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

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

doi:10.1038/s41467-025-60008-9

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

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

Energy Storage and Conversion Manufactur

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

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.

Original language	English
Article number	4850
Journal	Nature Communications
Volume	16
Issue number	1
DOIs	https://doi.org/10.1038/s41467-025-60008-9
State	Published - Dec 2025

Funding

This work is supported by the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy under IEDO contract DE-EE0010836. Y.S. acknowledges the support of the National Science Foundation (NSF) grant CHE 2328176. T.P.S. and P.W. acknowledge support by the NSF grant CBET 2143941. S.Y. acknowledges the use of facilities within the Eyring Materials Center at Arizona State University, supported in part by NNCI-ECCS-1542160. Z.L. acknowledges the URC Graduate Student Stipend awarded by the Office of Research at the University of Cincinnati. A.I.F. and S.X. acknowledge support by the NSF grant CHE 2102299. S.D.S. is supported by a DOE Early Career Award. J.D.J. is supported by the Brookhaven National Laboratory Goldhaber Distinguished Fellowship. The work carried out at Brookhaven National Laboratory was supported by the DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences (GSGB) Division, Catalysis Science Program under contract DE-SC0012704. The XAS measurements used resource 8-ID of the National Synchrotron Light Source II, a DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract DE-SC0012704. We would like to thank E. Stavitski for helping with XAFS data collection. X.L. acknowledges that the research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the DOE. Z.L. and G.H. appreciate experimental support by G. Li.

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Li, Z., Wang, P., Han, G., Yang, S., Roy, S., Xiang, S., Jimenez, J. D., Kondapalli, V. K. R., Lyu, X., Li, J., Serov, A., Li, R., Shanov, V., Senanayake, S. D., Frenkel, A. I., Ajayan, P. M., Sun, Y., Senftle, T. P., & Wu, J. (2025). Ampere-level co-electrosynthesis of formate from CO₂ reduction paired with formaldehyde dehydrogenation reactions. Nature Communications, 16(1), Article 4850. https://doi.org/10.1038/s41467-025-60008-9

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title = "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 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.",

author = "Zhengyuan Li and Peng Wang and Guanqun Han and Shize Yang and Soumyabrata Roy and Shuting Xiang and Jimenez, \{Juan D.\} and Kondapalli, \{Vamsi Krishna Reddy\} and Xiang Lyu and Jianlin Li and Alexey Serov and Ruizhi Li and Vesselin Shanov and Senanayake, \{Sanjaya D.\} and Frenkel, \{Anatoly I.\} and Ajayan, \{Pulickel M.\} and Yujie Sun and Senftle, \{Thomas P.\} and Jingjie Wu",

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doi = "10.1038/s41467-025-60008-9",

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Li, Z, Wang, P, Han, G, Yang, S, Roy, S, Xiang, S, Jimenez, JD, Kondapalli, VKR, Lyu, X, Li, J, Serov, A, Li, R, Shanov, V, Senanayake, SD, Frenkel, AI, Ajayan, PM, Sun, Y, Senftle, TP & Wu, J 2025, 'Ampere-level co-electrosynthesis of formate from CO₂ reduction paired with formaldehyde dehydrogenation reactions', Nature Communications, vol. 16, no. 1, 4850. https://doi.org/10.1038/s41467-025-60008-9

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AU - Han, Guanqun

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AU - Roy, Soumyabrata

AU - Xiang, Shuting

AU - Jimenez, Juan D.

AU - Kondapalli, Vamsi Krishna Reddy

AU - Lyu, Xiang

AU - Li, Jianlin

AU - Serov, Alexey

AU - Li, Ruizhi

AU - Shanov, Vesselin

AU - Senanayake, Sanjaya D.

AU - Frenkel, Anatoly I.

AU - Ajayan, Pulickel M.

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AU - Senftle, Thomas P.

AU - Wu, Jingjie

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N2 - 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.

AB - 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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DO - 10.1038/s41467-025-60008-9

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JO - Nature Communications

JF - Nature Communications

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M1 - 4850

ER -

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

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