Hollow Rh-COF@COF S-Scheme Heterojunction for Photocatalytic Nicotinamide Cofactor Regeneration

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6619 - 6629

Published: April 28, 2023

Photocatalytic regeneration of a nicotinamide cofactor, adenine dinucleotide phosphate (NADPH), has emerged as an ideal cascade partner for combination with enzymatic transformations, but it still suffers from low efficiency due to the recombination photogenerated charge carriers. Herein, hierarchical Rh-covalent organic framework (COF)@COF core–shell hollow sphere (CSHS) S-scheme heterojunction is proposed enhance carrier transfer and utilization in photocatalysis regenerate expensive NADPH. The Rh-COFBpy@ spherical COF (HCOF) CSHS was prepared by simple sequential situ growth. turnover frequency Rh-COFBpy@HCOF25 NADPH reached 2.6 mmol·gRh-COF–1·h–1, which 3.7 times that pure Rh-COFBpy under visible light. Density functional theory calculation X-ray photoelectron spectroscopy analysis showed internal electric field directed HCOF formed Rh-COFBpy@HCOF CSHS, accelerated electron Rh-COFBpy. In irradiated XPS analyses photoirradiated Kelvin probe measurement revealed charge-transfer mechanism within Rh-COFBpy@HCOF. photocatalytic system further coupled reduction C═C, achieving photoenzyme reaction. This work provides protocol design COF-based artificial photosynthetic systems.

Language: Английский

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Recent advances in porous materials for photocatalytic NADH regeneration

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(6), P. 3209 - 3229

Published: Jan. 1, 2024

This review focuses on recent research progress porous photocatalysts ( e.g. , g-C 3 N 4 COFs, MOFs, CMPs, and transition metal compounds) for photocatalytic NADH regeneration.

Language: Английский

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Cadmium sulfide nanoparticles compositing with chitosan and metal-organic framework: Enhanced photostability and increased carbon dioxide reduction

Advanced Composites and Hybrid Materials, Journal Year: 2024, Volume and Issue: 7(1)

Published: Jan. 27, 2024

Language: Английский

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Enhancing Photocatalytic CO₂ Reduction and Photo-oxidative Coupling over CdS/S-g-C₃N₄ Heterojunction Interface into Solar Chemicals

Energy & Fuels, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 12, 2025

Graphitic carbon nitride (g-C3N4) has gained attention as a metal-free photocatalyst to generate solar chemicals via efficient solar-driven CO2 reduction reactions. Even though the pristine g-C3N4 and its analogous ones have excellent chemical properties, disordered structure observed in various types of hinders charge separation process well transport photoexcited carriers linked photocatalytic performance. To overcome this limitation, we employed introduction heterojunction architecture into sulfur-doped with CdS. By using self-assembled method, fabricated CdS/S-g-C3N4 designed hybrid artificial photosynthetic module including biological enzyme for generation HCOOH from CO2. From test, it was confirmed that presence interfacial showed enhanced production formic acid is much higher than S-g-C3N4. The systematic spectroscopic measurements provide mechanistic insights photoinduced electronic dynamics macroscopic performance photocatalyst. Our study suggests photosynthesis based on architecture-embedded will offer promising sustainable strategy fixing generating chemicals.

Language: Английский

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Direct Z-Scheme Polymer/Polymer Double-Shell Hollow Nanostructures for Efficient NADH Regeneration and Biocatalytic Artificial Photosynthesis under Visible Light

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4433 - 4443

Published: March 17, 2023

The design of a highly efficient polymer photocatalyst is an essential prerequisite for photo-biocatalysis in polymer–enzyme coupled system, which offers important platform the synthesis pharmaceuticals and fine chemicals. However, current polymers still suffer drawbacks poor water wettability, low visible light absorption, high recombination rate photoinduced electron/hole pairs, severely limit their application photo-biocatalysis. Herein, we demonstrate polymer/polymer double-shell hollow nanostructure (PCN@PDBTS-HN) via facile two-step polymerization with polymeric carbon nitride (PCN) poly-dibenzothiophene sulfone (PDBTS) as internal external shells, respectively. covalent connection those two layers ensures spontaneous electron transfer from PDBTS to PCN, reflected X-ray photoelectron spectroscopy (XPS), paramagnetic resonance (EPR), fluorescence spectra, could effectively accelerate charge separation migration. Thanks its improved light-harvesting, increased hydrophilicity, enhanced redox capacity, obtained PCN@PDBTS-HN demonstrates excellent catalytic efficiency visible-light-promoted NADH regeneration conversion 85.4% being achieved 40 min (turnover frequency 0.859 mmol g–1 h–1). This value 1.4 2.6 times higher than that pristine PCN PDBTS, respectively, indicating role Z-scheme heterojunction improving efficiency. In addition, also displays photocatalytic selectivity 1,4-NADH regeneration, remarkable photostability, good biocompatibility. A total amount 2.12 mM methanol 8.39 l-glutamate was accumulated polymer/alcohol dehydrogenase (YADH) polymer/glutamate (GDH) implying flexibility chemical production photo-biocatalytic approach.

