《Small》: Ultra-Durable Photoreduction of Atmospheric CO₂ into Exclusive CO over Cu₇Te₄ Nanorods with Tellurium Vacancies

Zequn Han,⁺ Mengqian Li,⁺ Jinyu Ding,⁺ Haohao Duan, Wenxiu Liu, Wensheng Yan, Jun Hu, Junfa Zhu, Yang Pan, Jiaqi Xu,* Qingxia Chen,* and Xingchen Jiao*

The impact of defects on the carbon dioxide (CO₂) photoreduction is not always well understood and can be inconsistent at times due to the absence of a clear model. Herein, we clearly disclose the clear structure−property relationship between tellurium defects and CO₂ photoreduction property. As a prototype, we built an ideal model of Cu₇Te₄ nanorods with tunable defect concentrations, in which the defect type and distribution are verified by electron paramagnetic resonance spectra. Photoluminescence spectra demonstrate the presence of tellurium defects can promote carrier separation rates. In situ Fourier transform infrared spectroscopy shows that the primary intermediate is the COOH* group, while quasi in situ X-ray photoelectron spectroscopy confirms that Cu atoms serve as the active sites during CO₂ photoreduction. Density-functional calculations certify the reduced formation energy of the COOH* intermediate following the introduction of tellurium defects. Consequently, the Cu₇Te₄ nanorods with more tellurium defects exhibit a carbon monoxide formation rate of 8.74 μL g⁻¹ h⁻¹ with a stability up to 400 h during photoreduction of atmospheric CO₂. This performance establishes them as the most durable photocatalysts reported under similar conditions to date.

Figure 1. Scheme for the photoreduction atmospheric CO₂ into CO on the Cu₇Te₄ NRs with tellurium defects.