Ampere-level co-electrosynthesis of formate from CO2 reduction paired with formaldehyde dehydrogenation reactions
Current catalysts face challenges with low formate selectivity at high current densities during the CO<sub>2</sub> 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/In<sub>2</sub>O<sub>3</sub>) 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<sup>-2</sup>. In situ Raman spectroscopy and theoretical calculations reveal that the oxophilic Rh site facilitates *OCHO formation by optimizing its adsorption energy, placing Rh/In<sub>2</sub>O<sub>3</sub> near the volcano-shaped apex. A bipolar electrosynthesis system, coupling the CO<sub>2</sub> 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.
Authors
- Xiang Lyu (ORCID: https://orcid.org/0000-0002-0867-3248)
- Zhengyuan Li (ORCID: https://orcid.org/0000-0002-1525-4981)
- Shize Yang (ORCID: https://orcid.org/0000-0002-0421-006X)
- Vamsi Krishna Reddy Kondapalli (ORCID: https://orcid.org/0000-0002-0539-7102)
- Juan D. Jiménez (ORCID: https://orcid.org/0000-0003-4710-1047)
- Pulickel Madhavapanicker Ajayan (ORCID: https://orcid.org/0000-0001-8323-7860)
- Sanjaya D. Senanayake (ORCID: https://orcid.org/0000-0003-3991-4232)
- Soumyabrata Roy (ORCID: https://orcid.org/0000-0003-3540-1341)
- Anatoly I. Frenkel (ORCID: https://orcid.org/0000-0002-5451-1207)
- Vesselin Shanov (ORCID: https://orcid.org/0000-0002-0041-7821)
- Yujie Sun (ORCID: https://orcid.org/0000-0002-4122-6255)
- Thomas P. Senftle (ORCID: https://orcid.org/0000-0002-5889-5009)
- Jingjie Wu (ORCID: https://orcid.org/0000-0001-6617-0895)
- Shuting Xiang (ORCID: https://orcid.org/0000-0001-9423-3347)
- Alexey Serov (ORCID: https://orcid.org/0000-0003-3182-4726)
- Peng Wang (ORCID: https://orcid.org/0000-0003-4250-8104)
- Guan‐Qun Han (ORCID: https://orcid.org/0000-0002-3016-575X)
- Jianlin Li (ORCID: https://orcid.org/0000-0002-8710-9847)
- Ruizhi Li (ORCID: https://orcid.org/0000-0003-2326-6285)
Institutions
- Argonne National Laboratory (US)
- Oak Ridge National Laboratory (US)
- Brookhaven National Laboratory (US)
- Arizona State University (US)
- Stony Brook University (US)
- University of Cincinnati (US)
- Rice University (US)
- Indian Institute of Technology Kanpur (IN)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-05-24
- DOI
- https://doi.org/10.1038/s41467-025-60008-9
- Citations
- 27
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 9.81
Funders
- Office of Science
- Office of Energy Efficiency and Renewable Energy
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- Division of Chemistry