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

Abstract

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.

Authors:
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)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1419868
Grant/Contract Number:  
FG02-07ER15909; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, and Wang, Hailiang. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. United States: N. p., 2018. Web. doi:10.1038/s41467-018-02819-7.
Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, & Wang, Hailiang. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. United States. https://doi.org/10.1038/s41467-018-02819-7
Weng, Zhe, Wu, Yueshen, Wang, Maoyu, Jiang, Jianbing, Yang, Ke, Huo, Shengjuan, Wang, Xiao-Feng, Ma, Qing, Brudvig, Gary W., Batista, Victor S., Liang, Yongye, Feng, Zhenxing, and Wang, Hailiang. Mon . "Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction". United States. https://doi.org/10.1038/s41467-018-02819-7. https://www.osti.gov/servlets/purl/1419868.
@article{osti_1419868,
title = {Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction},
author = {Weng, Zhe and Wu, Yueshen and Wang, Maoyu and Jiang, Jianbing and Yang, Ke and Huo, Shengjuan and Wang, Xiao-Feng and Ma, Qing and Brudvig, Gary W. and Batista, Victor S. and Liang, Yongye and Feng, Zhenxing and Wang, Hailiang},
abstractNote = {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.},
doi = {10.1038/s41467-018-02819-7},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Mon Jan 29 00:00:00 EST 2018},
month = {Mon Jan 29 00:00:00 EST 2018}
}

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Figures / Tables:

Fig. 1 Fig. 1: Molecular structures of three Cu-complex materials and their electrocatalytic performance for CO2 reduction. Molecular structures of a CuPc, b HKUST-1, and c [Cu(cyclam)]Cl2. Potential-dependent d Faradaic efficiencies and e partial current densities of products for CO2 electroreduction reaction catalyzed by CuPc. Comparison of f Faradaic efficiency and gmore » partial current density distributions among CO2 electroreduction reactions catalyzed by the three materials at – 1.06 V vs RHE. Error bars represent the SD from multiple measurements« less

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Active sites of ligand-protected Au 25 nanoparticle catalysts for CO 2 electroreduction to CO
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Electrocatalytic CO2 Conversion to Oxalate by a Copper Complex
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A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
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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

  • Karapinar, Dilan; Huan, Ngoc Tran; Ranjbar Sahraie, Nastaran
  • Angewandte Chemie, Vol. 131, Issue 42
  • DOI: 10.1002/ange.201907994

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
journal, November 2019

  • Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha
  • Angewandte Chemie, Vol. 131, Issue 52
  • DOI: 10.1002/ange.201909312

Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring
journal, November 2019

  • Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
  • Angewandte Chemie, Vol. 131, Issue 47
  • DOI: 10.1002/ange.201910155

Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper
journal, March 2020


Highly Selective Photoreduction of CO 2 with Suppressing H 2 Evolution over Monolayer Layered Double Hydroxide under Irradiation above 600 nm
journal, July 2019

  • Tan, Ling; Xu, Si-Min; Wang, Zelin
  • Angewandte Chemie International Edition, Vol. 58, Issue 34
  • DOI: 10.1002/anie.201904246

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

  • Karapinar, Dilan; Huan, Ngoc Tran; Ranjbar Sahraie, Nastaran
  • Angewandte Chemie International Edition, Vol. 58, Issue 42
  • DOI: 10.1002/anie.201907994

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
journal, November 2019

  • Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha
  • Angewandte Chemie International Edition, Vol. 58, Issue 52
  • DOI: 10.1002/anie.201909312

Selective CO 2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring
journal, November 2019

  • Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
  • Angewandte Chemie International Edition, Vol. 58, Issue 47
  • DOI: 10.1002/anie.201910155

Hydroxide Is Not a Promoter of C 2+ Product Formation in the Electrochemical Reduction of CO on Copper
journal, January 2020

  • Li, Jing; Wu, Donghuan; Malkani, Arnav S.
  • Angewandte Chemie International Edition, Vol. 59, Issue 11
  • DOI: 10.1002/anie.201912412

Molecular Evidence for Metallic Cobalt Boosting CO 2 Electroreduction on Pyridinic Nitrogen
journal, February 2020

  • He, Chao; Zhang, Yun; Zhang, Yuefeng
  • Angewandte Chemie International Edition, Vol. 59, Issue 12
  • DOI: 10.1002/anie.201916520

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


Carbon‐Nanotube‐Supported Copper Polyphthalocyanine for Efficient and Selective Electrocatalytic CO 2 Reduction to CO
journal, November 2019


