Single-atom catalysts for photocatalytic energy conversion

Joule, Journal Year: 2022, Volume and Issue: 6(1), P. 92 - 133

Published: Jan. 1, 2022

Artificial photocatalytic energy conversion represents a highly intriguing strategy for solving the crisis and environmental problems by directly harvesting solar energy. The development of efficient photocatalysts is central task pushing real-world application reactions. Due to maximum atomic utilization efficiency distinct advantages outstanding catalytic activity, single-atom catalysts (SACs) have emerged as promising candidates photocatalysts. In current review, recent progresses challenges on SACs systems are presented. Fundamental principles focusing charge separation/transfer molecular adsorption/activation photocatalysis systemically explored. We outline how isolated reactive sites facilitate photogenerated electron–hole transfer promote construction photoactivation cycles. widespread adoption in diverse reactions also comprehensively introduced. By presenting these advances addressing some future with potential solutions related integral over SACs, we expect shed light forthcoming research conversion.

Language: Английский

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Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1861 - 1871

Published: Jan. 20, 2022

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion single-cluster catalyst is challenging. In this work, for first time, we present versatile strategy uniformly dispersed polyoxometalates (POMs) covalent organic frameworks (COFs) through confining POM cluster into regular nanopores COF by linkage. These COF-POM composites combine properties light absorption, electron transfer, and suitable catalytic active sites; as result, they exhibit outstanding activity artificial photosynthesis: that is, CO2 photoreduction with H2O donor. Among them, TCOF-MnMo6 achieved highest CO yield (37.25 μmol g-1 h-1 ca. 100% selectivity) gas-solid reaction system. Furthermore, mechanism study based on density functional theory (DFT) calculations demonstrated photoinduced transfer (PET) process occurs from to POM, then reduction oxidation occur COF, respectively. This work developed method single which also shows potential using materials photocatalysis.

Language: Английский

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Noble-metal single-atoms in thermocatalysis, electrocatalysis, and photocatalysis

Energy & Environmental Science, Journal Year: 2021, Volume and Issue: 14(5), P. 2954 - 3009

Published: Jan. 1, 2021

This review summarizes the recent advances about noble-metal single-atom catalysts in thermocatalysis, electrocatalysis, and photocatalysis.

Language: Английский

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Dual‐Single‐Atom Tailoring with Bifunctional Integration for High‐Performance CO₂ Photoreduction

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(49)

Published: Oct. 7, 2021

Single-atom photocatalysis has been demonstrated as a novel strategy to promote heterogeneous reactions. There is diversity of monoatomic metal species with specific functions; however, integrating representative merits into dual-single-atoms and regulating cooperative remain pressing challenge. For dual-single-atom catalysts, enhanced photocatalytic activity would be realized through bifunctional properties tuning the synergistic effect. Herein, supported on conjugated porous carbon nitride polymer are developed for effective CO2 reduction, featuring function cobalt (Co) ruthenium (Ru). A series in situ characterizations theoretical calculations conducted quantitative analysis structure-performance correlation. It concluded that active Co sites facilitate dynamic charge transfer, while Ru selective surface-bound interaction during photoreduction. The combination atom-specific traits synergy between lead high conversion corresponding apparent quantum efficiency (AQE) 2.8% at 385 nm, along turnover number (TON) more than 200 without addition any sacrificial agent. This work presents an example identifying roles different single-atom metals synergy, where two unique collaborate further boost performance.

Language: Английский

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Ordered Macroporous Carbonous Frameworks Implanted with CdS Quantum Dots for Efficient Photocatalytic CO₂ Reduction

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(35)

Published: July 24, 2021

Abstract Solar‐driven photocatalytic CO 2 reduction is regarded as a promising way to simultaneously mitigate the energy crisis and pollution. However, achieving high efficiency of reduction, especially without assistance sacrifice reagents or extra alkaline additives, remains critical issue. Herein, photocatalyst 3D ordered macroporous N‐doped carbon (NC) supported CdS quantum dots (3DOM CdSQD/NC) successfully fabricated toward via an in situ transformation strategy. Additionally, amines oxidation reaction introduced replace H O process further boost efficiency. Impressively, 3DOM CdSQD/NC exhibits superior activity selectivity coupled with oxidation, affording production rate 5210 µmol g −1 h absence any sacrificial agents additives. Moreover, achieves apparent 2.9% at 450 nm. Mechanism studies indicate that macropores NC matrix are beneficial transfer photogenerated carriers. Furthermore, highly dispersed QDs on skeleton able significantly promote adsorption both amine molecules depress activation barriers by stabilizing *COOH intermediate, directly contributing activity.

Language: Английский

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Porphyrin-based framework materials for energy conversion

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120009 - e9120009

Published: May 26, 2022

With the increasing demand for fuel causing serious environmental pollution, it is urgent to develop new and environmentally friendly energy conversion devices. These devices, however, require good, inexpensive materials electrodes so on. The multifunctional properties of porphyrins enable framework (e.g., metal-organic frameworks covalent organic frameworks) be applied in devices due their simple synthesis, high chemical stability, abundant metallic active sites, adjustable crystalline structure specific surface area. Herein, types porphyrin structural blocks are briefly reviewed. They can used as ligands or directly assembled with generate high-performance electro-/photo-catalysts. catalysts electro-/photo-catalytic water splitting, carbon dioxide reduction, electrocatalytic oxygen reduction also summarized introduced. At end article, we present challenges porphyrin-based above application corresponding solutions. We expect flourish coming years.

Language: Английский

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Transition metal-based layered double hydroxides for photo(electro)chemical water splitting: a mini review

Nanoscale, Journal Year: 2021, Volume and Issue: 13(32), P. 13593 - 13603

Published: Jan. 1, 2021

The review examines the areas: (i) routes for synthesis of transition metal-based LDHs, (ii) recent developments in LDHs photo(electro)chemical water splitting, (iii) a summary structure–property relationships therein.

Language: Английский

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Carbon Nitride Photocatalysts with Integrated Oxidation and Reduction Atomic Active Centers for Improved CO₂Conversion

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 18, 2022

Single-atom active-site catalysts have attracted significant attention in the field of photocatalytic CO2 conversion. However, designing active sites for reduction and H2 O oxidation simultaneously on a photocatalyst combining corresponding half-reaction system is still difficult. Here, we synthesized bimetallic single-atom with two compatible centers Mn Co carbon nitride (Mn1 Co1 /CN). Our experimental results density functional theory calculations showed that center promotes by accumulating photogenerated holes. In addition, activation increasing bond length angle molecules. Benefiting from synergistic effect atomic centers, Mn1 /CN exhibited CO production rate 47 μmol g-1 h-1 , which significantly higher than single-metal photocatalyst.

Language: Английский

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Challenges and Opportunities in Engineering the Electronic Structure of Single-Atom Catalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 2981 - 2997

Published: Feb. 14, 2023

Controlling the electronic structure of transition-metal single-atom heterogeneous catalysts (SACs) is crucial to unlocking their full potential. The ability do this with increasing precision offers a rational strategy optimize processes associated adsorption and activation reactive intermediates, charge transfer dynamics, light absorption. While several methods have been proposed alter characteristics SACs, such as oxidation state, band structure, orbital occupancy, spin, lack systematic approach application makes it difficult control effects. In Perspective, we examine how configuration SACs can be engineered for thermochemical, electrochemical, photochemical applications, exploring relationship activity, selectivity, stability. We discuss synthetic analytical challenges in controlling discriminating possible directions toward closing gap between computational experimental efforts. By bringing topic center, hope stimulate research understand, control, exploit effects ultimately spur technological developments.

Language: Английский

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Atomically Dispersed High‐Density Al–N₄ Sites in Porous Carbon for Efficient Photodriven CO₂ Cycloaddition

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(45)

Published: Sept. 18, 2021

Abstract Highly active catalysts that can directly utilize renewable energy (e.g., solar energy) are desirable for CO 2 value‐added processes. Herein, aiming at improving the efficiency of photodriven cycloaddition reactions, a catalyst composed porous carbon nanosheets enriched with high loading atomically dispersed Al atoms (≈14.4 wt%, corresponding to an atomic percent ≈7.3%) coordinated N (AlN 4 motif, Al–N–C catalyst) via versatile molecule‐confined pyrolysis strategy is reported. The performance catalytic under light irradiation (≈95% conversion, reaction rate = 3.52 mmol g −1 h ) significantly superior obtained thermal environment (≈57% 2.11 ). Besides efficient photothermal conversion induced by matrix, both experimental and theoretical analysis reveal favors photogenerated electron transfer from semiconductive epoxide reactant, facilitating formation ring‐opened intermediate through rate‐limiting step. This study not only provides advanced cycloaddition, but also furnishes new insight rational design photocatalysts diverse heterogeneous reactions in future.

Language: Английский

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