Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO2 Reduction

Xinxin Wang; Xu Ding; Tianyu Wang; Kang Wang; Yucheng Jin; Yuesheng Han; Pianpian Zhang; Ning Li; Hailong Wang; Jianzhuang Jiang

doi:10.1021/acsami.2c12542

Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO₂ Reduction

ACS Appl Mater Interfaces. 2022 Sep 14;14(36):41122-41130. doi: 10.1021/acsami.2c12542. Epub 2022 Aug 31.

Authors

Affiliation

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China.

PMID: 36044780
DOI: 10.1021/acsami.2c12542

Abstract

Two-dimensional (2D) porphyrin-based covalent organic frameworks (COFs) are one of the most promising candidates for photocatalytic carbon dioxide reduction reaction (CO₂RR), which however still suffer from the hindered mass transfer during the catalysis procedure associated with the close packing of 2D COF layers due to the strong axial π-π stacking. Herein, condensation between the porphyrinic aldehydes p-MPor-CHO (M = H₂, Co, and Ni) and 3,8-diamino-6-phenyl-phenanthridine (DPP) affords new porphyrin-based 2D COF architecture MPor-DPP-COFs (M = H₂, Co, and Ni). The bulky phenyl substituent at the phenanthridine periphery of the linking unit reduces the axial π-π stacking, providing an enlarged inter-layer spacing of 6.0 Å according to high-resolution transmission electron microscopy. This, in combination with the large surface area (1021 m² g^-1) revealed by nitrogen sorption measurements at 77 K for CoPor-DPP-COF possessing electroactive Co ions, endows it with excellent photocatalytic activity for CO₂RR with a CO generation rate of 10 200 μmol g^-1 h^-1 and a CO selectivity up to 82%. This work affords new ideas for achieving efficient photocatalytic CO₂RR upon fine-tuning the inter-layer spacing of 2D COFs.

Keywords: carbon dioxide reduction; covalent organic frameworks; inter-layer spacing; photocatalysis; porphyrin.