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

Ambient Preparation of Benzoxazine‐based Phenolic Resins Enables Long‐term Sustainable Photosynthesis of Hydrogen Peroxide DOI Creative Commons
Xinyao Wang, Xiaowei Yang, Chen Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 25, 2023

Rational design of polymer structures at the molecular level promotes iteration high-performance photocatalyst for sustainable photocatalytic hydrogen peroxide (H2 O2 ) production from oxygen and water, which also lays basis revealing reaction mechanism. Here we report a benzoxazine-based m-aminophenol-formaldehyde resin (APFac) polymerized ambient conditions, exhibiting superior H2 yield long-term stability to most polymeric photocatalysts. Benzoxazine structure was identified as crucial active segment in APFac. Favorable adsorption oxygen/intermediates on benzoxazine commendable product selectivity accelerated kinetically stepwise single-electron reduction reaction. The proposed phenolic provides possibility batches industrial application, sheds light de novo analysis metal-free

Language: Английский

Citations

75
Twistedly hydrophobic basis with suitable aromatic metrics in covalent organic networks govern micropollutant decontamination DOI Creative Commons

Chencheng Qin,

Yi Yang, Xiaodong Wu

et al.

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

Published: Oct. 24, 2023

Abstract The pre-designable structure and unique architectures of covalent organic frameworks (COFs) render them attractive as active porous medium for water crisis. However, the effect functional basis with different metrics on regulation interfacial behavior in advanced oxidation decontamination remains a significant challenge. In this study, we pre-design fabricate molecular interfaces by creating ordered π skeletons, incorporating pore sizes, engineering hydrophilic or hydrophobic channels. These synergically break through adsorption energy barrier promote inner-surface renewal, achieving high removal rate typical antibiotic contaminants (like levofloxacin) BTT-DATP-COF, compared BTT-DADP-COF BTT-DAB-COF. experimental theoretical calculations reveal that such enable hole-driven levofloxacin at interface BTT fragments to occur, accompanying electron-mediated oxygen reduction terphenyl motif radicals, endowing it facilitate balanced extraction holes electrons.

Language: Английский

Citations

70
Efficient Photosynthesis of Hydrogen Peroxide by Cyano‐Containing Covalent Organic Frameworks from Water, Air and Sunlight DOI

Yanghui Hou,

Peng Zhou,

Fuyang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 28, 2023

Abstract The insufficient exciton ( e − ‐ h + pair) separation/transfer and sluggish two‐electron water oxidation are two main factors limiting the H 2 O photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate reduce energy barrier in COFs via a dicyano functionalization. situ characterization theoretical calculations reveal that functionalization improves amount charge transfer channels between donor acceptor units from COF‐0CN without cyano three COF‐1CN with mono‐cyano four COF‐2CN functionalization, leading highest COF‐2CN. More importantly, group activates neighbouring C atom produce key *OH intermediate for effectively reducing rate‐determining photosynthesis. enhanced result high yield (1601 μmol g −1 ) oxygen using sacrificial reagent under visible‐light irradiation. can wide pH range, different real samples, scaled‐up reactor natural sunlight irradiation, continuous‐flow consecutively producing solution decontamination.

Language: Английский

Citations

69
Engineering 2D Photocatalysts for Solar Hydrogen Peroxide Production DOI
Jindi Yang, Xiangkang Zeng, Mike Tebyetekerwa

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(23)

Published: April 3, 2024

Abstract Solar energy can be utilized in photocatalysis technology to realize light‐driven hydrogen peroxide (H 2 O ) production, a green chemical synthesis route. Designing high‐performance photocatalysts is critical achieving practical solar H production. During the past decade, significant research progress made photocatalytic materials for Particularly 2D materials‐based stand out due their unique physical and properties. This review highlights intricate relationship between material innovation photochemical It starts with fundamental principles of generation, focusing on crucial steps such as photon absorption, carrier dynamics, surface reactions, challenges that solve at each step. Then, various production are introduced detail. Engineering strategies optimize performance discussed afterward. Finally, future opportunities designing outlined. expected inspire engineering conversion other chemicals.

