Linker length-dependent hydrogen peroxide photosynthesis performance over crystalline covalent organic frameworks

Abstract

Molecular engineering-tuned covalent organic frameworks (COFs) have demonstrated as the promising photocatalysts for photocatalytic hydrogen peroxide (H2O2) production by two-electron oxygen reduction in water. Herein a simple strategy by altering...

Solar‐to‐H2O2 Catalyzed by Covalent Organic Frameworks

“…Three imine-based linkers (4,4''-p-terphenyldiamine (DTP), 4,4'-biphenyldiamine (BD), and 1,4-benzenediamine (PA)) production rate observed in the longer linker. [52] Such performance was ascribed to the more efficient e À /h + dissociation and higher surface area in the longer linker. Very recently, Thomas's group also reported two kinds of quinoline-linked COFs (DMCR-1NH and PMCR-1), exhibiting excellent chemical stability and photostability than imine-lined COFs.…”

Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Generation

“…Kong and co-workers also showed that the photocatalytic activity for H 2 O 2 generation can be regulated by changing the length of the linkers used in the construction of the imine-based COFs with similar alkynyl and phenolic groups. 112 respectively (Figure 14a). Among them, COF-BPDA-DTP with the longest linker showed a higher H 2 O 2 generation rate of 1164 μmol h −1 g −1 with better stability in O 2 -presaturated water (Figure 14c).…”

“…(c) Time course photocatalytic H 2 O 2 generation (5 mg of the catalyst, λ > 420 nm, 40 mL of deionized water). Reproduced with permission from ref . Copyright 2023, Royal Society of Chemistry.…”

“…The catalytic performance of COFs is known to be tunable by precisely designing their molecular and electronic structures. Kong and co-workers also showed that the photocatalytic activity for H 2 O 2 generation can be regulated by changing the length of the linkers used in the construction of the imine-based COFs with similar alkynyl and phenolic groups . To investigate a set of three imine-linked alkyne-containing COFs (COF-BPDA-PA, COF-BPDA-BD and COF-BPDA-DTP) were prepared via a Schiff-base condensation reaction of 4,4′,4″-(benzene-1,3,5-triyltris­(ethyne-2,1-diyl)) tris­(2-hydroxybenzaldehyde) (BDPA) with different amine linkers of variable molecular length such as, 1,4-benzenediamine (PA), 4,4′-biphenyldiamine (BD) and 4,4″- p -terphenyldiamine (DTP), respectively (Figure a).…”

Covalent organic framework based photocatalysts for efficient visible-light driven hydrogen peroxide production

“…It was found that the obtained COF with a longer linker (COF-BPDA-DTP) exhibited better photocatalytic performance due to its more negative conductor band, higher specific surface area and enhanced photogenerated carrier separation efficiency. 43 To systematically examine the effects of different functional groups on the photocatalytic performance of a specific COF, Wang and co-workers synthesized a series of imine-linked COFs (TAPB-PDA-X) by the condensation of 1,3,5-tris(4-aminophenyl) benzene (TAPB) and the teraphthaldehyde with different functional groups (PDA-X, X = H 2 , CH 3 , OH, and OCH 3 ). Among all the obtained COFs, the TAPB-PDA-OH modified with hydroxyl groups exhibited the best H 2 O 2 production rate of 2117.6 μmol g −1 h −1 and an AQY of 2.99% at 420 nm in H 2 O : EtOH (9 : 1) aqueous solution.…”