Energy Environ. Sci.: Molecular Modulation of Nickel-Salophen Organic Frameworks Enables Selective Photoreduction of CO2 at Varying Concentrations

Title：

Molecular Modulation of Nickel-Salophen Organic Frameworks Enables Selective Photoreduction of CO₂ at Varying Concentrations

Authors：

Xiaohan Yu^1,2#, Mingzi Sun^3#, Tianran Yan^1,2, Lin Jia^1,2, Mingyu Chu^1,2,Liang Zhang^1,2, Wei Huang^1,2*, Bolong Huang^3,5* and Yanguang Li^1,2,4*

Institutions：

¹Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, 215123 China.

²Jiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, China.

³Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR 999077, China.

⁴Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa 999078, Macau SAR, China.

⁵Research Centre for Carbon-Strategic Catalysis, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR 999077, China

Abstract：

Photocatalytic CO₂ reduction to value-added chemicals is appealing but challenging, especially under dilute CO₂ conditions. Herein, we present a molecular modulation strategy for porous metal–salophen organic frameworks (M-SOFs), involving cooperative regulation of the catalytically active metal centers and their local coordination environments for selective photocatalytic CO₂ reduction across a wide range of CO₂ concentrations. The optimal Ni-SOF shows a remarkable photocatalytic CO production rate of 16908 μmol h⁻¹ g⁻¹ and near-unity selectivity under a pure CO₂ atmosphere, along with excellent structural stability. More impressively, it largely preserves the catalytic activity and selectivity even when exposed to dilute CO₂ (5–20 vol%). Both experimental and theoretical analyses support that the specific Ni–N₂O₂ coordination environment in the Ni-SOF endows it with strong CO₂ binding capacity. This, coupled with nanoporous skeletons, enhances local CO₂ enrichment and facilitates its subsequent conversion at the catalytic centers, thereby leading to superior photocatalytic performances at various CO₂ concentrations.

IF：

39.714

Link：

https://pubs.rsc.org/en/content/articlelanding/2024/ee/d3ee04121b