Engineering Single‐Atom Sites with the Irving–Williams Series for the Simultaneous Co‐photocatalytic CO<sub>2</sub> Reduction and CH<sub>3</sub>CHO Oxidation
Jian Li, Minghao Du, Zhenfa Wu, Xinru Zhang, Wenjuan Xue, Hongliang Huang, Chongli Zhong
Abstract
Abstract The bonding effects between 3d transition‐metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition‐metal atoms of the spontaneous geometrical distortions, that is the Jahn–Teller effect, can alter CFSE, thereby leading to the Irving–Williams series. However, engineering single‐atom sites (SASs) using the Irving–Williams series as an ideal guideline has not been reported to date. Herein, alkynyl‐linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d 5 to d 10 (Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ). The Irving–Williams series was employed to accurately predict the bonding effects between 3d transition‐metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu‐SASs/CPFs exhibits higher stability and faster charge‐transfer efficiency, far surpassing other metal‐SASs/CPFs. As expected, Cu‐SASs/CPFs demonstrates a high photoreduction of CO 2 ‐to‐CO activity (~30.3 μmol ⋅ g −1 ⋅ h −1 ) and an exceptional photooxidation of CH 3 CHO‐to‐CH 3 COOH activity (~24.7 μmol ⋅ g −1 ⋅ h −1 ). Interestingly, the generated *O 2 − is derived from the process of CO 2 reduction, thereby triggering a CH 3 CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving–Williams to regulate the catalytic performances.