A wavelength‐dispersive X‐ray spectrometer for in/ex situ resonant inelastic X‐ray scattering studies
journal, April 2019

  • Mei, Bingbao; Gu, Songqi; Du, Xianlong
  • X-Ray Spectrometry, Vol. 49, Issue 1
  • DOI: 10.1002/xrs.3132

Heterogeneous molecular catalysts for electrocatalytic CO2 reduction
journal, May 2019


In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts
journal, June 2019


Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO2
journal, October 2018


Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides
journal, April 2019


Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction
journal, June 2019


Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells
journal, October 2018


Designing materials for electrochemical carbon dioxide recycling
journal, July 2019


A water stable microporous metal–organic framework based on rod SBUs: synthesis, structure and adsorption properties
journal, January 2018

  • Yuan, Jiaqi; Mu, Li; Li, Jiantang
  • CrystEngComm, Vol. 20, Issue 15
  • DOI: 10.1039/c8ce00064f

Efficient electroreduction of CO 2 to C2 products over B-doped oxide-derived copper
journal, January 2018

  • Chen, Chunjun; Sun, Xiaofu; Lu, Lu
  • Green Chemistry, Vol. 20, Issue 20
  • DOI: 10.1039/c8gc02389a

Superaerophilic copper nanowires for efficient and switchable CO 2 electroreduction
journal, January 2019

  • Zhang, Yusheng; Cai, Zhao; Zhao, Yuxin
  • Nanoscale Horizons, Vol. 4, Issue 2
  • DOI: 10.1039/c8nh00259b

Nanoassemblies of ultrasmall clusters with remarkable activity in carbon dioxide conversion into C1 fuels
journal, January 2019

  • Halder, Avik; Kioseoglou, Joseph; Yang, Bing
  • Nanoscale, Vol. 11, Issue 11
  • DOI: 10.1039/c8nr06664g

Two unique copper cluster-based metal–organic frameworks with high performance for CO 2 adsorption and separation
journal, January 2019

  • Yuan, Jiaqi; Li, Jiantang; Che, Songtian
  • Inorganic Chemistry Frontiers, Vol. 6, Issue 2
  • DOI: 10.1039/c8qi01315b

Enhanced CO 2 electroreduction via interaction of dangling S bonds and Co sites in cobalt phthalocyanine/ZnIn 2 S 4 hybrids
journal, January 2019

  • Chen, Chunjun; Sun, Xiaofu; Yang, Dexin
  • Chemical Science, Vol. 10, Issue 6
  • DOI: 10.1039/c8sc03986k

Cathodized copper porphyrin metal–organic framework nanosheets for selective formate and acetate production from CO 2 electroreduction
journal, January 2019

  • Wu, Jian-Xiang; Hou, Shu-Zhen; Zhang, Xiang-Da
  • Chemical Science, Vol. 10, Issue 7
  • DOI: 10.1039/c8sc04344b

Sub-5 nm SnO 2 chemically coupled hollow carbon spheres for efficient electrocatalytic CO 2 reduction
journal, January 2018

  • Yiliguma, Yiliguma; Wang, Zhijie; Yang, Chao
  • Journal of Materials Chemistry A, Vol. 6, Issue 41
  • DOI: 10.1039/c8ta08058e

3D core–shell porous-structured Cu@Sn hybrid electrodes with unprecedented selective CO 2 -into-formate electroreduction achieving 100%
journal, January 2019

  • Hou, Xiaofan; Cai, Yixiao; Zhang, Dan
  • Journal of Materials Chemistry A, Vol. 7, Issue 7
  • DOI: 10.1039/c8ta10650a

Surface strategies for catalytic CO 2 reduction: from two-dimensional materials to nanoclusters to single atoms
journal, January 2019

  • Wang, Liming; Chen, Wenlong; Zhang, Doudou
  • Chemical Society Reviews, Vol. 48, Issue 21
  • DOI: 10.1039/c9cs00163h

An MOF-derived copper@nitrogen-doped carbon composite: the synergistic effects of N-types and copper on selective CO 2 electroreduction
journal, January 2019

  • Cheng, Yuan-Sheng; Chu, Xin-Ping; Ling, Min
  • Catalysis Science & Technology, Vol. 9, Issue 20
  • DOI: 10.1039/c9cy01131e

3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity
journal, January 2019

  • Qiao, Zhi; Hwang, Sooyeon; Li, Xing
  • Energy & Environmental Science, Vol. 12, Issue 9
  • DOI: 10.1039/c9ee01899a

