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Title: Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction

Journal Article · · Nature Communications
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5];  [6];  [2];  [2];  [7];  [3]; ORCiD logo [2]
  1. South University of Science and Technology of China, Shenzhen (China); Yale Univ., New Haven, CT (United States)
  2. Yale Univ., New Haven, CT (United States)
  3. Oregon State Univ., Corvallis, OR (United States)
  4. Yale Univ., New Haven, CT (United States); Shanghai University (China)
  5. University of South China, Hengyang, Hunan (China)
  6. Northwestern Univ., Evanston, IL (United States)
  7. South University of Science and Technology of China, Shenzhen (China)

Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design of high-performance catalyst materials. We study three coppercomplex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far the highest activity for yielding methane with a Faradaic efficiency of 66% and a partial current density of 13 mA cm-2 at the potential of – 1.06 V versus the reversible hydrogen electrode. Utilizing in-situ and operando X-ray absorption spectroscopy, we find that under the working conditions copper(II) phthalocyanine undergoes reversible structural and oxidation state changes to form ~ 2 nm metallic copper clusters, which catalyzes the carbon dioxide-to-methane conversion. Density functional calculations rationalize the restructuring behavior and attribute the reversibility to the strong divalent metal ion–ligand coordination in the copper(II) phthalocyanine molecular structure and the small size of the generated copper clusters under the reaction conditions.

Research Organization:
Yale Univ., New Haven, CT (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
Grant/Contract Number:
FG02-07ER15909; AC02-06CH11357
OSTI ID:
1419868
Journal Information:
Nature Communications, Vol. 9, Issue 1; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 445 works
Citation information provided by
Web of Science

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Tailoring Copper Nanocrystals towards C 2 Products in Electrochemical CO 2 Reduction journal April 2016
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Evaluation of the Impact of Surface Reconstruction on Rough Electrodeposited Copper-Based Catalysts for Carbon Dioxide Electroreduction journal December 2016
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Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO 2 Reduction journal May 2017
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Structure-Sensitive CO 2 Electroreduction to Hydrocarbons on Ultrathin 5-fold Twinned Copper Nanowires journal January 2017
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Reconstruction of Clean and Adsorbate-Covered Metal Surfaces journal January 1996
A Pt-Cluster-Based Heterogeneous Catalyst for Homogeneous Catalytic Reactions: X-ray Absorption Spectroscopy and Reaction Kinetic Studies of Their Activity and Stability against Leaching journal August 2011
Covalent Attachment of Catalyst Molecules to Conductive Diamond: CO 2 Reduction Using “Smart” Electrodes journal September 2012
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Catalysts Transform While Molecules React: An Atomic-Scale View journal January 2013
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A nickel iron diselenide-derived efficient oxygen-evolution catalyst journal August 2016
Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures journal March 2017
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers journal January 2016
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A Porphyrin/Graphene Framework: A Highly Efficient and Robust Electrocatalyst for Carbon Dioxide Reduction journal July 2018
MOFs-Based Heterogeneous Catalysts: New Opportunities for Energy-Related CO 2 Conversion journal October 2018
A Water-Soluble Cu Complex as Molecular Catalyst for Electrocatalytic CO 2 Reduction on Graphene-Based Electrodes journal November 2018
Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO 2 by Molecular Catalysts journal May 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
Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO 2 Reduction to Formate journal November 2019
Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity journal June 2018
Electroreduction of CO 2 on Single‐Site Copper‐Nitrogen‐Doped Carbon Material: Selective Formation of Ethanol and Reversible Restructuration of the Metal Sites journal September 2019
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction journal November 2019
Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring journal November 2019
Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal March 2020
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Electroreduction of CO 2 on Single-Site Copper-Nitrogen-Doped Carbon Material: Selective Formation of Ethanol and Reversible Restructuration of the Metal Sites journal September 2019
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Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring journal November 2019
Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper journal January 2020
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Small and Narrowly Distributed Copper Nanoparticles Supported on Carbon Prepared by Surface Organometallic Chemistry for Selective Hydrogenation and CO 2 Electroconversion Processes journal October 2019
A Facile Route for Constructing Effective Cu−N x Active Sites for Oxygen Reduction Reaction journal December 2019
Structure‐Tunable Copper–Indium Catalysts for Highly Selective CO 2 Electroreduction to CO or HCOOH journal August 2019
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Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO2 journal October 2018
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Figures / Tables (4)