Solar‐to‐H₂O₂ Catalyzed by Covalent Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 14, 2023

Abstract Benefiting from the excellent structural tunability, robust framework, ultrahigh porosity, and rich active sites, covalent organic frameworks (COFs) are widely recognized as promising photocatalysts in chemical conversions, emerged hydrogen peroxide (H 2 O ) photosynthesis 2020. H , serving an environmental‐friendly oxidant a liquid fuel, has attracted increasing researchers to explore its potential. Over past few years, numerous COFs‐based developed with encouraging achievements production, whereas no comprehensive review articles exist summarize this specific significant area. Herein we provide systematic overview of advances challenges COFs photocatalytic production. We first introduce priorities photosynthesis. Then, various strategies improve efficiency discussed. The perspective outlook for future emerging field finally offered. This timely will pave way development highly efficient practical production value‐added chemicals not limited .

Language: Английский

---

Covalent Organic Frameworks for Energy Conversion in Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: April 24, 2023

Abstract Intensifying energy crises and severe environmental issues have led to the discovery of renewable sources, sustainable conversion, storage technologies. Photocatalysis is a green technology that converts eco‐friendly solar into high‐energy chemicals. Covalent organic frameworks (COFs) are porous materials constructed by covalent bonds show promising potential for converting chemicals owing their pre‐designable structures, high crystallinity, porosity. Herein, we highlight recent progress in synthesis COF‐based photocatalysts applications water splitting, CO 2 reduction, H O production. The challenges future opportunities rational design COFs advanced discussed. This Review expected promote further development toward photocatalysis.

Language: Английский

---

Thiophene‐Containing Covalent Organic Frameworks for Overall Photocatalytic H₂O₂ Synthesis in Water and Seawater

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: Aug. 1, 2023

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

Language: Английский

---

Linkage-engineered donor–acceptor covalent organic frameworks for optimal photosynthesis of hydrogen peroxide from water and air

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(2), P. 195 - 206

Published: Feb. 13, 2024

Language: Английский

---

Regulating Relative Nitrogen Locations of Diazine Functionalized Covalent Organic Frameworks for Overall H₂O₂ Photosynthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 26, 2023

Nitrogen-heterocycle-based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H2 O2 ). However, effects relative nitrogen locations remain obscured and photocatalytic performances COFs need to be further improved. Herein, a collection functionalized by various diazines including pyridazine, pyrimidine, pyrazine have been judiciously designed synthesized photogeneration H2 without sacrificial agents. Compared with pyrimidine pyrazine, pyridazine embedded in TpDz tends stabilize endoperoxide intermediate species, leading toward more efficient direct 2e- oxygen reduction reaction (ORR) pathway. Benefiting from effective electron-hole separation, low charge transfer resistance, high-efficiency ORR pathway, an excellent production rate 7327 μmol g-1 h-1 solar-to-chemical conversion (SCC) value 0.62 % has achieved TpDz, which ranks one best COF-based photocatalysts. This work might shed fresh light on rational design functional targeting photocatalysts production.

Language: Английский

---

Efficient photocatalytic production of hydrogen peroxide using dispersible and photoactive porous polymers

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 28, 2023

Developing efficient artificial photocatalysts for the biomimetic photocatalytic production of molecular materials, including medicines and clean energy carriers, remains a fundamentally technologically essential challenge. Hydrogen peroxide is widely used in chemical synthesis, medical disinfection, energy. However, current industrial production, predominantly by anthraquinone oxidation, suffers from hefty penalties toxic byproducts. Herein, we report hydrogen protonation-induced dispersible porous polymers with good charge-carrier transport properties. Significant generation occurs under ambient conditions at an unprecedented rate 23.7 mmol g-1 h-1 apparent quantum efficiency 11.3% 450 nm. Combined simulations spectroscopies indicate that sub-picosecond ultrafast electron "localization" both free carriers exciton states catalytic reaction centers underlie remarkable performance polymers.

Language: Английский

---

Solar Light Driven H₂O₂ Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 8, 2023

A chemically stable 2D microporous COF (PMCR-1) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term photocatalytic H2 O2 production rate (60 h) from pure sea water under visible light. The is markedly enhanced when benzyl alcohol (BA) added as reductant, which also due to strong π-π interaction of BA with dangling phenyl moieties in pores introduced by Motivated concomitant oxidation benzaldehyde during formation, various organic substrates such amine methyl sulfide derivatives investigated. It shown that well-defined micropores enable size-selective oxidation.

Language: Английский

---

Enaminone‐Linked Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: May 31, 2023

Covalent organic frameworks (COFs), possessing pre-designable structures and tailorable functionalities, are promising candidates for photocatalysis. Nevertheless, the most studied imine-linked COFs (Im-COFs) usually suffer from unsatisfactory stability photocatalytic performance. To meet this challenge, a series of highly stable enaminone-linked (En-COFs) have been synthesized afford much improved visible-light-driven hydrogen production activities, ranging 44 to 1078 times that isoreticular Im-COFs, with only difference being linkages (enaminone vs. imine) in their structures. The enhanced light-harvesting ability, facilitated exciton dissociation chemical account superior activity. Furthermore, quinoline-linked (Qu-COFs) further obtained via post-modification Im-COFs. Compared activities Qu-COFs significantly after modification, but still below those corresponding En-COFs (3-107 times). facile synthesis, excellent activity, high demonstrate platform

Language: Английский

---

The photocatalytic H2O2 production by metal-free photocatalysts under visible-light irradiation

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 341, P. 123271 - 123271

Published: Sept. 6, 2023

Language: Английский

---

Clean Production of Hydrogen Peroxide: A Heterogeneous Solar‐Driven Redox Process

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(36)

Published: Aug. 6, 2023

Abstract Hydrogen peroxide is an essential chemical that attracting strong attention for energy and environmental applications. However, the struggle between growing market demand unsustainability of conventional anthraquinone method motivates exploration alternative H 2 O production processes. Although several new processes have been proposed, environmental‐friendly solar‐driven attracts most because only inputs water, oxygen, light energy. The rational design functional photo‐responsive catalysts promotes in photocatalytic photoelectrocatalytic approaches. These are, general, achieved by facilitating preferential adsorption key intermediates OOH*/OH*/O*, enhancing absorption, promoting charge separation, accelerating surface transfer with selective number involved charges. This review systematically summarizes strategies photo(electro)catalysts toward via both water oxidation oxygen reduction pathways. Though route perceived as more popular community, emerging a convincing alternative. Furthermore, prevailing hypotheses, state‐of‐the‐art catalysts, critical challenges, perspectives are discussed depth. aims to enhance comprehension this research field promote interest sustainable production.

Language: Английский

---