Electrocatalytic reduction of carbon dioxide: opportunities with heterogeneous molecular catalysts
journal, January 2020

  • Sun, Libo; Reddu, Vikas; Fisher, Adrian C.
  • Energy & Environmental Science, Vol. 13, Issue 2
  • DOI: 10.1039/c9ee03660a

Facile synthesis of polymerized cobalt phthalocyanines for highly efficient CO 2 reduction
journal, January 2019

  • Chen, Jiacheng; Li, Jiayu; Liu, Weiliang
  • Green Chemistry, Vol. 21, Issue 22
  • DOI: 10.1039/c9gc02705j

Engineering ultrasmall metal nanoclusters for photocatalytic and electrocatalytic applications
journal, January 2019

  • Chai, Osburg Jin Huang; Liu, Zhihe; Chen, Tiankai
  • Nanoscale, Vol. 11, Issue 43
  • DOI: 10.1039/c9nr07272a

Accelerated proton transmission in metal–organic frameworks for the efficient reduction of CO 2 in aqueous solutions
journal, January 2019

  • Mao, Fangxin; Jin, Yan-Huan; Liu, Peng Fei
  • Journal of Materials Chemistry A, Vol. 7, Issue 40
  • DOI: 10.1039/c9ta07967j

Current progress in electrocatalytic carbon dioxide reduction to fuels on heterogeneous catalysts
journal, January 2020

  • Liu, Anmin; Gao, Mengfan; Ren, Xuefeng
  • Journal of Materials Chemistry A, Vol. 8, Issue 7
  • DOI: 10.1039/c9ta11966c

The Impact of Different Si Surface Terminations in the (100) p-Si | n + -Si | Cu Junction with Respect to the Photo Electrochemical Performance
journal, January 2019

  • Steinert, Céline; Tengeler, Sven; Kaiser, Bernhard
  • Journal of The Electrochemical Society, Vol. 166, Issue 5
  • DOI: 10.1149/2.0291905jes

Emerging Carbon‐Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value‐Added Chemicals
journal, December 2018


Copper and Copper-Based Bimetallic Catalysts for Carbon Dioxide Electroreduction
journal, October 2018

  • Birhanu, Mulatu Kassie; Tsai, Meng-Che; Kahsay, Amaha Woldu
  • Advanced Materials Interfaces, Vol. 5, Issue 24
  • DOI: 10.1002/admi.201800919

Molecular Evidence for Metallic Cobalt Boosting CO 2 Electroreduction on Pyridinic Nitrogen
journal, February 2020


Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity
journal, June 2018

  • Cai, Zhao; Zhou, Daojin; Wang, Maoyu
  • Angewandte Chemie International Edition, Vol. 57, Issue 30
  • DOI: 10.1002/anie.201804881

Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution
journal, December 2018


From CO 2 methanation to ambitious long-chain hydrocarbons: alternative fuels paving the path to sustainability
journal, January 2019

  • Marques Mota, Filipe; Kim, Dong Ha
  • Chemical Society Reviews, Vol. 48, Issue 1
  • DOI: 10.1039/c8cs00527c

Highly efficient electroconversion of carbon dioxide into hydrocarbons by cathodized copper–organic frameworks
journal, January 2019

  • Yang, Fan; Chen, Aling; Deng, Pei Lin
  • Chemical Science, Vol. 10, Issue 34
  • DOI: 10.1039/c9sc02605c

Ultrafast X-ray Absorption Studies of the Structural Dynamics of Molecular and Biological Systems in Solution
journal, May 2011

  • Milne, Christopher J.; Van der Veen, Renske M.; Pham, Van-Thai
  • CHIMIA International Journal for Chemistry, Vol. 65, Issue 5
  • DOI: 10.2533/chimia.2011.303

Selective $CO_{2}$ Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring
text, January 2019

  • Gao, Dunfeng; Sinev, Ilya; Scholten, Fabian
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2020-00548

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


Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2
journal, April 2018


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


Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides
journal, April 2019


Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction
journal, June 2019


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


Membrane-Modified Metal Triazole Complexes for the Electrocatalytic Reduction of Oxygen and Carbon Dioxide
journal, November 2018


In-situ Spectroscopic Techniques as Critical Evaluation Tools for Electrochemical Carbon dioxide Reduction: A Mini Review
journal, March 2020

  • Adarsh, K. S.; Chandrasekaran, Naveen; Chakrapani, Vidhya
  • Frontiers in Chemistry, Vol. 8
  • DOI: 10.3389/fchem.2020.00137

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.