Researchers Develop Pb1Cu Catalyst for CO2-to-formate Conversion

The next big thing: A new technology for directly converting carbon dioxide into pure formic acid. Novel electrochemical device based on solid-state electrolyte

A research team led by Prof. ZENG Jie from University of Science and Technology of China (USTC), and their collaborators, realized highly selective CO2-to-formate conversion via Pb1Cu catalyst. The study was published in Nature Nanotechnology.

8 liters of 0.1 M pure formic acid aqueous solution generated from electrochemical conversion of carbon dioxides
Photograph of 8 liters of 0.1 M pure formic acid aqueous solution generated from electrochemical conversion of carbon dioxides. © ZHENG Tingting et al.

Converting CO2 into valuable chemicals and fuels with renewable electricity offers a sustainable way toward realizing carbon neutral goals. The reported HCOOH-selective electrocatalysts, such as Bi, Sn, In, Pb and Pd, do not yield satisfactory performance in either activity or stability, and are unqualified for industrial applications. In comparison, Cu has both high activity and low cost, yet with limited selectivity.

In this work, researchers obtained single-atom alloyed Cu catalysts modified by Pb, Bi, and In through epoxide gelation approach followed by electrochemical reduction. The atomic dispersion of single atoms in the Cu matrix was then verified, indicating that the single-atom alloyed Cu catalysts were successfully synthesized.

Next, researchers evaluated the catalytic activity of single-atom alloyed Cu catalysts in electrochemical CO2 reduction (CO2RR) in a flow cell. They discovered that the catalysts selectively favored formate formation, and Pb single-atom alloyed Cu catalyst (Pb1Cu) could exclusively convert CO2 into formate (~96% Faradaic efficiency) with high activity greater than 1 A cm-2during the reaction. 

In addition, researchers revealed that oxygen protonation was suppressed while carbon protonation was promoted during CO2RR due to the tuning effect of isolated heteroatoms on the Cu-based catalyst. Thus, the main intermediate during CO2RR was HCOO* instead of COOH*. The former induced the formation of formate while the latter led to formation of a series of unwanted products. It explained the mechanism of the selectivity of single-atom alloyed Cu catalysts.

Further, to eliminate the cost of separation of liquid electrolyte andproducts, researchers developed a solid electrolyte to directly generate pure HCOOH. As a result, the continuous preparation of pure formic acid solution for over 180h was achieved.

The study offers a new design principle for efficient Cu catalysts that selectively generate single product.

Original publication


University of Science and Technology of China, press release, 2021-12-24.