Locking Photosensitizers into Staggered-Stacking and DNA-Interlocked Metal–Organic Frameworks for Outstanding CO 2 Photoreduction Activity

Yong LiMinistry of Education of the People's Republic of China

Jing-Wen ShiMinistry of Education of the People's Republic of China

Guo-Ping YangMinistry of Education of the People's Republic of China

Ya-Qian LanMinistry of Education of the People's Republic of China

Jiang LiuMinistry of Education of the People's Republic of China

Yao-Yu WangMinistry of Education of the People's Republic of China

Journal of the American Chemical Society·February 6, 2026

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Abstract

Photosensitizers (PSs) play crucial roles in photocatalysis by efficiently harvesting light and facilitating photoinduced charge transfer. However, whether they are applied in a homogeneous solution or immobilized on catalysts, PSs are prone to deactivation through leaching or desorption, leading to a significant decline in photocatalytic performance. Herein, two highly photoactive metal-organic frameworks (MOFs) denoted as NWUM-Cd-s and NWUM-Cd were constructed from Cd(II) ions, 4,4',4''-nitrilotribenzoic acid (H3TCA), and a classic [Ru(bpy)3]2+ PS via cocrystallization. These MOFs can firmly lock the [Ru(bpy)3]2+ PS through the structural characteristics of DNA-like double-helix and "···ABABA···" dislocation stacking. This prevents the PS from deactivating during the photocatalytic process, which enables these MOFs to exhibit excellent photocatalytic activity and long-term cycling stability in the model CO2 photoreduction reaction. The CO production rate of interpenetrated NWUM-Cd-s (13.9 mmol g-1 h-1) is 5.3 times that of dislocated monolayer NWUM-Cd (2.6 mmol g-1 h-1). In situ characterizations and theoretical calculations reveal that the interpenetrated structure of NWUM-Cd-s significantly enhances the separation of photogenerated charges, which in turn reduces the overall reaction energy barrier and promotes electron-proton transfer cooperativity, thus leading to more outstanding photoactivity than that of NWUM-Cd. This work demonstrates unprecedented staggered stacking and DNA-like interlocking strategies to lock PSs in catalysts, thereby tackling the long-standing challenges in traditional photocatalysis of low light utilization efficiency, PS deactivation, and slow charge transfer.

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