Selective Photocatalytic Conversion of CO2 to Ethanol via Unsaturated Cu-O Domains

Qiang Wang; Mingqi He; Pengxin Yang; Yanan Zhou; Xing Wang; Kaifu Zhang; Zhuo Jiang; Qiquan Luo; Shan Gao; Jinlong Yang

doi:10.1021/acsnano.4c11842

Selective Photocatalytic Conversion of CO₂ to Ethanol via Unsaturated Cu-O Domains

ACS Nano. 2024 Nov 22. doi: 10.1021/acsnano.4c11842. Online ahead of print.

Authors

Qiang Wang¹, Mingqi He², Pengxin Yang¹, Yanan Zhou², Xing Wang¹, Kaifu Zhang^{1

3}, Zhuo Jiang⁴, Qiquan Luo⁵, Shan Gao¹, Jinlong Yang²

Affiliations

¹ Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039, China.
² Department of Chemical Physics, Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, China.
³ Key Laboratory of Functional Inorganic Material Chemistry Ministry of Education, Heilongjiang University, Harbin 150080, China.
⁴ School of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, China.
⁵ Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China.

PMID: 39576814
DOI: 10.1021/acsnano.4c11842

Abstract

Enhancing the selectivity of photocatalytic CO₂ reduction to valuable multicarbon (C₂₊) products remains a significant challenge in green synthetic chemistry. Here, we present a dual-center strategy for metal oxides that boosts the photochemical conversion of CO₂ to ethanol by regulating the coordination number of metal and oxygen sites. Notably, CuO catalysts rich in low-coordinated Cu-O domains have achieved nearly perfect ethanol selectivity (96.9%), extraordinary durability (60 h), and a superior yield rate of 30.5 μmol·g^-1·h^-1, surpassing the performance of many existing photocatalysts in water vapor and CO₂. Density functional theory calculations and operando spectroscopic results provide conclusive evidence that tricoordinated copper (Cu_3c) increases the coverage of key *CO species, while bicoordinated oxygen (O_2c) controls the migration of *CO species, thereby effectively reducing the energy requirement for *CO dimerization into *OC-CO intermediates (ΔG_*OC-CO = -0.56 eV) in the ethanol pathway. This work offers valuable insights for designing photocatalysts that exhibit improved selectivity for C₂₊ fuels.

Keywords: charge transfer; low-coordinated Cu–O domains; metal oxides; photocatalysis; selectivity.