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Stabilization of a co-bound intermediate via molecular tuning promotes CO2-to-ethylene conversion

Patent ·
OSTI ID:2222302
; ; ; ; ;
Aspects included herein include an electrolytic system for electrochemical reduction of carbon dioxide, the system comprising: a cathode comprising: a porous gas-diffusion membrane permeable to CO2; an electrocatalyst layer adjacent to a second side of the gas-diffusion membrane; the electrocatalyst layer comprising: an electrically conductive catalyst; and a selectivity-determining organic material attached to at least a portion of the electrically conductive catalyst; wherein: the organic material is formed of a plurality of oligomers; each oligomer comprises a plurality of covalently bonded base units; each base unit comprises at least one heterocyclic group having at least one nitrogen in its structure; and an anion exchange membrane adjacent to the electrocatalyst layer and positioned between the anode and the cathode; wherein anion exchange membrane is characterized by anion conductivity and the cathode is in ionic communication with the anode via the anion exchange membrane.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); California Institute of Technology (CalTech), Pasadena, CA (United States); Univ. of Toronto, ON (Canada)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC02-06CH11357; SC0004993
Assignee:
California Institute of Technology (Pasadena, CA); The Governing Council of the University of Toronto (Toronto, CA)
Patent Number(s):
11,746,426
Application Number:
16/925,833
OSTI ID:
2222302
Country of Publication:
United States
Language:
English

References (127)

Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations journal December 2007
Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO 2 journal April 2016
Selective Electroreduction of CO 2 toward Ethylene on Nano Dendritic Copper Catalysts at High Current Density journal January 2017
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry journal January 2003
Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes journal June 2013
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts journal February 2015
Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO 2 over Cu Nanowire Arrays journal April 2016
Morphology-Directed Selective Production of Ethylene or Ethane from CO 2 on a Cu Mesopore Electrode journal December 2016
Nanostructured Materials for Heterogeneous Electrocatalytic CO 2 Reduction and their Related Reaction Mechanisms journal July 2017
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes journal February 2017
Bridging the Gap between Industrial and Well-Defined Supported Catalysts journal March 2018
Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction Investigated with 18 O Labeling journal December 2017
Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO 2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry journal March 2018
Dynamic Changes in the Structure, Chemical State and Catalytic Selectivity of Cu Nanocubes during CO 2 Electroreduction: Size and Support Effects journal April 2018
In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO 2 Reduction to Ethylene journal October 2019
Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO 2 Electroreduction by Process Conditions journal December 2014
CO 2 Electroreduction with Enhanced Ethylene and Ethanol Selectivity by Nanostructuring Polycrystalline Copper journal April 2016
X-ray Photoelectron Spectroscopy of Pyridinium-Based Ionic Liquids: Comparison to Imidazolium- and Pyrrolidinium-Based Analogues journal May 2015
Study of Pyridine-Mediated Electrochemical Reduction of CO 2 to Methanol at High CO 2 Pressure journal June 2016
Evaluation of the Impact of Surface Reconstruction on Rough Electrodeposited Copper-Based Catalysts for Carbon Dioxide Electroreduction journal December 2016
Vibrational modes of CO adsorbed on disordered copper films journal December 1991
Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions journal October 2005
Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights journal November 2014
The coordination chemistry of 2-pyridone and its derivatives journal February 1995
Polypyrrole films containing metal complexes: syntheses and applications journal January 1996
Electrocatalytic reduction of CO2 on electrodes modified by fac-Re(2,2'-bipyridine)(CO)3Cl complexes bonded to polypyrrole films journal May 1988
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Study of the electrochemical reduction of CO2 on a polypyrrole electrode modified by rhenium and copper–rhenium microalloy in methanol media journal September 2002
Oxygen electrosorption on copper single crystal electrodes in sodium hydroxide solution journal September 1980
