic and Thermodynamic Analysis of 2 e – and 4 e – Reduction of Oxygen on Metal Surfaces journal March 2014
Electrochemical Reduction of CO at a Copper Electrode journal September 1997
Structure of the First Solvation Shell of the Hydroxide Anion. A Model Study Using OH - (H 2 O) n ( n = 4, 5, 6, 7, 11, 17) Clusters journal October 1997
Controlling Catalytic Selectivities during CO 2 Electroreduction on Thin Cu Metal Overlayers journal July 2013
Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption journal February 2013
Understanding trends in electrochemical carbon dioxide reduction rates journal May 2017
Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion journal May 2017
Construction of Pd-Zn dual sites to enhance the performance for ethanol electro-oxidation reaction journal September 2021
Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction journal January 2018
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces journal January 2012
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
Hydration of metal surfaces can be dynamically heterogeneous and hydrophobic journal February 2013
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal September 2009
Combining theory and experiment in electrocatalysis: Insights into materials design journal January 2017
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces text January 2003

Cited By (22)

Electrode Materials Engineering in Electrocatalytic CO 2 Reduction: Energy Input and Conversion Efficiency journal October 2019
Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal March 2020
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal March 2020
Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal January 2020
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal February 2020
Structure‐Tunable Copper–Indium Catalysts for Highly Selective CO 2 Electroreduction to CO or HCOOH journal August 2019
Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane journal July 2019
Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold journal January 2020
Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen journal December 2019
Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface journal August 2019
Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface journal January 2020
Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate journal April 2019
Designing materials for electrochemical carbon dioxide recycling journal July 2019
Mechanistic study on Cu-catalyzed CO 2 electroreduction into CH 4 at simulated low overpotentials based on an improved electrochemical model 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
Atomically dispersed asymmetric Cu–B pair on 2D carbon nitride synergistically boosts the conversion of CO into C 2 products journal January 2020
Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials journal January 2020
Selective reduction of CO to acetaldehyde with CuAg electrocatalysts journal January 2020
Cover Picture: Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper (Angew. Chem. Int. Ed. 11/2020) journal January 2020
Titelbild: Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper (Angew. Chem. 11/2020) journal March 2020
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

Figures / Tables (5)

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