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Mixed-valence Cu-based metal-organic framework enables highly efficient CO2 electroreduction to C1 liquid fuels

2025-05-29
(Press-News.org)

Rising atmospheric CO2 levels from fossil fuel dependence have intensified climate threats, driving demand for technologies that convert CO2 into value-added chemicals. Electrocatalytic CO2 reduction (CO2RR) holds promise but faces challenges such as high energy costs, low product selectivity, and competition from hydrogen evolution reactions (HER). A breakthrough by researchers at Tongji University, China, introduces a new catalyst design that overcomes these limitations, paving the way for green chemistry solutions.

 

The team, led by Prof. Fengting Li and Prof. Yifan Gu, designed a mixed-valence copper-based metal-organic framework (TJE-ttfp) using a redox-active tetrathiafulvalene-derived ligand. Published in Nano Research, their study demonstrates that TJE-ttfp achieves a Faradaic efficiency of 99.2% for C1 liquid fuels (formic acid and methanol) at a reduction potential of −0.1 V versus the reversible hydrogen electrode (RHE). This performance surpasses commercial copper foam catalyst and rivals state-of-the-art copper-based materials.

 

“The dynamic interplay between Cu(I) and Cu(II) sites creates an adaptive electronic structure,” explained Prof. Yifan Gu, corresponding author of the study. “This synergy not only accelerates electron transfer but also stabilizes reaction intermediates, enabling high selectivity and energy efficiency.” Experimental and theoretical analysis confirmed that the Cu(I)/Cu(II) equilibrium suppresses HER by raising its energy barrier, while the MOF’s isolated single-copper sites prevent undesirable C-C coupling, ensuring exclusive C1 product formation.

 

The catalyst’s stability was validated through 46 hours of continuous operation, retaining 95.1% efficiency for C1 products. Structural integrity was maintained post-reaction, as shown by unchanged X-ray diffraction patterns. Density functional theory (DFT) calculations further revealed that the CO2-to-methanol pathway involves a key COOH* intermediate with a manageable energy barrier, while HER requires significantly higher overpotential.

 

“This work highlights how tailored MOF architectures can address critical bottlenecks in electrocatalysis,” added Prof. Fengting Li. “By integrating mixed-valence metal centers and redox-active linkers, we’ve created a system that balances activity, selectivity, and durability—key metrics for industrial adoption.”

 

Looking ahead, the research team hopes that this new electrocatalyst can be further optimized and scaled up for industrial use. "We believe that our findings provide important insights into the rational design of MOF electrocatalysts for sustainable CO2 conversion," said Prof. Fengting Li. "The next step is to explore its large-scale production and integration into real - world applications, such as in electrochemical reactors for CO2 capture and conversion."

 

The first author of this work is Luyao Wang from Tongji University in Shanghai, China. This research was funded by the National Natural Science Foundation of China (22376161, 52373216), the National Key Research and Development Program of China (2022YFE0110500), and the Fundamental Research Funds for the Central Universities of China.

About the Authors

Prof. Fengting Li
Prof. Fengting Li leads research in advanced functional nanomaterials for gas separation, storage, and energy applications, as well as climate change mitigation and carbon neutrality technologies. His pioneering work spans water treatment, industrial recycling systems, clean production of new energy materials, and battery technologies. Since 2000, he has overseen 50+ national and international projects funded by organizations such as China’s Ministry of Science and Technology, the United Nations Environment Programme, and industry partners. With over 400 publications, 90 authorized Chinese and U.S. patents, 27 national standards, and 21 industry standards, Prof. Li’s innovations have been adopted by 60+ companies. His accolades include two Shanghai Municipal Technology Invention First Prizes, two National Teaching Achievement Second Prizes, the UN South-South Cooperation Special Contribution Award, and the Second Prize of National Environmental Protection Science and Technology Award.

 

Prof. Yifan Gu
Prof. Yifan Gu specializes in the synthesis and application of environmental functional materials, with a focus on porous materials for gas separation, CO₂ capture, volatile organic compounds (VOCs) adsorption, and energy gas storage. To date, he has published over 40 papers in top-tier journals, including Nature Climate Change, Nature Communications, Angewandte Chemie International Edition, and Environmental Science & Technology. Prof. Gu serves as a Youth Editorial Board Member for Nano-Micro Letters and Carbon Capture Science & Technology.

 

About Nano Research

Nano Research is a peer-reviewed, open access, international and interdisciplinary research journal, sponsored by Tsinghua University and the Chinese Chemical Society, published by Tsinghua University Press on the platform SciOpen. It publishes original high-quality research and significant review articles on all aspects of nanoscience and nanotechnology, ranging from basic aspects of the science of nanoscale materials to practical applications of such materials. After 17 years of development, it has become one of the most influential academic journals in the nano field. Nano Research has published more than 1,000 papers every year from 2022, with its cumulative count surpassing 7,000 articles. In 2023 InCites Journal Citation Reports, its 2023 IF is 9.6 (9.0, 5 years), and it continues to be the Q1 area among the four subject classifications. Nano Research Award, established by Nano Research together with TUP and Springer Nature in 2013, and Nano Research Young Innovators (NR45) Awards, established by Nano Research in 2018, have become international academic awards with global influence.

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[Press-News.org] Mixed-valence Cu-based metal-organic framework enables highly efficient CO2 electroreduction to C1 liquid fuels