Electroreduction of CO2 catalyzed by polymeric [Ru(bpy)(CO)2]n films in aqueous media: Parameters influencing the reaction selectivity journal March 1998
Chemical constitution and activity of bipyridylium herbicides—II journal January 1968
Chemical constitution and activity of bipyridylium herbicides—III journal January 1968
An Ir-based anode for a practical CO2 electrolyzer journal June 2017
Electrocatalytic pathways towards sustainable fuel production from water and CO2 journal November 2012
Nitrogen-containing polymers as a platform for CO2 electroreduction journal June 2017
A fast and robust algorithm for Bader decomposition of charge density journal June 2006
Nanoscale corrosion behavior of polycrystalline copper fine wires in dilute NaCl solution investigated by in-situ atomic force microscopy journal April 2016
Potential–pH diagrams for hydroxyl and hydrogen adsorbed on a copper surface journal October 2005
Electrochemical specific adsorption of halides on Cu 111 , 100 , and 211 : A Density Functional Theory study journal August 2015
Continuous Carbon Dioxide Electroreduction to Concentrated Multi-carbon Products Using a Membrane Electrode Assembly journal November 2019
One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer journal January 2016
An efficient ultrasonic-assisted synthesis of imidazolium and pyridinium salts based on the Zincke reaction journal April 2010
Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts journal March 2016
Structure- and Electrolyte-Sensitivity in CO 2 Electroreduction journal October 2018
General Techno-Economic Analysis of CO 2 Electrolysis Systems journal February 2018
CO 2 Reduction on Cu at Low Overpotentials with Surface-Enhanced in Situ Spectroscopy journal July 2016
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction journal June 2017
Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO 2 Reduction journal May 2017
Revealing the Synergy of Mono/Bimetallic PdPt/TiO 2 Heterostructure for Enhanced Photoresponse Performance journal October 2017
Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO 2 Reduction journal October 2017
Potential Routes and Mitigation Strategies for Contamination in Interfacial Specific Infrared Spectroelectrochemical Studies journal September 2018
First-Principles Determination of CO Adsorption and Desorption on Pt(111) in the Free Energy Landscape journal August 2018
Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction journal May 2015
High-Density Nanosharp Microstructures Enable Efficient CO 2 Electroreduction journal October 2016
Structure-Sensitive CO 2 Electroreduction to Hydrocarbons on Ultrathin 5-fold Twinned Copper Nanowires journal January 2017
Synthesis of Conjugated Polycyclic Quinoliniums by Rhodium(III)-Catalyzed Multiple C–H Activation and Annulation of Arylpyridiniums with Alkynes journal May 2016
Impurity Ion Complexation Enhances Carbon Dioxide Reduction Catalysis journal June 2015
In Situ Spectroscopic Study of CO 2 Electroreduction at Copper Electrodes in Acetonitrile journal March 2016
Tuning the Catalytic Activity and Selectivity of Cu for CO 2 Electroreduction in the Presence of Halides journal February 2016
Insight into Electrochemical CO 2 Reduction on Surface-Molecule-Mediated Ag Nanoparticles 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
Improved CO 2 Electroreduction Performance on Plasma-Activated Cu Catalysts via Electrolyte Design: Halide Effect journal July 2017
Prism-Shaped Cu Nanocatalysts for Electrochemical CO 2 Reduction to Ethylene journal December 2017
Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH journal July 2018
CO 2 Reduction Selective for C ≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives journal July 2017
Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction journal September 2017
Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives journal February 2017
Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm journal December 2018
Achieving Highly Efficient, Selective, and Stable CO 2 Reduction on Nitrogen-Doped Carbon Nanotubes journal April 2015
Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols journal April 2017
Selective Electrocatalytic Reduction of CO2 on Electroprepared [Ru(L)(CO)2]n Polymeric Film: L = 2,2′-Bipyridine Derivatives book October 2002
Comparative Study of Imidazole and Pyridine Catalyzed Reduction of Carbon Dioxide at Illuminated Iron Pyrite Electrodes journal July 2012
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts journal March 2015
Soluble Redox-Active Polymetallic Chains [{Ru0(CO)(L)(bpy)}m]n (bpy = 2,2′-bipyridine, L = PrCN, Cl−; m = 0, −1): Electrosynthesis and Characterization journal August 2009
Using a One-Electron Shuttle for the Multielectron Reduction of CO2 to Methanol: Kinetic, Mechanistic, and Structural Insights
  • Barton Cole, Emily; Lakkaraju, Prasad S.; Rampulla, David M.