Language: Английский

Citations

68
In-situ formatting donor-acceptor polymer with giant dipole moment and ultrafast exciton separation DOI Creative Commons
Chang Cheng, Jiaguo Yu, Difa Xu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 13, 2024

Abstract Donor-acceptor semiconducting polymers present countless opportunities for application in photocatalysis. Previous studies have showcased their advantages through direct bottom-up methods. Unfortunately, these approaches often involve harsh reaction conditions, overlooking the impact of uncontrolled polymerization degrees on Besides, mechanism behind separation electron-hole pairs (excitons) donor-acceptor remains elusive. This study presents a post-synthetic method involving light-induced transformation building blocks hyper-cross-linked from donor-carbon-donor to donor-carbon-acceptor states, resulting polymer with substantial intramolecular dipole moment. Thus, excitons are efficiently separated transformed polymer. The utility this strategy is exemplified by enhanced photocatalytic hydrogen peroxide synthesis. Encouragingly, our observations reveal formation charge transfer states using time-resolved techniques, confirming transient exciton behavior and relaxation. not only guides development highly efficient photocatalysts but also applies various fields, including organic solar cells, light-emitting diodes, sensors.

Language: Английский

Citations

67
Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation DOI Open Access

Liujun Yang,

Zhengxi Chen,

Qiang Cao

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(3)

Published: Oct. 22, 2023

Ring-opening of phenol in wastewater is the pivotal step photocatalytic degradation. The highly selective generation catalytical active species (•OH) to facilitate this process presents a significant scientific challenge. Therefore, novel approach for designing photocatalysts with single-atom containment metal-covalent organic frameworks (M-COFs) proposed. selection imine-linked COFs containing abundant N and O-chelate sites provides solid foundation anchoring metal atom. These dispersed atom possess rapid accumulation transfer capabilities photogenerated electrons, while periodic π-conjugated structure 2D-COFs establishes an effective platform. Additionally, Lewis acid properties imine bonds can enhance adsorption capacity toward gases base properties, such as O

Language: Английский

Citations

63
Structural Motifs in Covalent Organic Frameworks for Photocatalysis DOI

Liyang Qin,

Chengdi Ma,

Jian Zhang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: March 10, 2024

Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization

Language: Английский

Citations

61
Vinyl‐Group‐Anchored Covalent Organic Framework for Promoting the Photocatalytic Generation of Hydrogen Peroxide DOI
Hong Yu,

Fengtao Zhang,

Qian Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 16, 2024

The artificial photosynthesis of H

Language: Английский

Citations

59
Three-Motif Molecular Junction Type Covalent Organic Frameworks for Efficient Photocatalytic Aerobic Oxidation DOI
Mingyi Yang, Shuai‐Bing Zhang, Mi Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3396 - 3404

Published: Jan. 24, 2024

Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction functional groups, have aroused broad interest in field photocatalysis. However, due to low light absorption intensity, photoelectron conversion efficiency, lack suitable active sites, it remains a great challenge achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed series three-motif molecular junction type COFs, which formed dual photosensitizer coupled redox junctions containing multifunctional COF photocatalysts. Significantly, strong adsorption ability units integrated reduction features, PY-BT exhibited highest activity for oxidation. Especially, achieved benzylamine efficiency 99.9% 2.5 h, is much higher than that two-motif only one or unit lacking COFs. The mechanism selective was studied through comprehensive experiments density theory calculations. results showed photoinduced electron transfer occurred from PY then triphenylamine BT. Furthermore, thermodynamics energy lower others, confirmed synergistic effect This work provided new strategy design COFs also represented insight into catalytic

Language: Английский

Citations

56
Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction DOI
Xuewen Li, Shuai Yang, Minghao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 28, 2023

Metal-free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms groups linked by imine bonds were used create catalytic COFs. However, roles of linkages COFs in ORR not investigated. In this work, linkage engineering has modulate behaviors. single sites while avoiding other possible sites, we synthesized from benzene units bonds, such as imine, amide, azine, oxazole bonds. Among these COFs, oxazole-linkage enables with highest activity, which achieved a half-wave potential 0.75 V limited current density 5.5 mA cm-2 . Moreover, oxazole-linked COF conversion frequency (TOF) value 0.0133 S-1 , 1.9, 1.3, 7.4-times that azine-, amide- imine-COFs, respectively. The theoretical calculation showed carbon atoms facilitated formation OOH* promoted protonation O* form OH*, thus advancing activity. This work guides us on are suitable for ORR.

Language: Английский

Citations

51