Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4855 - 4933

Опубликована: Март 27, 2023

Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of active sites at atomic and molecular level is very challenging due to structural complexity catalysts. Comparing features catalytic performances different entities will favor formation unified structure-reactivity relationships heterogeneous thereby facilitate upgrading current In this review, we discuss geometric electronic structures three representative types (bimetallic binuclear sites, nanoclusters, nanoparticles) then summarize synthesis methodologies characterization techniques for entities, with emphasis recent progress made past decade. The supported nanoparticles series important reactions are discussed. Finally, future research directions catalysis based and, more generally, prospective developments both practical applications.

Язык: Английский

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In Situ Synthesis of Chemically Bonded 2D/2D Covalent Organic Frameworks/O‐Vacancy WO₃ Z‐Scheme Heterostructure for Photocatalytic Overall Water Splitting

Advanced Materials, Год журнала: 2023, Номер 35(33)

Опубликована: Июнь 15, 2023

Abstract Covalent organic frameworks (COFs) have shown great promise for photocatalytic hydrogen evolution via water splitting. However, the four‐electron oxidation of remains elusive toward oxygen evolution. Enabling this pathway is critical to improve yield and maximize atom utilization efficiency. A Z‐scheme heterojunction proposed overcoming fundamental issues in COF‐based overall splitting (OWS), such as inefficient light absorption, charge recombination, poor ability. It that construction a novel 2D/2D through situ growth COFs on O‐vacancy WO 3 nanosheets (Ov‐WO ) WOC chemical bond can remarkably promote OWS. Benefiting from synergistic effect between enhanced built‐in electric field by interfacial bond, strong ability Ov‐WO 3, ultrathin structure TSCOF, both separation efficiency photogenerated electron–hole pairs be significantly enhanced. An impressive half‐rection rate 593 mmol h −1 g 146 (hydrogen) 68 (oxygen) µmol are achieved COF‐WO (TSCOFW) composite. This with two‐step excitation precisely cascaded charge‐transfer makes it responsible efficient solar‐driven OWS without sacrificial agent.

Язык: Английский

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Simultaneous CO₂and H₂O Activation via Integrated Cu Single Atom and N Vacancy Dual‐Site for Enhanced CO Photo‐Production

Advanced Functional Materials, Год журнала: 2023, Номер 33(28)

Опубликована: Апрель 23, 2023

Abstract Photocatalytic conversion of CO 2 into fuels using pure water as the proton source is immense potential in simultaneously addressing climate‐change crisis and realizing a carbon‐neutral economy. Single‐atom photocatalysts with tunable local atomic configurations unique electronic properties have exhibited outstanding catalytic performance past decade. However, given their single‐site features they are usually only amenable to activations involving single molecules. For photoreduction entailing complex activation dissociation process, designing multiple active sites on photocatalyst for both reduction H O still daunting challenge. Herein, it precisely construct Cu single‐atom centers two‐coordinated N vacancies dual CN (Cu 1 /N 2C V‐CN). Experimental theoretical results show that promote chemisorption via accumulating photogenerated electrons, V enhance O, thereby facilitating from COO* COOH*. Benefiting dual‐functional sites, V‐CN exhibits high selectivity (98.50%) decent production rate 11.12 µmol g −1 h . An ingenious atomic‐level design provides platform integrating modified catalyst deterministic identification property during process.

Язык: Английский

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Heterogeneous Fe-Co dual-atom catalyst outdistances the homogeneous counterpart for peroxymonosulfate-assisted water decontamination: New surface collision oxidation path and diatomic synergy

Water Research, Год журнала: 2023, Номер 241, С. 120164 - 120164

Опубликована: Июнь 1, 2023

Язык: Английский

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Structural engineering of atomic catalysts for electrocatalysis

Chemical Science, Год журнала: 2024, Номер 15(14), С. 5082 - 5112

Опубликована: Янв. 1, 2024

This review systematically introduces how to regulate the electronic structure and geometric configuration of atomic catalysts achieve high-efficiency electrocatalysis performances by analyzing detailed electrocatalytic applications mechanisms.

Язык: Английский

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Chlorine bridge bond-enabled binuclear copper complex for electrocatalyzing lithium–sulfur reactions

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 15, 2024

Abstract Engineering atom-scale sites are crucial to the mitigation of polysulfide shuttle, promotion sulfur redox, and regulation lithium deposition in lithium–sulfur batteries. Herein, a homonuclear copper dual-atom catalyst with proximal distance 3.5 Å is developed for batteries, wherein two adjacent atoms linked by pair symmetrical chlorine bridge bonds. Benefiting from their unique coordination, increased active interface concentration synchronously guide evolutions species. Such delicate design breaks through activity limitation mononuclear metal center represents concept battery realm. Therefore, remarkable areal capacity 7.8 mA h cm −2 achieved under scenario content 60 wt. %, mass loading 7.7 mg electrolyte dosage 4.8 μL −1 .

