Exciton Dipole Orientation and Dynamic Reactivity Synergistically Enable Overall Water Splitting in Covalent Organic Frameworks DOI

Qing Niu,

Wenfeng Deng,

Yanlei Chen

et al.

ACS Energy Letters, Journal Year: 2024, Volume and Issue: unknown, P. 5830 - 5835

Published: Nov. 11, 2024

Covalent organic frameworks (COFs) are promising semiconductor photocatalysts but still limited in overall water splitting mainly owing to a lack of clear design approaches with which ameliorate catalytic activities. Here, we demonstrate synergy exciton dipole orientation and dynamic reactivity COFs that enables for stoichiometric evolution H2 O2. The is responsible driving the spatial separation photoinduced charges, while imine bonds holes proven initiating oxidation. Accordingly, rationally designed BtS-COF benzotrithiophene sulfone units exhibits much-improved performance O2 neutral under visible light. Its efficiency even superior some metal-based oxidation cocatalyst.

Language: Английский

Thiophene‐Containing Covalent Organic Frameworks for Overall Photocatalytic H2O2 Synthesis in Water and Seawater DOI
Jieyu Yue, Liping Song,

Yanfei Fan

et al.

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

Citations

152
COF/In2S3 S‐Scheme Photocatalyst with Enhanced Light Absorption and H2O2‐Production Activity and fs‐TA Investigation DOI
Junyi Qiu, Kai Meng, Yong Zhang

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(24)

Published: Feb. 27, 2024

Photocatalytic hydrogen peroxide (H

Language: Английский

Citations

105
Donor-acceptor-based conjugated polymers for photocatalytic energy conversion DOI
Chao Yang, Bei Cheng, Jingsan Xu

et al.

EnergyChem, Journal Year: 2023, Volume and Issue: 6(1), P. 100116 - 100116

Published: Nov. 29, 2023

Language: Английский

Citations

54
Molecular‐Level Regulation Strategies Toward Efficient Charge Separation in Donor−Acceptor Type Conjugated Polymers for Boosted Energy‐Related Photocatalysis DOI
Lu Wang,

Linghao Liu,

Yan Li

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(5)

Published: Dec. 11, 2023

Abstract The development of efficient photocatalysts for artificial photocatalytic energy conversion is an intriguing strategy. Promisingly, conjugated polymers (CPs) have been actively investigated as alternatives to traditional inorganic semiconductors photocatalysis due their molecularly tunable optoelectronic properties, thus providing a great platform molecular design. Incorporating donor (D) and acceptor (A) units into the backbone CPs ensures adequate D−A interface, which essential facilitating charge separation. This approach also allows bandgaps leading significant progress in conversions recent years. Here, fundamentals D–A type are initially outlined, followed by advanced experimental methods density functional theory (DFT) calculations investigating carrier dynamics. Then, detailed exposition synthetic strategies carried out. Their extensive applications diverse energy‐related conversions, such hydrogen evolution, oxygen overall water splitting, CO 2 reduction, N H O evolution comprehensively presented. review provides new comprehensive insights molecular‐level design catalysts boosted conversion, expected further advance photocatalysis.

Language: Английский

Citations

48
Dual Cocatalysts Synergistically Promote Perylene Diimide Polymer Charge Transfer for Enhanced Photocatalytic Water Oxidation DOI
Wenlu Li, Zhen Wei,

Yuqiang Sheng

et al.

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(6), P. 2652 - 2660

Published: May 18, 2023

Water oxidation is a critical reaction in artificial photosynthesis which limited by high energy barrier and often requires matching cocatalysts. Dual cocatalysts Co3O4 Pt are combined with perylene diimide (PDI) polymer, accomplishing photocatalytic O2 production rate of 24.4 mmol g–1 h–1 under visible light irradiation, 5.4-fold enhancement compared PDI alone. Moreover, the apparent quantum yield evolution reaches 6.9% at 420 nm remains 1.2% 590 nm. The dual cocatalysts-constructed interfacial electric fields provide an anisotropic driving force for photogenerated holes to electrons Pt, synergistically improving spatial charge separation efficiency water oxidation. molecules serve as active sites improve utilization on surface. This work provides valuable demonstration interaction process mechanism cocatalysts, guiding selection high-efficiency solar conversion.

