Single‐Atom Catalysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: March 15, 2023

Single-atom catalysts hold the potential to significantly impact chemical sector, pushing boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist many coordination environments, all which have shown important functions specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging gap between homogeneous heterogeneous catalysis. This Review outlines impressive progress made recent years regarding use single-atom organic synthesis. We illustrate knowledge gaps search more sustainable, earth-abundant synthetic applications.

Language: Английский

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Single‐Atom Phosphorus Defects Decorated CoP Cocatalyst Boosts Photocatalytic Hydrogen Generation Performance of Cd_0.5Zn_0.5S by Directed Separating the Photogenerated Carriers

Small, Journal Year: 2023, Volume and Issue: 19(20)

Published: Feb. 17, 2023

Abstract Design and preparation of an efficient nonprecious cocatalysts, with structural features functionality necessary for improving photocatalytic performance semiconductors, remain a formidable challenge until now. Herein, the first time, novel CoP cocatalyst single‐atom phosphorus vacancies defects (CoP‐V p ) is synthesized coupled Cd 0.5 Zn S to build CoP‐V @Cd @CZS) heterojunctions photocatalysts via liquid phase corrosion method following by in suit growth process. The nanohybrids deliver attractive hydrogen production activity 2.05 mmol h −1 30 mg under visible‐light irradiation, which 14.66 times higher than that pristine ZCS samples. As expected, further enhances charge‐separation efficiency ZCS, addition improvement electron transfer efficiency, confirmed ultrafast spectroscopies. Mechanism studies based on density functional theory calculations verify Co atoms adjacent V play key role translation, rotation, transformation electrons H 2 O reduction. This scalable strategy focusing defect engineering provides new insight into designing highly active cocatalysts boost application.

Language: Английский

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S-Scheme Heterojunction/Single-Atom Dual-Driven Charge Transport for Photocatalytic Hydrogen Production

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7308 - 7320

Published: April 25, 2024

The rational design and modification of heterojunction photocatalysts aimed at achieving fast charge transport efficient photocatalytic performance is a central goal solar-light-driven water splitting hydrogen evolution, yet this remains challenge. Herein, we prepare hierarchical photocatalyst composed few-layer violet phosphorene (VP), cadmium sulfide (CdS) nanoparticles (NPs), Pd single atoms (SAs) by facile one-step ball-milling strategy. underlying VP/CdS p–n heterojunctions are verified to adopt S-scheme directional transfer combining in situ irradiated X-ray photoelectron spectroscopy electron paramagnetic resonance. atomically dispersed sites the low-valence state coupled with synergistically achieve ultrafast (2.2 ps), which interfacial Pd–S Pd–P bonds serve as channels. In addition, density-functional theory calculations reveal key role enhancement light-harvesting capacity optimization proton adsorption thermodynamics. A visible-light production rate 82.5 mmol h–1 g–1 attained an optimal 1 wt % Pd–5 photocatalyst, manifests 54-fold increase respect that CdS NPs, addition apparent quantum efficiency (AQE) 25.7% 420 nm. This work showcases valid combination SAs for separation promoting others.

Language: Английский

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Lattice Defects and Electronic Modulation of Flower‐Like Zn₃In₂S₆ Promote Photocatalytic Degradation of Multiple Antibiotics

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

Published: Jan. 2, 2024

Abstract Photocatalysis is an effective technique to remove antibiotic residues from aquatic environments. Typical metal sulfides like Zn 3 In 2 S 6 have been applied a wide range of photocatalytic applications. However, there are currently no readily accessible methods increase its antibiotic‐degrading activity. Here, facile hydrothermal approach developed for the preparation flower‐like with tunable sulfur lattice defects. Photogenerated carriers can be separated and transferred more easily when adequate amount Moreover, defect‐induced electronic modulation enhances light utilization adsorption properties. The modified demonstrates outstanding degradation activity levofloxacin, ofloxacin, tetracycline. This work sheds on exploring defects enhancing

Language: Английский

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Energy band engineering of hydroxyethyl group grafted on the edge of 3D g-C3N4 nanotubes for enhanced photocatalytic H2 production

Materials Today Physics, Journal Year: 2022, Volume and Issue: 27, P. 100806 - 100806

Published: Aug. 5, 2022

Language: Английский

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Surface Unsaturated Sulfur Modulates Pt Sub‐Nanoparticles on Tandem Homojunction CdS for Efficient Electron Extraction

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(14)