Language: Английский

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Formate‐Mediated Electroenzymatic Synthesis via Biological Cofactor NADH

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 22, 2024

Abstract Synthetic biohybrid systems by coupling artificial system with nature's machinery may offer a disruptive solution to address the global energy crisis. We developed versatile electroenzymatic pathway for continuous synthesis of valuable chemicals, facilitated formate‐driven NADH regeneration. Utilizing bismuth electrocatalyst, we achieved stable CO 2 reduction formate approximately 90 % Faraday efficiency at current density 150 mA cm −2 . The generated acts as mediator regenerate NADH, which is then coupled immobilized redox enzymes—alcohol dehydrogenase (ADH), L ‐lactate (LDH), and ‐glutamate (GDH)—to produce targeted chemicals significant rates exceptionally high turnover numbers (1.8×10 6 3.1×10 ). These achievements not only underscore but also its practical applicability in industrial settings. By leveraging situ formate, this innovative approach demonstrates potential integrating electrocatalysis enzymatic reactions sustainable efficient chemical production on scale.

Language: Английский

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Regeneration of NAD(P)H and its Analogues by Photocatalysis with Ionized Carbon Nitride

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5868 - 5878

Published: April 3, 2024

The regeneration of NAD(P)H and its analogues is crucial for biocatalytic processes. However, despite the efficiency enzymatic catalysis in regenerating NAD(P)H, sustainability enzymes often compromised, particularly under extreme catalytic conditions. Moreover, artificial cofactors may present advantages certain reactions due to their stability versatility, yet substrate specificity poses significant challenges through method. Therefore, it imperative develop a highly stable method that can be adapted both natural cofactors. In this work, employing potassium-ion-doped carbon nitride (ionCN-0.2) as catalyst not only achieves high-efficiency photocatalytic comparable glucose dehydrogenase (GDH), but also remarkable ability regenerate nicotinamide analogues. This enhanced performance stems from tunable negative ζ-potential, which effectively adsorbs positively charged [Cp*Rh(bpy)H2O]2+ mediator, resulting kinetics moiety. demonstrates superior compared reported systems; optimal rate reaches 0.55 mmol L–1 gcat–1 min–1 approaches efficiency. Expanding reaction conditions wider temperature pH range confirms effectiveness sufficient system, offering promising strategy cofactor

Language: Английский

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Emerging conjugated polymers for heterogeneous photocatalytic chemical transformation

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(60), P. 9167 - 9181

Published: Jan. 1, 2023

Design strategies for efficient π-conjugated polymer-based photocatalysts, and the progress achieved in light-driven chemical transformations using them.

Language: Английский

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Carbazole‐Based Donor‐Acceptor Conjugated Microporous Polymers for Efficient Visible‐Light‐Driven Photocatalytic H₂ Evolution^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(19), P. 2518 - 2524

Published: May 26, 2023

Comprehensive Summary Conjugated microporous polymers (CMPs) featuring extended π‐structures, large specific surface area and tailor‐made functionalities are a class of promising organic photocatalysts for hydrogen evolution reaction (HER) from water. However, the photocatalytic activities most CMPs severely hindered by slow charge transfer rate fast recombination process. Herein, we develop strategy synthesis donor‐acceptor through nickel(0)‐catalyzed Yamamoto cross‐coupling 3,6‐dibromo‐9‐(4‐bromophenyl)carbazole (CZ) with 5,5'‐dibromo‐2,2'‐bipyridine (DBPy) efficient HER The PCZN‐4 prepared 2 : 3 stoichiometric ratio CZ to DBPy exhibited highest 7160 μmol·g –1 ·h , which was nearly equal 179 times 143 that PCZN‐1 (40 ) PCZN‐6 (50 obtained homocoupling DBPy, respectively. Compared counterparts, enhanced activity results improved separation efficiency carriers. Interestingly, H performance could be further up 17080 adjusting pH aqueous solution. This work offers novel approach improving tuning chemical structures surrounding microenvironment polymer backbone.

Language: Английский

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Metal-Free Light-Driven 1,4-NADH Regeneration System from Nitrogen and Sulfur Codoped Carbon Dots

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(21), P. 14233 - 14240

Published: Oct. 23, 2023

Light-driven regeneration of nicotinamide cofactors, primarily NADH, is great significance for enzyme-photocoupled artificial photosynthesis, which strongly relies on the utilization noble metal-based cocatalysts to ensure high selectivity 1,4-NADH. Herein, we report a metal-free photocatalytic NADH system enabled by nitrogen and sulfur codoped carbon dots (N,S-CDs). The temporary occupation S element during catalyst synthesis increased proportion pyrrolic N 2.05 times. (88.44%) in N,S-CDs affords appropriate adsorption energy toward #4 NAD+ pyridine ring. As result, exhibited 82.00 ± 5.64% 1,4-NADH, highest value existing systems, also showed size-dependent 1,4-NADH yield with an optimal 42.92 2.24%.

Language: Английский

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