skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Copper nanoparticle ensembles for selective electroreduction of CO 2 to C 2 –C 3 products

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
ORCiD logo; ; ;

Direct conversion of carbon dioxide to multicarbon products remains as a grand challenge in electrochemical CO2 reduction. Various forms of oxidized copper have been demonstrated as electrocatalysts that still require large overpotentials. Here in this paper, we show that an ensemble of Cu nanoparticles (NPs) enables selective formation of C2–C3 products at low overpotentials. Densely packed Cu NP ensembles underwent structural transformation during electrolysis into electrocatalytically active cube-like particles intermixed with smaller nanoparticles. Ethylene, ethanol, and n-propanol are the major C2–C3 products with onset potential at -0.53 V (vs. reversible hydrogen electrode, RHE) and C2–C3 faradaic efficiency (FE) reaching 50% at only -0.75 V. Thus, the catalyst exhibits selective generation of C2–C3 hydrocarbons and oxygenates at considerably lowered overpotentials in neutral pH aqueous media. In addition, this approach suggests new opportunities in realizing multicarbon product formation from CO2, where the majority of efforts has been to use oxidized copper-based materials. Robust catalytic performance is demonstrated by 10 h of stable operation with C2–C3 current density 10 mA/cm2 (at -0.75 V), rendering it attractive for solar-to-fuel applications. Lastly, Tafel analysis suggests reductive CO coupling as a rate determining step for C2 products, while n-propanol (C3) production seems to have a discrete pathway.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1392689
Alternate ID(s):
OSTI ID: 1426737
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 114 Journal Issue: 40; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 418 works
Citation information provided by
Web of Science

References (52)

Mesostructure-Induced Selectivity in CO 2 Reduction Catalysis journal November 2015
Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes journal June 2013
Electrochemical CO 2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution journal June 2016
Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO 2 over Ag and Cu journal September 2016
Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid journal July 2016
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper journal April 2014
Electrochemical CO2 Reduction on Metal Electrodes book January 2008
Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO 2 Electroreduction by Process Conditions journal December 2014
Morphology Matters: Tuning the Product Distribution of CO 2 Electroreduction on Oxide-Derived Cu Foam Catalysts journal May 2016
Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS journal November 2016
Electrocatalytic Production of C3-C4 Compounds by Conversion of CO 2 on a Chloride-Induced Bi-Phasic Cu 2 O-Cu Catalyst journal October 2015
Active and Selective Conversion of CO 2 to CO on Ultrathin Au Nanowires journal November 2014
Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals journal January 2015
Ag–Sn Bimetallic Catalyst with a Core–Shell Structure for CO 2 Reduction journal January 2017
Mechanistic Insights into the Selective Electroreduction of Carbon Dioxide to Ethylene on Cu 2 O-Derived Copper Catalysts journal September 2016
Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes journal May 2003
Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel journal January 2016
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH journal February 2016
Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu x Zn Catalysts journal November 2016
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts journal February 2015
Electrochemical Reduction of Carbon Dioxide to Ethane Using Nanostructured Cu 2 O-Derived Copper Catalyst and Palladium(II) Chloride journal November 2015
Electrochemical CO 2 reduction on Cu 2 O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons journal January 2014
Synergistic Electrochemical CO 2 Reduction and Water Oxidation with a Bipolar Membrane journal November 2016
Nanoporous Copper Films by Additive-Controlled Electrodeposition: CO 2 Reduction Catalysis journal April 2017
Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols journal April 2017
A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates journal December 2016
Electrochemical Reduction of CO 2 Using Copper Single-Crystal Surfaces: Effects of CO* Coverage on the Selective Formation of Ethylene journal February 2017
Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts journal September 2014
High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode journal September 2016
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts journal March 2015
Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions journal January 2016
Mechanistic Insights into the Enhanced Activity and Stability of Agglomerated Cu Nanocrystals for the Electrochemical Reduction of Carbon Dioxide to n -Propanol journal December 2015
Tailoring Copper Nanocrystals towards C 2 Products in Electrochemical CO 2 Reduction journal April 2016
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration journal August 2016
Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst journal September 2014
Artificial Photosynthesis for Sustainable Fuel and Chemical Production journal January 2015
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene journal June 2016
Insights into an autonomously formed oxygen-evacuated Cu 2 O electrode for the selective production of C 2 H 4 from CO 2 journal January 2015
Selectivity on Etching: Creation of High-Energy Facets on Copper Nanocrystals for CO 2 Electrochemical Reduction journal March 2016
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles journal September 2014
Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface journal June 2016
CO 2 Electroreduction with Enhanced Ethylene and Ethanol Selectivity by Nanostructuring Polycrystalline Copper journal April 2016
Electrolysis of CO 2 to Syngas in Bipolar Membrane-Based Electrochemical Cells journal November 2016
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces journal January 2012
Water splitting–biosynthetic system with CO 2 reduction efficiencies exceeding photosynthesis journal June 2016
Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation journal March 2015
Research opportunities to advance solar energy utilization journal January 2016
Aqueous CO 2 Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles journal November 2012
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes journal February 2017
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide journal September 2015
Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction journal December 2016
One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer journal January 2016

Similar Records

The presence and role of the intermediary CO reservoir in heterogeneous electroreduction of CO 2
Journal Article · Fri Apr 29 00:00:00 EDT 2022 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1392689
+4 more
Photoelectrochemical CO2 Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles
Journal Article · Wed Apr 27 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1392689
+3 more
Switching CO2 Electroreduction Selectivity Between C1 and C2 Hydrocarbons on Cu Gas-Diffusion Electrodes
Journal Article · Tue Nov 02 00:00:00 EDT 2021 · Energy & Environmental Materials · OSTI ID:1392689
+6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
30 DIRECT ENERGY CONVERSION
heterogeneous catalysis
electrocatalysis
CO2 reduction
copper nanoparticles
in situ structural transformation