Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions

Abstract Current catalysts face challenges with low formate selectivity at high current densities during the CO2 electroreduction. Here, we showcase a versatile strategy to enhance the formate production on p-block metal-based catalysts by incorporating noble metal atoms on their surface, refining o...

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Main Authors: Zhengyuan Li, Peng Wang, Guanqun Han, Shize Yang, Soumyabrata Roy, Shuting Xiang, Juan D. Jimenez, Vamsi Krishna Reddy Kondapalli, Xiang Lyu, Jianlin Li, Alexey Serov, Ruizhi Li, Vesselin Shanov, Sanjaya D. Senanayake, Anatoly I. Frenkel, Pulickel M. Ajayan, Yujie Sun, Thomas P. Senftle, Jingjie Wu
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-60008-9
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author Zhengyuan Li
Peng Wang
Guanqun Han
Shize Yang
Soumyabrata Roy
Shuting Xiang
Juan D. Jimenez
Vamsi Krishna Reddy Kondapalli
Xiang Lyu
Jianlin Li
Alexey Serov
Ruizhi Li
Vesselin Shanov
Sanjaya D. Senanayake
Anatoly I. Frenkel
Pulickel M. Ajayan
Yujie Sun
Thomas P. Senftle
Jingjie Wu
author_facet Zhengyuan Li
Peng Wang
Guanqun Han
Shize Yang
Soumyabrata Roy
Shuting Xiang
Juan D. Jimenez
Vamsi Krishna Reddy Kondapalli
Xiang Lyu
Jianlin Li
Alexey Serov
Ruizhi Li
Vesselin Shanov
Sanjaya D. Senanayake
Anatoly I. Frenkel
Pulickel M. Ajayan
Yujie Sun
Thomas P. Senftle
Jingjie Wu
author_sort Zhengyuan Li
collection DOAJ
description Abstract Current catalysts face challenges with low formate selectivity at high current densities during the CO2 electroreduction. Here, we showcase a versatile strategy to enhance the formate production on p-block metal-based catalysts by incorporating noble metal atoms on their surface, refining oxygen affinity, and tuning adsorption of the critical oxygen-bound *OCHO intermediate. The formate yield is observed to afford a volcano-like dependence on the *OCHO binding strength across a series of modified catalysts. The rhodium-dispersed indium oxide (Rh/In2O3) catalyst exhibits impressive performances, achieving Faradaic efficiencies (FEs) of formate exceeding 90% across a broad current density range of 0.20 to 1.21 A cm−2. In situ Raman spectroscopy and theoretical calculations reveal that the oxophilic Rh site facilitates *OCHO formation by optimizing its adsorption energy, placing Rh/In2O3 near the volcano-shaped apex. A bipolar electrosynthesis system, coupling the CO2 reduction at the cathode with the formaldehyde oxidative dehydrogenation at the anode, further boosts the FE of formate to nearly 190% with pure hydrogen generation under an ampere-level current density and a low cell voltage of 2.5 V in a membrane electrode assembly cell.
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spelling doaj-art-3d85c742c5a54225a0d993d3a9ffd2bd2025-08-20T03:48:19ZengNature PortfolioNature Communications2041-17232025-05-011611910.1038/s41467-025-60008-9Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactionsZhengyuan Li0Peng Wang1Guanqun Han2Shize Yang3Soumyabrata Roy4Shuting Xiang5Juan D. Jimenez6Vamsi Krishna Reddy Kondapalli7Xiang Lyu8Jianlin Li9Alexey Serov10Ruizhi Li11Vesselin Shanov12Sanjaya D. Senanayake13Anatoly I. Frenkel14Pulickel M. Ajayan15Yujie Sun16Thomas P. Senftle17Jingjie Wu18Department of Chemical and Environmental Engineering, University of CincinnatiDepartment of Chemical and Biomolecular Engineering, Rice UniversityDepartment of Chemistry, University of CincinnatiEyring Materials Center, Arizona State UniversityDepartment of Sustainable Energy Engineering, Indian Institute of Technology KanpurDepartment of Materials Science and Chemical Engineering, Stony Brook UniversityChemistry Division, Brookhaven National LaboratoryDepartment of Mechanical and Materials Engineering, University of CincinnatiElectrification and Energy Infrastructures Division, Oak Ridge National LaboratoryApplied Materials Division, Argonne National LaboratoryElectrification and Energy Infrastructures Division, Oak Ridge National LaboratoryDepartment of Chemistry, University of CincinnatiDepartment of Chemical and Environmental Engineering, University of CincinnatiChemistry Division, Brookhaven National LaboratoryDepartment of Materials Science and Chemical Engineering, Stony Brook UniversityDepartment of Materials Science and NanoEngineering, Rice UniversityDepartment of Chemistry, University of CincinnatiDepartment of Chemical and Biomolecular Engineering, Rice UniversityDepartment of Chemical and Environmental Engineering, University of CincinnatiAbstract Current catalysts face challenges with low formate selectivity at high current densities during the CO2 electroreduction. Here, we showcase a versatile strategy to enhance the formate production on p-block metal-based catalysts by incorporating noble metal atoms on their surface, refining oxygen affinity, and tuning adsorption of the critical oxygen-bound *OCHO intermediate. The formate yield is observed to afford a volcano-like dependence on the *OCHO binding strength across a series of modified catalysts. The rhodium-dispersed indium oxide (Rh/In2O3) catalyst exhibits impressive performances, achieving Faradaic efficiencies (FEs) of formate exceeding 90% across a broad current density range of 0.20 to 1.21 A cm−2. In situ Raman spectroscopy and theoretical calculations reveal that the oxophilic Rh site facilitates *OCHO formation by optimizing its adsorption energy, placing Rh/In2O3 near the volcano-shaped apex. A bipolar electrosynthesis system, coupling the CO2 reduction at the cathode with the formaldehyde oxidative dehydrogenation at the anode, further boosts the FE of formate to nearly 190% with pure hydrogen generation under an ampere-level current density and a low cell voltage of 2.5 V in a membrane electrode assembly cell.https://doi.org/10.1038/s41467-025-60008-9
spellingShingle Zhengyuan Li
Peng Wang
Guanqun Han
Shize Yang
Soumyabrata Roy
Shuting Xiang
Juan D. Jimenez
Vamsi Krishna Reddy Kondapalli
Xiang Lyu
Jianlin Li
Alexey Serov
Ruizhi Li
Vesselin Shanov
Sanjaya D. Senanayake
Anatoly I. Frenkel
Pulickel M. Ajayan
Yujie Sun
Thomas P. Senftle
Jingjie Wu
Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
Nature Communications
title Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
title_full Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
title_fullStr Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
title_full_unstemmed Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
title_short Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
title_sort ampere level co electrosynthesis of formate from co2 reduction paired with formaldehyde dehydrogenation reactions
url https://doi.org/10.1038/s41467-025-60008-9
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