Polymorphism in covalent organic frameworks (COFs) offers a unique platform to decipher structure-property relationships, yet its impact on excited-state dynamics remains unexplored. Herein, we construct two chemically identical but topologically distinct 1D and 2D COF polymorphs to correlate framework architecture with photocatalytic performance. Impressively, in H2O2 photosynthesis coupled with furfuryl alcohol valorization, the 1D-TBPP-COF showed an exceptional H2O2 generation rate (18.75 mmol g-1 h-1) and selective oxidation of furfuryl alcohol to high-value 6-hydroxy-2H-pyran-3(6H)-one (PN) with PN formation rate of 28.14 mmol·g-1·h-1, substantially outperforming the 2D-TBPP-COF counterpart. Mechanistic investigations revealed that the intercalated dual-chain edges in 1D-TBPP-COF impose steric constraints on aromatic ring rotation, effectively suppressing vibrational relaxation losses and prolonging the charge-transfer state lifetime. In contrast, the conformationally flexible 2D-TBPP-COF permits greater rotational freedom, leading to non-radiative energy dissipation. This work establishes polymorphism engineering as a powerful strategy to manipulate excited-state dynamics in COFs for photocatalysis.
Covalent organic frameworks (COFs) have attracted considerable attention as promising photocatalysts for hydrogen peroxide (H2O2) production. To further improve their catalytic performance, a quaternary ammonium functionality was introduced into the bipyridine units of the COF via a post-synthetic modification strate...
Zhi-Hui Sun, Jia-Jia Li, Long-Yang Yang et al.· ACS Applied Energy Materials· 0 citations
Covalent organic frameworks (COFs) are promising photocatalysts for solar-driven hydrogen evolution due to their tunable structures and intrinsic porosity. In this work, a series of Tp-Pa-based COFs bearing different electron-withdrawing groups was synthesized via a scalable mechanochemical route to examine the impact...
Kiran Asokan, S. S. Babu· Chemistry - An Asian Journal· 0 citations
Covalent organic frameworks (COFs) provide a polymer platform for exploring covalent linkages to design ordered skeletal and porous architectures. However, the role of linkages in controlling structural and functional evolutions remains to be well explored. In this study, we reported hexaphenyltriphenylene COF photocat...
Yong-Zhi Chen, Xinyu Mu, Sailun Ji et al.· Angewandte Chemie· 1 citation
Solar-driven biomass valorization is pivotal for defossilizing the chemical industry. The oxidation of abundant, low-cost 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA)─a key monomer for next-generation bioplastics─is a long-sought goal yet hampered by sluggish kinetics, poor selectivity, and alkali...
Xiaomeng Zhao, Jianhui Sun, Linlu Bai et al.· Journal of the American Chem...· 0 citations
Covalent organic frameworks (COFs) have emerged as promising candidates for singlet oxygen (1O2) generation via peroxymonosulfate (PMS) activation, yet their structure-property-activity relationships remain poorly understood. Herein, three constitutionally isomeric donor-acceptor COFs (TF-22Bpy, TA-22Bpy and TA-33Bpy)...
Chengming Xiao, Meng-Ting He, Wen-Bo Yang et al.· Nature Communications· 0 citations
Covalent organic frameworks (COFs) hold promises for overall H2O2 photosynthesis. However, their efficiency is constrained by rapid charge recombination at the universal C=N linkages due to the nitrogen lone pairs acting as efficient hole traps. Here, we report a molecular-level electronic isolation strategy through...
Ziling Li, Zi-He Wang, Donghui Lan et al.· ACS Catalysis· 0 citations
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