Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration.

Photocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD-COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 µmol g-1 h-1 in O2 and air) than TBC-COF with hcb topology through the O2-O2⋅--H2O2, O2-O2⋅--O2 1-H2O2, and H2O-H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2⋅- generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O2 1, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high-performance photocatalysts for H2O2 production by topological structure modulation.

Mixed-Linkage Donor-Acceptor Covalent Organic Framework as a Turn-On Fluorescent Sensor for Aliphatic Amines.

Amine determination is crucial to our daily life, including the prevention of pollution, the treatment of certain disorders, and the evaluation of food quality. Herein, a mixed-linkage donor-acceptor covalent organic framework (named DSE-COF) was first constructed by the polymerization between 2,4-dihydroxybenzene-1,3,5-tricarbaldehyde (DTA) and 4,4'-(benzo[c][1,2,5]selenadiazole-4,7-diyl)dianiline (SEZ). DSE-COF displayed superior turn-on fluorescent responses to primary, secondary, and tertiary aliphatic amines, such as cadaverine, isopropylamine, sec-butylamine, cyclohexylamine, hexamethylenediamine, di-n-butylamine, and triethylamine in absolute acetonitrile than other organic species. Further experiments and theoretical calculations demonstrated that the combination of intramolecular charge transfer (ICT) and photoinduced electron transfer (PET) effects between the DSE-COF and aliphatic amines resulted in enhanced fluorescence. Credibly, DSE-COF can quantitatively detect cadaverine content in actual pork samples with satisfactory results. In addition, DSE-COF-based test papers could rapidly monitor cadaverine from real pork samples, manifesting the potential application of COFs in food quality inspection.

Thiophene-Containing Covalent Organic Frameworks for Overall Photocatalytic H2 O2 Synthesis in Water and Seawater.

H2 O2 is a significant chemical widely utilized in the environmental and industrial fields, with growing global demand. Without sacrificial agents, simultaneous photocatalyzed H2 O2 synthesis through the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) dual channels from seawater is green and sustainable but still challenging. Herein, two novel thiophene-containing covalent organic frameworks (TD-COF and TT-COF) were first constructed and served as catalysts for H2 O2 synthesis via indirect 2e- ORR and direct 2e- WOR channels. The photocatalytic H2 O2 production performance can be regulated by adjusting the N-heterocycle modules (pyridine and triazine) in COFs. Notably, with no sacrificial agents, just using air and water as raw materials, TD-COF exhibited high H2 O2 production yields of 4060 µmol h-1 g-1 and 3364 µmol h-1 g-1 in deionized water and natural seawater, respectively. Further computational mechanism studies revealed that the thiophene was the primary photoreduction unit for ORR, while the benzene ring (linked to the thiophene by the imine bond) was the central photooxidation unit for WOR. The current work exploits thiophene-containing COFs for overall photocatalytic H2 O2 synthesis via ORR and WOR dual channels and provides fresh insight into creating innovative catalysts for photocatalyzing H2 O2 synthesis.

Chiral Ionic Covalent Organic Framework as an Enantioselective Fluorescent Sensor for Phenylalaninol Determination.

Phenylalaninol (PAL) is a significant chemical intermediate widely utilized in drug development and chiral synthesis, for instance, as a reactant for bicyclic lactams and oxazoloisoindolinones. Since the absolute stereochemical configuration significantly impacts biological action, it is crucial to evaluate the concentration and enantiomeric content of PAL in a quick and convenient manner. Herein, an effective PAL enantiomer recognition method was reported based on a chiral ionic covalent organic framework (COF) fluorescent sensor, which was fabricated via one-step postquaternization modification of an achiral COF by (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl-carbonochloridate (L-MTE). The formed chiral L-TB-COF can be applied as a chiral fluorescent sensor to recognize the stereochemical configuration of PAL, which displayed a turn-on fluorescent response for R-PAL over that of S-PAL with an enantioselectivity factor of 16.96. Nonetheless, the single L-MTE molecule had no chiral recognition ability for PAL. Moreover, the ee value of PAL can be identified by L-TB-COF. Furthermore, density functional theory (DFT) calculations demonstrated that the chiral selectivity came from the stronger binding affinity between L-TB-COF and R-PAL in comparison to that with S-PAL. L-TB-COF is the first chiral ionic COF employed to identify chiral isomers by fluorescence. The current work expands the range of applications for ionic COFs and offers fresh suggestions for creating novel chiral fluorescent sensors.