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

Spatially Separated Photoredox in a Covalent Organic Frameworks Heterostructure Boosting Overall Water Splitting DOI Creative Commons

Qing Niu,

Wei Chen,

Guodong Pan

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: 6(4), P. 1411 - 1417

Published: March 11, 2024

Covalent organic frameworks (COFs) with excellent structural tunability have emerged as fascinating photocatalysts to fulfill future energy demands. Here, we developed a COFs heterostructure by assembling two for photocatalytic overall water splitting. The resulting exhibited an effective spatial separation of photoredox sites originating from the efficient photoinduced charge carriers through orientated interfacial electron transfer pathway. Accordingly, displays activity stoichiometric splitting into H2 and O2 under 5 W white LED light irradiation. Our efficiencies evolution rates up 120 58 μmol g–1 h–1 are significantly higher than those reported previously. combination experiments theoretical calculations shows that oxidation proceeds metal-free hydration-mediated This work sheds on rational design COF spatially separated

Language: Английский

Citations

11
Single-Atom Catalysts on Covalent Organic Frameworks for Energy Applications DOI
Yurong Wu, Rui Wang, Yoonseob Kim

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 8, 2024

Single-atom catalysts (SACs) have been investigated and applied to energy conversion devices. However, issues of metal agglomeration, low loading, substrate stability hindered realization the SACs' full potential. Recently, covalent organic framework (COF)-based SACs emerged as promising materials enable highly efficient catalytic reactions. Here, we summarize representative COF-based their wide application in clean devices reactions, such hydrogen evolution reaction, carbon dioxide reduction nitrogen oxygen reaction. Based on catalysis conditions, these reactions are categorized into photocatalyzed electrocatalyzed We also design strategies, including heteroatom inclusion, donor–acceptor pairs, pore engineering, interface etc. Although promising, more efforts, linkage functional groups, ionization, multifunctional sites for cocatalyzed systems, etc., could improve them be ideal SAC materials. At end, provide our perspectives where field will proceed next 5 years.

Language: Английский

Citations

9
The crystalline linear polyimide with oriented photogenerated electron delivery powering CO2 reduction DOI Open Access
Huizhen Li,

Yanlei Chen,

Qing Niu

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 49, P. 152 - 159

Published: June 1, 2023

Language: Английский

Citations

21
Site-Selective Zn-Metalation in Poly-Triphenyl Amine-based Porous Organic Polymer for Solid–Gas Phase CO2 Photoreduction DOI
Ankita Boruah, Bishal Boro, Ratul Paul

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(27), P. 34437 - 34449

Published: June 28, 2024

Harvesting solar energy to produce value-added chemicals from carbon dioxide (CO2) presents a promising route for addressing the complexities of sustainable systems and environmental issues. In this context, development metal-coordinated porous organic polymers (POPs) offers vital avenue improving photocatalytic performance motifs. The current study metal-integrated system (namely, Zn@BP-POP) developed via one-pot Friedel–Crafts (F.C.) acylation strategy, solid–gas phase photochemical CO2 reduction CO (CO2RR). postsynthetic incorporation metal (Zn) active sites on host polymeric backbone BP-POP significantly influences catalytic activity. Notably, Zn@BP-POP demonstrates good in absence any cocatalyst photosensitizer yielding while impeding competitive hydrogen evolution reaction (HER) water. experimental findings collectively propose that observed activity selectivity arise synergistic interplay between singular zinc centers light-harvesting capacity highly conjugated backbone. Further, X-ray absorption spectroscopy (XAS) analysis has highlighted prominent role played by ZnN2O4 single framework activating gaseous molecules. time-dependent density functional theory (DFT) also reveals thermodynamic feasibility CO2RR over HER under optimized conditions. This work cumulatively an effective strategy demonstrate importance metal-active effectively establish their structure-activity relationship during photocatalysis.

Language: Английский

Citations

8
Charge Transport Approaches in Photocatalytic Supramolecular Systems Composing of Semiconductor and Molecular Metal Complex for CO2 Reduction DOI

Jiangqi Ning,

Wei Chen,

Qing Niu

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: May 4, 2024

Abstract The design of photocatalytic supramolecular systems composing semiconductors and molecular metal complexes for CO 2 reduction has attracted increasing attention. system combines the structural merits complexes, where semiconductor harvests light undertakes oxidative site, while complex provides activity reduction. intermolecular charge transfer plays crucial role in ensuring performance. Here, we review progress highlight interfacial pathways, as well their state‐of‐the‐art characterization methods. remaining challenges prospects further photocatalysts are also presented.

Language: Английский

Citations

6
Cheap transition metal reinforced donor–acceptor covalent organic frameworks for CO2 photoreduction DOI

Lvye Ai,

Qian Wang,

Xiaowen Chen

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 475, P. 146106 - 146106

Published: Sept. 16, 2023

Language: Английский

Citations

15
Isomerization of Covalent Organic Frameworks for Efficiently Activating Molecular Oxygen and Promoting Hydrogen Peroxide Photosynthesis DOI

Wenjiao Wang,

Rui Zhang,

Hongqi Chu

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

Abstract Constitutional‐isomerized covalent organic frameworks (COFs), constructed by swapping monomers around imine bonds, have attracted attention for their distinct optoelectronic properties, which significantly impact photocatalytic performance. However, limited research has delved into the inherent relationship between isomerization and enhancement of H 2 O photosynthesis. Herein, a pair isomeric COFs linked bonds (PB‐PT‐COF PT‐PB‐COF) is synthesized, it proved that exhibit different rate‐determining steps in generation process , resulting twofold increase efficiency. Specifically, PT‐PB‐COF demonstrates effective adsorption activation molecular oxygen (O + e − → •O ), leading to significant improvement In contrast, PB‐PT‐COF exhibits robust interaction with O, enabling direct oxidation (H h ). This study provides thorough understanding intrinsic mechanism underlying constitutional‐isomerized generation, offering insights further optimizing building units.

Language: Английский

Citations

5
In pursuit of a bifunctional designing toward highly efficient overall water splitting in a hydrogen-functionalized two-dimensional covalent organic framework via single transition metal mapping DOI
Chunyao Fang, Di Liu, Qiang Zhang

et al.

International Journal of Hydrogen Energy, Journal Year: 2024, Volume and Issue: 62, P. 48 - 61

Published: March 9, 2024

Language: Английский

Citations

4
Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen DOI
Shuailei Xie, Ruoyang Liu,

Nengyi Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π-stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy developing vertically expanded to expose originally inaccessible active sites hidden catalysis. We designed covalently linked two-dimensional cobalt(II) porphyrin explored coordination bonds connect the bidentate ligands via three-component one-pot polymerization. The resultant expand interlayer space greatly, where both up down faces of each layer are exposed reactants. Unexpectedly, increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity affinity water, facilitate water delivery. Remarkably, these positive effects work collectively photocatalysis into oxygen, an oxygen production rate 1155 μmol g

Language: Английский

Citations

4
Advancements and challenges in g-C3N4/ZnIn2S4 heterojunction photocatalysts DOI
Yi Lu, Zanyong Zhuang, Lingyun Li

et al.

Journal of Materials Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this review, a comprehensive summation of the heterojunction types, synthesis methodologies, engineering approaches, and potential photocatalytic applications pertaining to g-C 3 N 4 /ZnIn 2 S heterojunctions has been presented in-depth discussed.

Language: Английский

Citations

0