Language: Английский

Citations

43
Regulating the H2O2 Photosynthetic Activity of Covalent Organic Frameworks through Linkage Orientation DOI
Jieyu Yue,

Li-Ping Song,

Zi‐Xian Pan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4728 - 4737

Published: March 13, 2024

Imine-linked isomeric covalent organic frameworks (COFs) with opposite linkage orientations are not rare, but their structure and photocatalytic property corrections still puzzling, let alone the emerging photosynthetic H2O2 performance. Herein, a pair of COFs (TB-COF TA-COF) reversed imine linkages was fabricated. Compared to TA-COF, TB-COF exhibited larger dipole moments better charge carrier separation efficiency, resulting in superior photosynthesis capability via dominant oxygen reduction reaction (ORR) paths (O2–O2•––H2O2 O2–O2•––O21–H2O2) feeble water oxidation (WOR) paths. With no sacrificial agents air, rates were 5186 μmol g–1 h–1 4111 natural seawater, respectively. The seawater-produced can be directly utilized for tetracycline degradation, manifesting big picture wastewater treatment by H2O2. Theoretical calculations revealed that hydroxyl-rich benzene ring photooxidation part triazine unit primary photoreduction part. Through linkage-orientation regulation, electronic structures, migration property, energy barrier rate determination step 2e– ORR WOR well-modulated. current work provides insight into effect orientation on performance may enlighten design catalysts photosynthesis.

Language: Английский

Citations

35
Interface engineering in a nitrogen-rich COF/BiOBr S-scheme heterojunction triggering efficient photocatalytic degradation of tetracycline antibiotics DOI
Jinhong Bi,

Zhangtong Zhang,

Jinjin Tian

et al.

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 661, P. 761 - 771

Published: Feb. 3, 2024

Language: Английский

Citations

31
Self‐Accelerating H2 Evolution Activity by In Situ Transformation on Noble‐Metal‐Free Photocatalyst of Covalent Organic Framework and Cu2O Composite DOI

Yu‐Han Liu,

Xiaoyu Chu, Yanxia Jiang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(25)

Published: Feb. 9, 2024

Abstract It is expected that the activity of photocatalysts can remain same or decrease as little possible in photocatalysis reaction. Herein, for first time, a self‐accelerating H 2 production noble‐metal‐free Cu O/TpPa‐2‐COF photocatalyst reported. shows beginning rate 4.41 mmol h −1 g under visible light illuminance, while kept increasing to 27.27 after 25 reaction, which 6.2 times higher than and reaches record high. confirmed part O situ transformed 0 photocatalytic acting cocatalyst promotes separation photogenerated charge carriers. Further density functional theory calculations demonstrate Schottky barrier height Cu‐Cu (111) interface much smaller Pt‐Cu (111), supporting its more efficient effect with Pt cocatalyst.

Language: Английский

Citations

16
Multiple Heteroatom‐Hydrogen Bonds Bridging Electron Transport in Covalent Organic Framework‐Based Supramolecular System for Photoreduction of CO2 DOI

Yajun He,

Yun Zhao, Xiao‐Feng Wang

et al.

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

Published: June 7, 2023

Supramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction CO2 . Multiple heteroatom-hydrogen bonding between the COF is identified to play a decisive role in photoexcited electron transfer across liquid-solid interface. The diminution steric groups on or metal can optimize catalytic performance, which more attributable enhanced hydrogen-bond interaction rather than their intrinsic activity. photosystem with relatively strong strength hydrogen bonds exhibits remarkable -to-CO conversion, far superior photosystems supported atomic alone absence effect. Such bridging transport pathway confers supramolecular system high providing an avenue rationally design efficient steadily available photosystems.

Language: Английский

Citations

40
Review of covalent organic frameworks for single-site photocatalysis and electrocatalysis DOI

Qing Niu,

Linhua Mi,

Wei Chen

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 50, P. 45 - 82

Published: July 1, 2023

Language: Английский

Citations

32