Large-Area Conductive MOF Ultrathin Film Controllably Integrating Dinuclear-Metal Sites and Photosensitizers to Boost Photocatalytic CO2 Reduction with H2O as an Electron Donor

Kuo Yuan; Keying Tao; Tianqun Song; Ying Zhang; Tao Zhang; Fei Wang; Shuming Duan; Zheng Chen; Lujiang Li; Xiaotao Zhang; Dichang Zhong; Zhiyong Tang; Tong-Bu Lu; Wenping Hu

doi:10.1021/jacs.3c14036

Large-Area Conductive MOF Ultrathin Film Controllably Integrating Dinuclear-Metal Sites and Photosensitizers to Boost Photocatalytic CO₂ Reduction with H₂O as an Electron Donor

J Am Chem Soc. 2024 Mar 13;146(10):6893-6904. doi: 10.1021/jacs.3c14036. Epub 2024 Mar 1.

Authors

Kuo Yuan^{1

2

3}, Keying Tao¹, Tianqun Song^{1

2

3}, Ying Zhang¹, Tao Zhang⁴, Fei Wang⁵, Shuming Duan^{2

6}, Zheng Chen², Lujiang Li³, Xiaotao Zhang², Dichang Zhong¹, Zhiyong Tang⁵, Tong-Bu Lu¹, Wenping Hu^{2

6}

Affiliations

¹ Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, Tianjin University of Technology, Tianjin 300384, China.
² Department of Chemistry, School of Science & Key Laboratory of Organic Integrated Circuits, Ministry of Education, Tianjin University, Tianjin 300072, China.
³ Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China.
⁴ Wuhan National High Magnetic Field Center and School of Physics, Huazhong University of Science and Technology, Wuhan 430074, China.
⁵ CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, China.
⁶ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China.

PMID: 38426856
DOI: 10.1021/jacs.3c14036

Abstract

Owing to the electrical conductivity and periodic porosity, conductive metal-organic framework (cMOF) ultrathin films open new perspectives to photocatalysis. The space-selective assembly of catalytic sites and photosensitizers in/on cMOF is favorable for promoting the separation of photogenerated carriers and mass transfer. However, the controllable integration of functional units into the cMOF film is rarely reported. Herein, via the synergistic effect of steric hindrance and an electrostatic-driven strategy, the dinuclear-metal molecular catalysts (DMC) and perovskite (PVK) quantum dot photosensitizers were immobilized into channels and onto the surface of cMOF ultrathin films, respectively, affording [DMC@cMOF]-PVK film photocatalysts. In this unique heterostructure, cMOF not only facilitated the charge transfer from PVK to DMC but also guaranteed mass transfer. Using H₂O as an electron donor, [DMC@cMOF]-PVK realized a 133.36 μmol·g^-1·h^-1 CO yield in photocatalytic CO₂ reduction, much higher than PVK and DMC-PVK. Owing to the excellent light transmission of films, multilayers of [DMC@cMOF]-PVK were integrated to increase the CO yield per unit area, and the 10-layer device realized a 1115.92 μmol·m^-2 CO yield in 4 h, which was 8-fold higher than that of powder counterpart. This work not only lightens the development of cMOF-based composite films but also paves a novel avenue for an ultrathin film photocatalyst.