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

---

Recent advances in TiO2-based S-scheme heterojunction photocatalysts

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 55, P. 137 - 158

Published: Dec. 1, 2023

Language: Английский

---

Constructing Chiral Covalent‐Organic Frameworks for Circularly Polarized Light Detection

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: Aug. 17, 2023

Abstract The use of chiral covalent organic frameworks (COFs) as active elements in photodetectors to directly identify circularly polarized light (CPL) can meet the requirement integration and miniaturization as‐fabricated devices. Herein, design synthesis two isoreticular two‐dimensional (2D) COFs (CityU‐7 CityU‐8) by introducing photosensitive porphyrin‐based amines (5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin) enhance optical absorption aldehyde linkage (2,5‐bis((S/R))‐2‐methylbutoxy)terephthalaldehyde) engender chirality for direct CPL detection are reported. Their crystalline structures were confirmed powder X‐ray diffraction, Fourier‐transform infrared spectroscopy, low‐dose transition electron microscopy. Employing both layers photodetectors, left‐handed (LHC) right‐handed (RHC) at 405 nm be well distinguishable with short response time, high responsivity, satisfying detectivity. study provides first example on CPL.

Language: Английский

---

Linker Engineering for Reactive Oxygen Species Generation Efficiency in Ultra-Stable Nickel-Based Metal–Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18931 - 18938

Published: Aug. 17, 2023

Interfacial charge transfer on the surface of heterogeneous photocatalysts dictates efficiency reactive oxygen species (ROS) generation and therefore aerobic oxidation reactions. Reticular chemistry in metal-organic frameworks (MOFs) allows for rational design donor-acceptor pairs to optimize interfacial charge-transfer kinetics. Herein, we report a series isostructural fcu-topology Ni8-MOFs (termed JNU-212, JNU-213, JNU-214, JNU-215) with linearly bridged bipyrazoles as organic linkers. These crystalline can maintain their structural integrity 7 M NaOH at 100 °C 24 h. Experimental studies reveal that linker engineering by tuning electron-accepting capacity pyrazole-bridging units renders these significantly improved separation under visible-light irradiation. Among them, one containing benzoselenadiazole unit (JNU-214) exhibits best photocatalytic performance benzylamines conversion rate 99% Recycling experiments were carried out confirm stability reusability JNU-214 robust catalyst. Significantly, systematic modulation bridging donor-acceptor-donor MOFs provides new pathway develop viable noble-metal-free

Language: Английский

---

Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation

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

---

Structural Motifs in Covalent Organic Frameworks for Photocatalysis

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

---

Engineering photocatalytic ammonia synthesis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(20), P. 6938 - 6956

Published: Jan. 1, 2023

This review is organized based on an engineering perspective, including materials engineering, structure and reaction spanning photocatalyst preparation to photocatalytic process intensification.

Language: Английский

---

Optimization Strategies of Covalent Organic Frameworks and Their Derivatives for Electrocatalytic Applications

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(11)

Published: Nov. 27, 2023

Abstract Covalent organic frameworks (COFs) are crystalline porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in field electrocatalysis. The precise control channel/dopant positions highly ordered network structures COFs provide an ideal material system applications advanced In this paper, topological structure design synthesis methods reviewed detail, their principles deeply analyzed. addition, derivatives electrocatalysis systematically summarized optimization strategies proposed. Finally, application prospects challenges may encountered future prospected, providing helpful guidance research.

Language: Английский

---

Interfacial Chemical-Bonded MoS₂/In–Bi₂MoO₆ Heterostructure for Enhanced Photocatalytic Nitrogen-to-Ammonia Conversion

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6292 - 6304

Published: April 10, 2024

Photocatalytic nitrogen reduction reaction (pNRR) is considered an ideal NH3 synthetic technology. Although catalysts prepared for pNRR under mild conditions have been extensively developed, they still face limitations of insufficient N2 adsorption/activation and low selectivity. Herein, a MoS2/In–Bi2MOO6 heterojunction catalyst with interfacial chemical bond was constructed by the electrostatic self-assembly method. Efficient spatial separation photogenerated electron/hole pairs accelerated carrier transfer dynamics were facilitated due to formation Mo–S at interface between MoS2 In–Bi2MoO6. The crystal orbital Hamiltonian population (COHP) analysis further confirmed that electrons transferred from into antibonding activate adsorbed N2, favoring nitrogen-to-ammonia (N2-to-NH3) conversion. resultant NH3/NH4+ production rate 3% MoS2/In–Bi2MoO6 reached 90 μmol·g–1·h–1, representing significant improvement over pure Bi2MoO6, while NO3– minimal. Introducing as cocatalyst effectively inhibited oxidation NO3–, achieving selective pNRR. This work provides foundation photocatalytic fixation, offering valuable insights clean NH3.

Language: Английский

---