Published: Feb. 19, 2023

Abstract The metal‐semiconductor interfacial photocarrier extraction and utilization are crucial for boosting photocatalytic activity, the construction of chemical bonds to anchor metal active sites is an emerging direction facilitate extraction. Herein, PtS designed via in situ photoreduction precisely Pt sub‐nanoclusters (SNCs) on tandem homojunction CdS (Pt‐CdS x ‐T). optimized 0.02 ‐CdS ‐T photocatalyst exhibits impressive hydrogen evolution rate 854.2 µmol h −1 with apparent quantum yield 43.55% at 470 nm, which nearly 13 times that pristine CdS. Systematic investigations reveal abundant coordination‐unsaturated S atoms act as SNCs thus formed accelerate interface directional photocarriers transfer. its potential barrier promotes separation internal electrostatic field, electron transfer kinetics H* adsorption capacity depend size confirmed by surface photovoltage spectroscopy density functional theory calculations. This work affords a new perspective exploitation dispersed cocatalysts catalysts achieve high‐efficiency evolution.

Language: Английский

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NiS/Cd_0.6Zn_0.4S Schottky Junction Bifunctional Photocatalyst for Sunlight‐Driven Highly Selective Catalytic Oxidation of Vanillyl Alcohol Towards Vanillin Coupled with Hydrogen Evolution Reaction

Small, Journal Year: 2023, Volume and Issue: 19(39)

Published: May 31, 2023

Abstract Selective oxidation of biomass‐based molecules to high‐value chemicals in conjunction with hydrogen evolution reaction (HER) is an innovative photocatalysis strategy. The key challenge design bifunctional photocatalysts suitable band structures, which can achieve highly efficient generation and hydrogen. Herein, NiS/Cd 0.6 Zn 0.4 S Schottky junction catalysts are constructed for sunlight‐driven catalytic vanillyl alcohol (VAL) selective towards vanillin (VN) coupling HER. At optimal conditions, the 8% photocatalyst achieves high activity VN production (3.75 mmol g −1 h ) HER (3.84 ). It also exhibits remarkable VAL conversion (66.9%), yield (52.1%), selectivity (77.8%). photocatalytic proceeds a carbon‐centered radical mechanism via cleavage α C–H bond. Experimental results theoretical calculations show that NiS metallic properties enhances electron transfer capability. Importantly, Ni‐S‐Cd “electron bridge” formed at interface further improves separation/transfer electrone/h + pairs furnishes active sites due its smaller |ΔG H* | value, thereby resulting remarkably activity. This work sheds new light on HER, pathway achieving efficiency.

Language: Английский

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Killing two birds with one stone: State-of-the-art progress in dual-functional photoredox catalysis for solar fuel conversion and selective organic transformation

EnergyChem, Journal Year: 2023, Volume and Issue: 5(6), P. 100112 - 100112

Published: Nov. 1, 2023

Language: Английский

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Photocatalytic Methanol Dehydrogenation Promoted Synergistically by Atomically Dispersed Pd and Clustered Pd

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24440 - 24449

Published: Aug. 20, 2024

Supported metal in the form of single atoms, clusters, and particles can individually or jointly affect activity supported heterogeneous catalysts. While individual contribution to overall photocatalysts has been identified, joint mixed species is overlooked because their different photoelectric properties. Here, atomically dispersed Pd (Pd1) clusters are loaded onto CdS, serving as oxidation reduction sites for methanol dehydrogenation. The Pd1 substitutes Cd2+, forming hole-trapping states assisting dispersion photodeposited clusters. Therefore, dehydrogenation on CdS with exhibits highest turnover frequency 1.14 s–1 based content affords H2 HCHO a similar apparent quantum yield 87 ± 1% at 452 nm under optimized reaction conditions. This work highlights synergistic catalysis improved photocatalytic activity.

Language: Английский

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In‐Situ Anchoring of Co Single‐Atom Synergistically with Cd Vacancy of Cadmium Sulfide for Boosting Asymmetric Charge Distribution and Photocatalytic Hydrogen Evolution

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

Published: Oct. 10, 2024

In the context of reshaping energy pattern, designing and synthesizing high-performance noble metal-free photocatalysts with ultra-high atomic utilization for hydrogen evolution reaction (HER) still remains a challenge. streamlined synthesis process, in-situ single atom anchoring is performed in parallel HER by irradiating precursory defect-state CdS/Co suspension (Co-DCdS-Ss) system under simulated sunlight single-atom Co photocatalyst (Co5:DCdS) exhibits further improved catalytic performance (60.10 mmol g

Language: Английский

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