Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products

Abstract CO2 electroreduction is a potential pathway to achieve net-zero emissions in the chemical industry. Yet, CO2 loss, resulting from (bi)carbonate formation, renders the process energy-intensive. Acidic environments can address the issue but at the expense of compromised product Faradaic effic...

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Main Authors: Huiying Deng, Tingting Liu, Wenshan Zhao, Jundong Wang, Yuesheng Zhang, Shuzhen Zhang, Yu Yang, Chao Yang, Wenzhi Teng, Zhuo Chen, Gengfeng Zheng, Fengwang Li, Yaqiong Su, Jingshu Hui, Yuhang Wang
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54107-2
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author Huiying Deng
Tingting Liu
Wenshan Zhao
Jundong Wang
Yuesheng Zhang
Shuzhen Zhang
Yu Yang
Chao Yang
Wenzhi Teng
Zhuo Chen
Gengfeng Zheng
Fengwang Li
Yaqiong Su
Jingshu Hui
Yuhang Wang
author_facet Huiying Deng
Tingting Liu
Wenshan Zhao
Jundong Wang
Yuesheng Zhang
Shuzhen Zhang
Yu Yang
Chao Yang
Wenzhi Teng
Zhuo Chen
Gengfeng Zheng
Fengwang Li
Yaqiong Su
Jingshu Hui
Yuhang Wang
author_sort Huiying Deng
collection DOAJ
description Abstract CO2 electroreduction is a potential pathway to achieve net-zero emissions in the chemical industry. Yet, CO2 loss, resulting from (bi)carbonate formation, renders the process energy-intensive. Acidic environments can address the issue but at the expense of compromised product Faradaic efficiencies (FEs), particularly for multi-carbon (C2+) products, as rapid diffusion and migration of protons (H+) favors competing H2 and CO production. Here, we present a strategy of tuning the 2-position substituent length on benzimidazole (BIM)-based copper (Cu) coordination polymer (CuCP) precatalyst – to enhance CO2 reduction to C2+ products in acidic environments. Lengthening the substituent from H to nonyl enhances H+ diffusion retardation and decreases Cu-Cu coordination numbers (CNs), favoring further reduction of CO. This leads to a nearly 24× enhancement of selectivity towards CO hydrogenation and C-C coupling at 60 mA cm−2. We report the highest C2+ product FE of more than 70% at 260 mA cm−2 on pentyl-CuCP and demonstrate a CO2-to-C2+ single-pass conversion (SPC) of ~54% at 180 mA cm−2 using pentyl-CuCP in zero-gap electrolyzers.
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publishDate 2024-11-01
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spelling doaj-art-1718fbe5e10c40f698f6426c6d7cc9ab2024-11-10T12:32:17ZengNature PortfolioNature Communications2041-17232024-11-0115111010.1038/s41467-024-54107-2Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon productsHuiying Deng0Tingting Liu1Wenshan Zhao2Jundong Wang3Yuesheng Zhang4Shuzhen Zhang5Yu Yang6Chao Yang7Wenzhi Teng8Zhuo Chen9Gengfeng Zheng10Fengwang Li11Yaqiong Su12Jingshu Hui13Yuhang Wang14Institute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversityJiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow UniversityXi’an Key Laboratory of Sustainable Energy Materials Chemistry, School of Chemistry, Xi’an Jiaotong UniversityInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversityInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversitySchool of Chemical and Biomolecular Engineering and ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide, The University of SydneySchool of Chemical and Biomolecular Engineering and ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide, The University of SydneyLaboratory of Advanced Materials, Fudan UniversityInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversityInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversityLaboratory of Advanced Materials, Fudan UniversitySchool of Chemical and Biomolecular Engineering and ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide, The University of SydneyXi’an Key Laboratory of Sustainable Energy Materials Chemistry, School of Chemistry, Xi’an Jiaotong UniversityJiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow UniversityInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow UniversityAbstract CO2 electroreduction is a potential pathway to achieve net-zero emissions in the chemical industry. Yet, CO2 loss, resulting from (bi)carbonate formation, renders the process energy-intensive. Acidic environments can address the issue but at the expense of compromised product Faradaic efficiencies (FEs), particularly for multi-carbon (C2+) products, as rapid diffusion and migration of protons (H+) favors competing H2 and CO production. Here, we present a strategy of tuning the 2-position substituent length on benzimidazole (BIM)-based copper (Cu) coordination polymer (CuCP) precatalyst – to enhance CO2 reduction to C2+ products in acidic environments. Lengthening the substituent from H to nonyl enhances H+ diffusion retardation and decreases Cu-Cu coordination numbers (CNs), favoring further reduction of CO. This leads to a nearly 24× enhancement of selectivity towards CO hydrogenation and C-C coupling at 60 mA cm−2. We report the highest C2+ product FE of more than 70% at 260 mA cm−2 on pentyl-CuCP and demonstrate a CO2-to-C2+ single-pass conversion (SPC) of ~54% at 180 mA cm−2 using pentyl-CuCP in zero-gap electrolyzers.https://doi.org/10.1038/s41467-024-54107-2
spellingShingle Huiying Deng
Tingting Liu
Wenshan Zhao
Jundong Wang
Yuesheng Zhang
Shuzhen Zhang
Yu Yang
Chao Yang
Wenzhi Teng
Zhuo Chen
Gengfeng Zheng
Fengwang Li
Yaqiong Su
Jingshu Hui
Yuhang Wang
Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
Nature Communications
title Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
title_full Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
title_fullStr Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
title_full_unstemmed Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
title_short Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products
title_sort substituent tuning of cu coordination polymers enables carbon efficient co2 electroreduction to multi carbon products
url https://doi.org/10.1038/s41467-024-54107-2
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