The order–disorder conundrum: a trade-off between crystalline and amorphous porous organic polymers for task-specific applications

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(33), P. 17077 - 17121

Published: Jan. 1, 2022

The review unravels the order–disorder conundrum in porous organic polymers view of task-specific applications through a comparative deliberation.

Language: Английский

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Thermally Induced Orderly Alignment of Porphyrin Photoactive Motifs in Metal–Organic Frameworks for Boosting Photocatalytic CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 18148 - 18159

Published: Aug. 2, 2023

Efficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO2 reduction, but it still challenging effectively modulate the electronic between photoactive motifs by feasible chemical means. In this work, we propose thermally induced strategy precisely electron formed porphyrin metal–organic framework using thorium ion with large ionic radius and high coordination number as coordination-labile metal node. As result, stacking pattern molecules before after crystal transformations has changed dramatically, which leads significant differences separation efficiency photogenerated MOFs. The rate CO IHEP-22(Co) reaches 350.9 μmol·h–1·g–1, 3.60 times that IHEP-21(Co) 1.46 IHEP-23(Co). Photoelectrochemical characterizations theoretical calculations suggest channels inhibit recombination carriers, resulting for reduction. interaction mechanism was clarified in-situ paramagnetic resonance, diffuse reflectance infrared Fourier transform spectroscopy, extended X-ray absorption fine structure calculations. These results provide new method regulate efficient migration photocatalysts will be helpful guide design synthesis superior production solar fuels.

Language: Английский

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Molecular engineering of biomimetic donor-acceptor conjugated microporous polymers with full-spectrum response and an unusual electronic shuttle for enhanced uranium(VI) photoreduction

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 466, P. 143285 - 143285

Published: May 2, 2023

Language: Английский

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Engineering Single Cu Sites into Covalent Organic Framework for Selective Photocatalytic CO₂ Reduction

Small, Journal Year: 2023, Volume and Issue: 19(22)

Published: March 3, 2023

Photocatalytic CO2 conversion into value-added chemicals is a promising route but remains challenging due to poor product selectivity. Covalent organic frameworks (COFs) as an emerging class of porous materials are considered candidates for photocatalysis. Incorporating metallic sites COF successful strategy realize high photocatalytic activities. Herein, 2,2'-bipyridine-based bearing non-noble single Cu fabricated by chelating coordination dipyridyl units reduction. The coordinated not only significantly enhance light harvesting and accelerate electron-hole separation also provide adsorption activation molecules. As proof concept, the Cu-Bpy-COF representative catalyst exhibits superior activity reducing CO CH4 without photosensitizer, impressively, selectivity can be readily modulated changing reaction media. Experimental theoretical results reveal crucial role in promoting photoinduced charge solvent effect regulating selectivity, which provides important sight onto design photocatalysts selective photoreduction.

Language: Английский

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Extending the π-Conjugated System in Conjugated Microporous Polymers to Modulate Excitonic Effects for Metal-Free Selective CO₂ Photoreduction to CH₄

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12142 - 12152

Published: Aug. 31, 2023

Photocatalytic CO2 reduction into CH4 is an appealing approach to alleviate the current energy and environmental crisis; however, achieving high selectivity conversion efficiency still remains challenging. The rational design of photocatalysts for adsorption activation thus crucial. Here, we designed synthesized two redox-active truxene-based conjugated microporous polymers linked by thiazolo[5,4-d]thiazole metal-free photocatalytic CH4. Significantly, optimized polymer with extended π-conjugated system, denoted Tx-TzTz-CMP-2, presented a higher production rate 300.6 μmol g–1 h–1 71.2% without any metal cocatalyst photosensitizer, which outperformed most previously reported photocatalysts. Experimental theoretical investigations revealed that introducing phenyl as π-bridge extending electron delocalization system might effectively minimize exciton binding energy, thereby boosting intramolecular charge transfer separation abilities. Meanwhile, N-site thiazole unit acted reservoir catalytic center activating adsorbed forming subsequent hydrogenation. This work highlights significance in improve activity photoreduction

Language: Английский

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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

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Construction of Low-Cost Z-Scheme Heterojunction Cu₂O/PCN-250 Photocatalysts Simultaneously for the Enhanced Photoreduction of CO₂ to Alcohols and Photooxidation of Water

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(39), P. 15963 - 15970

Published: Sept. 19, 2023

Solar-driven high-efficiency conversion of CO2 with water vapor into high-value-added alcohols is a promising approach for reducing emissions and achieving carbon neutrality. However, the rapid recombination photogenerated carriers low adsorption capacity photocatalysts are usually factors that limit their applicability. Herein, series low-cost Z-scheme heterostructures Cu2O/PCN-250-x constructed by in situ growth ultrasmall Cu2O nanoparticles on PCN-250. A systematic investigation revealed there strong interaction between The resulting Cu2O/PCN-250-2 exhibits excellent carrier separation efficiency capacity, which dramatically promote alcohols. Notably, total yield 268 μmol gcat-1 production CH3OH CH3H2OH superior to isolated PCN-250 Cu2O. This study provides new perspective design nanoparticle/metal-organic framework heterojunction reduction vapor.

Language: Английский

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Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D−π–A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation

JACS Au, Journal Year: 2023, Volume and Issue: 3(5), P. 1424 - 1434

Published: May 6, 2023

Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor-π-acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN-5B2T D-π-A OCPs). The resultant PCN-5B2T OCPs extended the π-conjugate structure introduced abundant micro-, meso-, macro-pores, which greatly promoted transfer, light absorption, thus significantly enhanced photocatalytic performance pollutant degradation. apparent rate constant of optimized OCP 2-mercaptobenzothiazole (2-MBT) removal ∼10 times higher than that pure PCN. Density functional theory calculations reveal photogenerated electrons are much easier from donor tertiary amine group benzene π-bridge then acceptor imine group, while 2-MBT more easily adsorbed on reacts holes. A Fukui function calculation intermediates predicted real-time changing actual reaction sites during entire degradation process. Additionally, computational fluid dynamics further verified rapid OCPs. These results demonstrate novel concept toward highly photocatalysis remediation by improving both transport.

Language: Английский

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Donor-acceptor-based conjugated polymers for photocatalytic energy conversion

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

Published: Nov. 29, 2023

Language: Английский

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Photocatalytic CO₂ Reduction Based on a Re(I)-Integrated Conjugated Microporous Polymer: Role of a Sacrificial Electron Donor in Product Selectivity and Efficiency

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(9), P. 5969 - 5978

Published: April 18, 2023

One of the major challenges in photocatalytic CO2 reduction is achieving control over selective formation a single product while maintaining high conversion efficiency. Here, we report synthesis and characterization conjugated microporous polymer (TEB-BPY) formed by C–C coupling between 1,3,5-triethynylbenzene 5,5′-dibromo-2,2′-bipyridine. Further, [Re(CO)5Cl] covalently integrated with polymer, resulting metalated Re@TEB-BPY was used as catalyst for visible-light-driven reduction. displays photoconversion to CO production rate 91.7 μmol g–1 h–1 selectivity ∼68% presence triethylamine (TEA) sole sacrificial electron donor. Interestingly, CH4 produced instead when performed using 1-benzyl-1,4-dihydronicotinamide (BNAH) donor TEA base. In this reaction, produces 2.05 mmol (selectivity ∼96% apparent quantum efficiency 0.22%). From an situ diffuse reflectance FTIR spectroscopy (DRIFTS) study together DFT calculations, possible catalytic cycle or constructed. Theoretical calculations along experiments further reveal that acts mainly base BNAH suppress back transfer process, enhanced activity.

Language: Английский

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