Язык: Английский

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Inter‐Metal Interaction of Dual‐Atom Catalysts in Heterogeneous Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Июнь 14, 2023

Dual-atom catalysts (DACs) have been a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising enhance performance and even catalyze more complex reactions. However, precisely regulating site structure uncovering dual-atom metal interaction remain grand challenges. In this review, we clarify the significance of inter-metal DACs based on understanding center structures. Three diatomic configurations are elaborated, including isolated single-atom, N/O-bridged dual-atom, direct dual-metal bonding interaction. Subsequently, up-to-date progress oxidation reactions, hydrogenation/dehydrogenation electrocatalytic photocatalytic reactions summarized. structure-activity relationship catalytic is then discussed at an atomic level. Finally, challenges future directions engineer discussed. This review will offer prospects for rational design efficient toward catalysis.

Язык: Английский

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Development of Synergistically Efficient Ni–Co Pair Catalytic Sites for Enhanced Polysulfide Conversion in Lithium–Sulfur Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(37)

Опубликована: Март 29, 2024

Abstract The performance of Lithium–sulfur (Li–S) batteries is constrained by the migration lithium polysulfide (LiPS), slow conversion LiPS, and significant reaction barrier encountered during precipitation/dissolution Li 2 S throughout discharge/charge cycle. In this contribution, study presents Ni–Co dual‐atom catalytic sites on hollow nitrogen‐doped carbon (NiCoNC). Theoretical calculations experimental data reveal that catalysts (DACs) accelerate kinetic LiPSs facilitate formation/decomposition discharging charging, which minimizes LiPS migration. Consequently, utilization S/NiCoNC cathodes manifests a substantial initial capacity 1348.5 mAh g −1 at 0.1 C, exceptional cycling stability with an average degradation rate 0.028% per cycle over 900 cycles 0.5 noteworthy capability 626 C. Electrodes higher sulfur loading 4.5 mg cm −2 low electrolyte/sulfur ratio 8 µL exhibit specific capacities up to 1236 as well retention 494.2 after 200 0.2 This effectively showcases potential DACs for cathodes, thereby enhancing overall Li–S batteries.

Язык: Английский

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Direct Eight-Electron N₂O Electroreduction to NH₃ Enabled by an Fe Double-Atom Catalyst

Nano Letters, Год журнала: 2024, Номер 24(28), С. 8502 - 8509

Опубликована: Июль 1, 2024

N2O is a dominant atmosphere pollutant, causing ozone depletion and global warming. Currently, electrochemical reduction of has gained increasing attention to remove N2O, but its product worthless N2. Here, we propose direct eight-electron (8e) pathway electrochemically convert into NH3. As proof concept, using density functional theory calculation, an Fe2 double-atom catalyst (DAC) anchored by N-doped porous graphene (Fe2@NG) was screened out be the most active selective for electroreduction toward NH3 via novel 8e pathway, which benefits from unique bent adsorption configuration. Guided theoretical prediction, Fe2@NG DAC fabricated experimentally, it can achieve high N2O-to-NH3 Faradaic efficiency 77.8% with large yield rate 2.9 mg h–1 cm–2 at −0.6 V vs RHE in neutral electrolyte. Our study offers feasible strategy synthesize pollutant simultaneous removal.

Язык: Английский

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Spatial configuration of Fe–Co dual-sites boosting catalytic intermediates coupling toward oxygen evolution reaction

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(6)

Опубликована: Янв. 31, 2024

Oxygen evolution reaction (OER) is the pivotal obstacle of water splitting for hydrogen production. Dual-sites catalysts (DSCs) are considered exceeding single-site due to preternatural synergetic effects two metals in OER. However, appointing specific spatial configuration dual-sites toward more efficient catalysis still remains a challenge. Herein, we constructed configurations Fe-Co dual-sites: stereo sites (stereo-Fe-Co DSC) and planar (planar-Fe-Co DSC). Remarkably, planar-Fe-Co DSC has excellent OER performance superior stereo-Fe-Co DSC. DFT calculations experiments including isotope differential electrochemical mass spectrometry, situ infrared spectroscopy, Raman reveal *O intermediates can be directly coupled form *O-O* rather than *OOH by both DSCs, which could overcome limitation four electron transfer steps Especially, proper distance steric direction benefit cooperation dual dehydrogenate into rate-determining step. This work provides valuable insights support further research development dual-site catalysts.

Язык: Английский

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