  • Journal of the American Chemical Society, Vol. 132, Issue 33, p. 11539-11551 https://doi.org/10.1021/ja1023496
journal August 2010
CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films journal April 2012
Achieving Selective and Efficient Electrocatalytic Activity for CO 2 Reduction Using Immobilized Silver Nanoparticles journal October 2015
Mesostructure-Induced Selectivity in CO 2 Reduction Catalysis journal November 2015
Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111) journal January 2016
New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO 2 on a Silver Electrode journal June 2016
Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns journal December 2016
Electrochemical Activation of CO 2 through Atomic Ordering Transformations of AuCu Nanoparticles journal June 2017
Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO 2 Reduction journal June 2018
Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products journal July 2018
The “Missing” Bicarbonate in CO 2 Chemisorption Reactions on Solid Amine Sorbents journal June 2018
Solubility of Carbon Dioxide in Aqueous HCl and NaHCO 3 Solutions from 278 to 298 K journal May 2005
Preparation of (p-phenylene)bis(aryliodonium) ditriflates and their double substitution by some nucleophiles journal December 1992
Using a Two-Step Hydride Transfer To Achieve 1,4-Reduction in the Catalytic Hydrogenation of an Acyl Pyridinium Cation journal December 2008
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode journal November 2004
Effect of CO 2 Bubbling into Aqueous Solutions Used for Electrochemical Reduction of CO 2 for Energy Conversion and Storage journal December 2014
Diffusion and Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Nitrogen Dioxide through Polytetrafluoroethylene journal May 1970
Cyclic Diquaternary Salts of 1,10-Phenanthroline as One Electron Transfer Agents related to Bipyridylium Herbicides journal September 1967
Nanostructured electrocatalysts with tunable activity and selectivity journal March 2016
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper journal April 2014
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene journal June 2016
Materials for solar fuels and chemicals journal December 2016
Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons journal July 2018
Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction journal January 2018
Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction journal January 2018
Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts journal June 2018
Efficient electrocatalytic CO2 reduction on a three-phase interface journal July 2018
Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide journal October 2018
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels journal January 2014
Microporous carbonaceous adsorbents for CO 2 separation via selective adsorption journal January 2015
Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts journal January 2016
CO 2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions journal January 2019
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces journal January 2012
The kinetics of methoxydechlorination of 5-chloro-1,10-phenanthroline and some related reactions journal January 1979
Unusually Facile Syntheses of Diquat (6,7-Dihydrodipyrido[1,2- a :2′,1′- c ]pyrazinediium) and Related Cations journal January 2006
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Engineering Cu surfaces for the electrocatalytic conversion of CO 2 : Controlling selectivity toward oxygenates and hydrocarbons journal May 2017
Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2 , the first step in reduction of CO 2 journal June 2017
Cu metal embedded in oxidized matrix catalyst to promote CO 2 activation and CO dimerization for electrochemical reduction of CO 2 journal June 2017
Copper nanoparticle ensembles for selective electroreduction of CO 2 to C 2 –C 3 products journal September 2017
Ab initiomolecular dynamics for liquid metals journal January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal May 1994
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Generalized Gradient Approximation Made Simple journal October 1996
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials journal September 2011
Combining theory and experiment in electrocatalysis: Insights into materials design journal January 2017
CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface journal May 2018
What would it take for renewably powered electrosynthesis to displace petrochemical processes? journal April 2019
Analysis of Oxygen-Transport Diffusion Resistance in Proton-Exchange-Membrane Fuel Cells journal January 2011
PRODUCTION OF CO AND CH 4 IN ELECTROCHEMICAL REDUCTION OF CO 2 AT METAL ELECTRODES IN AQUEOUS HYDROGENCARBONATE SOLUTION journal November 1985

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