Regulating the Combinations of Donor and Acceptor Units via DFT Calculations for Photocatalysts with Efficient Electron–Hole Separation and Transfer Dynamics DOI

Lin-Fu Xie,

Ling Niu,

Tingting Xie

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Donor-acceptor (D-A)-type conjugated microporous polymers (CMPs) are considered promising photocatalytic materials due to their easily tunable structures and optical properties. However, the rational combination of D A units design D-A-type CMPs with efficient electron-hole separation transfer dynamics remains an ongoing challenge. Herein, we employed Density Functional Theory (DFT) calculations evaluate 16 potential D-A pair combinations respective dynamics. These consisted M-salens (M = Zn, Cu, Co, Ni) as bromine-containing monomers four alkyne-based monomers: 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT), 4,4″-diethyl-5'-(4-ethynylphenyl)-1, 1':3',1″-terphenyl (TEPB), tris(4-ethynylphenyl) amine (TEPA), 3,7-diethyl-10-(4-ethynylphenyl)-10H-phenothiazine (TEPP). Eight were obtained via DFT calculation, ranking follows: Zn-salen-TEPA > Zn-salen-TEPP Zn-salen-TEPT Cu-salen-TEPP Cu-salen-TEPA Cu-salen-TEPT Ni-salen-TEPT Co-salen-TEPT. Based on these results, three pairs exhibiting highest selected for synthesis corresponding subsequent photoelectric characterization. Experimental enhancements aligned closely predictions. Notably, aerobic oxidative amidation diverse aldehydes amines catalyzed by under blue LED irradiation achieved a yield up 97%, which surpassed performance most reported works. This work offers novel perspectives endowed highly activity.

Language: Английский

Donor-acceptor mixed-ligand MOF with energy transfer-mediated high-efficiency singlet oxygen generation for boosted organic photosynthesis DOI
Hong‐Guang Jin, Wei Lin, Pengcheng Zhao

et al.

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 689, P. 137231 - 137231

Published: March 6, 2025

Language: Английский

Citations

0
Arrangement of Ordered D–A Components in a Metal‐Organic Framework for Cocatalyst‐Free Photocatalytic Hydrogen Evolution with Efficient Proton Conduction DOI Open Access
Ning Liu, Jialong Jiang, Shiqi Zhang

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract The arrangement of donor–acceptor (D–A) components in order at a molecular level provides means to achieve efficient electron‐hole separation for promoting the activity photocatalysts. Herein, we report coordination assembly D–A molecules with desired staggered energy levels two isostructural metal‐organic frameworks (MOFs) 1 and 2 , which exhibit high photocatalytic hydrogen evolution without using any cocatalysts photosensitizers. modulation active metal sites MOFs leads an increase rates from 1260 3218 µmol h −1 g . A detailed mechanism study revealed that bond defined by assisted centers is key efficiently generating photogenerated charge carriers, has appropriate affinity proton reduce barrier evolution. Besides, enhanced transport kinetics based on arrayed free carboxyl groups hydrogen‐bonded network endows higher conductivity than thus usage rate reaction kinetics.

Language: Английский

Citations

0
Simulated design of Cu2N/BiOCl for selective synthesis of C2 alcohol products in photocatalytic reduction of CO2 via nitrogen vacancy on modified square copper sites DOI

Zigeng Wang,

Manman Mu,

Fahim A. Qaraah

et al.

Computational Materials Science, Journal Year: 2025, Volume and Issue: 253, P. 113839 - 113839

Published: March 17, 2025

Language: Английский

Citations

0
Design of Donor‐Acceptor Type 2D Covalent Organic Frameworks as Efficient Photocatalysts for Visible‐Light‐Driven Water Splitting DOI Open Access
Jiao Chen, Xiaotao Zhang, Xinyong Cai

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 23, 2025

Abstract Benefitting from the substantially accessible catalytic sites and porous architecture enhancing mass transport, 2D covalent organic frameworks (COFs) show great potential for photocatalytic overall water splitting (OWS). However, performance of many known COFs this application remains unsatisfactory, primarily due to stringent requirements precise band alignment, limitation posed by overpotentials in hydrogen evolution reaction (HER) oxygen (OER), mutual interference between two half‐reactions. Herein, incorporating donor‐acceptor (D‐A) pairs into with photosensitizer carbonyl‐bridged triphenylamine (CTPA) as a basic building block, few D‐A type CTPA‐based framework (CCFs) experimental synthesis possibilities verified Ullman C─C coupling mechanism are proposed. These CCFs exhibit significant intermolecular charge transfer anticipated, facilitating efficient carrier separation OWS. The combination D/A units these regulates their electronic structure bandgaps ranging 2.31 3.15 eV band‐edge arrangement suitable Crucially, co‐existence separate presentation HER OER active on surface without enables them capable spontaneous OWS under visible light. Among them, CTPA‐TPA COF shows best an ideal solar‐to‐hydrogen (STH) efficiency up 18.6%.

Language: Английский

Citations

0
Regulating the Combinations of Donor and Acceptor Units via DFT Calculations for Photocatalysts with Efficient Electron–Hole Separation and Transfer Dynamics DOI

Lin-Fu Xie,

Ling Niu,

Tingting Xie

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Donor-acceptor (D-A)-type conjugated microporous polymers (CMPs) are considered promising photocatalytic materials due to their easily tunable structures and optical properties. However, the rational combination of D A units design D-A-type CMPs with efficient electron-hole separation transfer dynamics remains an ongoing challenge. Herein, we employed Density Functional Theory (DFT) calculations evaluate 16 potential D-A pair combinations respective dynamics. These consisted M-salens (M = Zn, Cu, Co, Ni) as bromine-containing monomers four alkyne-based monomers: 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT), 4,4″-diethyl-5'-(4-ethynylphenyl)-1, 1':3',1″-terphenyl (TEPB), tris(4-ethynylphenyl) amine (TEPA), 3,7-diethyl-10-(4-ethynylphenyl)-10H-phenothiazine (TEPP). Eight were obtained via DFT calculation, ranking follows: Zn-salen-TEPA > Zn-salen-TEPP Zn-salen-TEPT Cu-salen-TEPP Cu-salen-TEPA Cu-salen-TEPT Ni-salen-TEPT Co-salen-TEPT. Based on these results, three pairs exhibiting highest selected for synthesis corresponding subsequent photoelectric characterization. Experimental enhancements aligned closely predictions. Notably, aerobic oxidative amidation diverse aldehydes amines catalyzed by under blue LED irradiation achieved a yield up 97%, which surpassed performance most reported works. This work offers novel perspectives endowed highly activity.

Language: Английский

Citations

0