Three-Dimensional Bicarbazole-Based Covalent Organic Frameworks as Efficient Yeager-Type Photocatalysts for H2O2 Generation in a Two-Phase System DOI
Aiguo Kong, Tao Yang, Hai Yan

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: June 5, 2025

Photocatalytic reduction of oxygen to hydrogen peroxide (H2O2) represents an attractive solar-to-chemical conversion pathway. Nevertheless, it remains a significant challenge achieve efficient H2O2 photosynthesis while simultaneously mitigating photocorrosion the catalysts owing presence superoxide radicals (•O2-) and accumulation photoexcited holes (h+). In present work, 1,2,3,4-tetrahydroisoquinoline (THIQ)-water two-phase system was developed high-efficiency durable production by suppressing •O2- intermediates rapidly consuming h+. The •O2--free direct two-electron reaction (2e- ORR) accomplished on special three-dimensional (3D) covalent organic framework (COF) metal-free photocatalysts consisting bicarbazole units (BCTB) as electron donors thiazole (BT) or triazine (TAPT) acceptors (COF-BCTB-BT COF-BCTB-TAPT). unique structures endow them with high rate in water phase ∼33.2 mmol gcat.-1 h-1 over COF-BCTB-BT. other phase, h+ also efficiently consumed semidehydrogenation THIQ (THIQ-SDR) 3,4-dihydroisoquinoline (DHIQ). Theoretical calculations revealed Yeager-type four-step 2e- ORR mechanism two COFs, lower energy barrier *O-O *O-OH for A THIQ-SDR DHIQ suggested. This work provides impressive strategy 3D bis-heterocyclic COF photocatalysts, effectively both formation accumulation.

Language: Английский

Three-Dimensional Bicarbazole-Based Covalent Organic Frameworks as Efficient Yeager-Type Photocatalysts for H2O2 Generation in a Two-Phase System DOI
Aiguo Kong, Tao Yang, Hai Yan

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: June 5, 2025

Photocatalytic reduction of oxygen to hydrogen peroxide (H2O2) represents an attractive solar-to-chemical conversion pathway. Nevertheless, it remains a significant challenge achieve efficient H2O2 photosynthesis while simultaneously mitigating photocorrosion the catalysts owing presence superoxide radicals (•O2-) and accumulation photoexcited holes (h+). In present work, 1,2,3,4-tetrahydroisoquinoline (THIQ)-water two-phase system was developed high-efficiency durable production by suppressing •O2- intermediates rapidly consuming h+. The •O2--free direct two-electron reaction (2e- ORR) accomplished on special three-dimensional (3D) covalent organic framework (COF) metal-free photocatalysts consisting bicarbazole units (BCTB) as electron donors thiazole (BT) or triazine (TAPT) acceptors (COF-BCTB-BT COF-BCTB-TAPT). unique structures endow them with high rate in water phase ∼33.2 mmol gcat.-1 h-1 over COF-BCTB-BT. other phase, h+ also efficiently consumed semidehydrogenation THIQ (THIQ-SDR) 3,4-dihydroisoquinoline (DHIQ). Theoretical calculations revealed Yeager-type four-step 2e- ORR mechanism two COFs, lower energy barrier *O-O *O-OH for A THIQ-SDR DHIQ suggested. This work provides impressive strategy 3D bis-heterocyclic COF photocatalysts, effectively both formation accumulation.

Language: Английский

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