Chemical state

Selectivity

Absorption spectroscopy

Physics

Absorption (acoustics)

Engineering

Physical chemistry

Composite material

Catalysis

Electrode

X-ray photoelectron spectroscopy

Organic chemistry

Inorganic chemistry

Chemistry

Materials science

Electrochemical reduction of carbon dioxide

Oxide

Spectroscopy

Electrocatalyst

Chemical engineering

Carbon monoxide

Electrochemistry

Carbon dioxide

Metal

Copper

X-ray absorption spectroscopy

Quantum mechanics

Photochemistry

Nature Communications

Copper electrocatalysts have been shown to selectively reduce carbon dioxide to hydrocarbons. Nevertheless, the absence of a systematic study based on time-resolved spectroscopy renders the functional agent—either metallic or oxidative Copper—for the selectivity still undecidable. Herein, we develop an operando seconds-resolved X-ray absorption spectroscopy to uncover the chemical state evolution of working catalysts. An oxide-derived Copper electrocatalyst is employed as a model catalyst to offer scientific insights into the roles metal states serve in carbon dioxide reduction reaction (CO 2 RR). Using a potential switching approach, the model catalyst can achieve a steady chemical state of half-Cu(0)-and-half-Cu(I) and selectively produce asymmetric C 2 products - C 2 H 5 OH. Furthermore, a theoretical analysis reveals that a surface composed of Cu-Cu(I) ensembles can have dual carbon monoxide molecules coupled asymmetrically, which potentially enhances the catalyst’s CO 2 RR product selectivity toward C 2 products. Our results offer understandings of the fundamental chemical states and insights to the establishment of selective CO 2 RR.

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction