Carbon nitride based materials: more than just a support for single-atom catalysis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(15), P. 4878 - 4932

Published: Jan. 1, 2023

Recently, the missing link between homogeneous and heterogeneous catalysis has been found it was named single-atom (SAC). However, SAC field still faces important challenges, one of which is controlling bonding/coordination single atoms support in order to compensate for increase surface energy when particle size reduced due atomic dispersion. Excellent candidates meet this requirement are carbon nitride (CN)-based materials. Metal can be firmly trapped nitrogen-rich coordination sites CN materials, makes them a unique class hosts preparing catalysts (SACs). As most promising two-dimensional supports stabilize isolated metal atoms, materials have increasingly employed SACs. Herein, we will cover recent advances single-atoms supported by In review, characterization techniques challenges faced topic discussed, commonly synthetic methods delineated different Finally, catalytic performance SACs based on nitrides reviewed with special focus their photocatalytic applications. particular, prove as non-innocent support. The relationship two-way, where change electronic properties support, while features matrix tune activity reactions. highlight frontiers field, including analytical method development, truly controlled methods, allowing fine control loading multi-element synthesis, how understanding two-way exchange behind push next level.

Language: Английский

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Boosting Activity and Stability of Metal Single-Atom Catalysts via Regulation of Coordination Number and Local Composition

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(45), P. 18854 - 18858

Published: Nov. 3, 2021

Controlling the chemical environments of active metal atom including both coordination number (CN) and local composition (LC) is vital to achieve stable single-atom catalysts (SACs), but remains challenging. Here we synthesized a series supported Pt1 SACs by depositing Pt atoms onto pretuned anchoring sites on nitrogen-doped carbon using atomic layer deposition. In hydrogenation para-chloronitrobenzene, SAC with higher CN about four less pyridinic nitrogen (Npyri) content exhibits remarkably high activity along superior recyclability compared those lower CNs more Npyri. Theoretical calculations reveal that four-coordinated 1 eV formation energy are resistant agglomerations than three-coordinated ones. Composition-wise decrease Pt-Npyri bond upshifts gradually Pt-5d center, minimal one features high-lying state largely facilitates H2 dissociation, boosting remarkably.

Language: Английский

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Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS)

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: April 20, 2023

This topical review focuses on the distinct role of carbon support coordination environment single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview atomic configurations in SACs, including a discussion advanced characterization techniques and simulation used understanding active sites. A summary key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), nitrogen (NRR), dioxide (CO

Language: Английский

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Peripheral-nitrogen effects on the Ru1 centre for highly efficient propane dehydrogenation

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(12), P. 1145 - 1156

Published: Dec. 12, 2022

Language: Английский

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Locking Effect in Metal@MOF with Superior Stability for Highly Chemoselective Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4659 - 4666

Published: Feb. 15, 2023

Ultrasmall metal nanoparticles (NPs) show high catalytic activity in heterogeneous catalysis but are prone to reunion and loss during the process, resulting low chemoselectivity poor efficiency. Herein, a locking effect strategy is proposed synthesize high-loading ultrafine NPs metal-organic frameworks (MOFs) for efficient chemoselective with stability. Briefly, MOF ZIF-90 aldehyde groups cooperating diamine chains via aldimine condensation was interlocked, which employed confine situ formation of Au NPs, denoted as Au@L-ZIF-90. The optimized Au@La-ZIF-90 has highly dispersed (2.60 ± 0.81 nm) loading amount around 22 wt % shows great performance toward 3-aminophenylacetylene (3-APA) from selective hydrogenation 3-nitrophenylacetylene (3-NPA) yield (99%) excellent durability (over 20 cycles), far superior contrast catalysts without other reported catalysts. In addition, experimental characterization systematic density functional theory calculations further demonstrate that locked modulates charge nanoparticles, making them specific nitro group obtain 3-APA selectivity (99%). Furthermore, this also applicable confined variety MOFs, all these (≥90%) 3-APA. work provides novel universal method precise control inherent accessible programmable microenvironment catalysis.

Language: Английский

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Altering the spin state of Fe-N-C through ligand field modulation of single-atom sites boosts the oxygen reduction reaction

Nano Energy, Journal Year: 2022, Volume and Issue: 105, P. 108020 - 108020

Published: Nov. 21, 2022

Language: Английский

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Atomically Dispersed Co–S–N Active Sites Anchored on Hierarchically Porous Carbon for Efficient Catalytic Hydrogenation of Nitro Compounds

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(10), P. 5786 - 5794

Published: April 29, 2022

It is highly desired but challenging to develop non-noble metal-based hydrogenation catalysts that can replace noble ones for selective reduction of nitro compounds into amino compounds. Herein, we reported a hierarchically porous carbon-supported N,S dual-coordinated cobalt single-atom catalyst (Co1/NSC-AT) The unique coordination environment Co centers, combined with the structure carbon supports, endows Co1/NSC-AT an excellent catalytic performance; reaction be efficiently performed under mild conditions (35 °C, ∼1bar H2) high conversion and selectivity. theoretical calculation reveals center (Co1S1N3) in acts as active site reaction. Co1S1N3 possesses lower barrier rate-determining step than Co1N4 nanoparticles. Moreover, environments tailor electronic structures single atoms, which facilitate desorption H from sites, thus promoting process.

Language: Английский

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Atomically Dispersed Pentacoordinated‐Zirconium Catalyst with Axial Oxygen Ligand for Oxygen Reduction Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 13, 2022

Single-atom catalysts (SACs), as promising alternatives to Pt-based catalysts, suffer from the limited choice of center metals and low single-atom loading. Here, we report a pentacoordinated Zr-based SAC with nontrivial axial O ligands (denoted O-Zr-N-C) for oxygen reduction reaction (ORR). The ligand downshifts d-band Zr confers sites stable local structure proper adsorption capability intermediates. Consequently, ORR performance O-Zr-N-C prominently surpasses that commercial Pt/C, achieving half-wave potential 0.91 V vs. reversible hydrogen electrode outstanding durability (92 % current retention after 130-hour operation). Moreover, site shows good resistance towards aggregation, enabling synthesis high loading (9.1 wt%). With high-loading catalyst, zinc-air battery (ZAB) delivers record-high power density 324 mW cm

Language: Английский

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Modulating the Electronic Metal‐Support Interactions in Single‐Atom Pt₁−CuO Catalyst for Boosting Acetone Oxidation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: March 29, 2022

The development of highly active single-atom catalysts (SACs) and identifying their intrinsic sites in oxidizing industrial hazardous hydrocarbons are challenging prospects. Tuning the electronic metal-support interactions (EMSIs) is valid for modulating catalytic performance SACs. We propose that modulation EMSIs a Pt1 -CuO SAC significantly promotes activity catalyst acetone oxidation. promote charge redistribution through unified Pt-O-Cu moieties, which modulates d-band structure atomic Pt sites, strengthens adsorption activation reactants. positively charged atoms superior activating at low temperatures, stretched Cu-O bonds facilitate lattice oxygen to participate subsequent believe this work will guide researchers engineer efficient SACs application hydrocarbon oxidation reactions.

Language: Английский

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Interlayer Charge Transfer Regulates Single-Atom Catalytic Activity on Electride/Graphene 2D Heterojunctions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4774 - 4783

Published: Feb. 17, 2023

Single-atom catalysts with structure and activity tunability have attracted significant attention for energy environmental applications. Herein we present a first-principles study of single-atom catalysis on two-dimensional graphene electride heterostructures. The anion electron gas in the layer enables colossal transfer to layer, degree being controllable by selection electride. charge tunes d-orbital occupancy single metal atom, enhancing catalytic hydrogen evolution reactions oxygen reduction reactions. strong correlation between adsorption Eads variation Δq suggests that interfacial is critical descriptor heterostructure-based catalysts. polynomial regression model proves importance accurately predicts ions molecules. This provides strategy obtain high-efficiency using

Language: Английский

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