Understanding the structure-performance relationship of active sites at atomic scale

Nano Research, Год журнала: 2022, Номер 15(8), С. 6888 - 6923

Опубликована: Июнь 14, 2022

Язык: Английский

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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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Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis

Nano Research, Год журнала: 2022, Номер 15(9), С. 7806 - 7839

Опубликована: Июнь 2, 2022

Язык: Английский

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Single‐atom catalysis for carbon neutrality

Carbon Energy, Год журнала: 2022, Номер 4(6), С. 1021 - 1079

Опубликована: Июль 14, 2022

Abstract Currently, more than 86% of global energy consumption is still mainly dependent on traditional fossil fuels, which causes resource scarcity and even emission high amounts carbon dioxide (CO 2 ), resulting in a severe “Greenhouse effect.” Considering this situation, the concept “carbon neutrality” has been put forward by 125 countries one after another. To achieve goals neutrality,” two main strategies to reduce CO emissions develop sustainable clean can be adopted. Notably, these are crucial for synthesis advanced single‐atom catalysts (SACs) energy‐related applications. In review, we highlight unique SACs conversion into high‐efficiency energy, example, through photocatalytic, electrocatalytic, thermal catalytic hydrogenation technologies, convert hydrocarbon fuels (CO, CH 4 , HCOOH, 3 OH, multicarbon [C 2+ ] products). addition, introduce technologies devices replace polluting such as photocatalytic electrocatalytic water splitting produce hydrogen oxygen reduction reaction (ORR) fuel cells. Impressively, several representative examples (including d ‐, ds p f ‐blocks) conversion, H ORR discussed describe methods, characterization, corresponding activity. Finally, review concludes with description challenges outlooks future applications contributing toward neutrality.

Язык: Английский

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Inter‐Metal Interaction with a Threshold Effect in NiCu Dual‐Atom Catalysts for CO₂ Electroreduction

Advanced Materials, Год журнала: 2022, Номер 35(11)

Опубликована: Ноя. 26, 2022

Dual-atom catalysts (DACs) have become an emerging platform to provide more flexible active sites for electrocatalytic reactions with multi-electron/proton transfer, such as the CO2 reduction reaction (CRR). However, introduction of asymmetric dual-atom causes complexity in structure, leaving incomprehensive understanding inter-metal interaction and catalytic mechanism. Taking NiCu DACs example, herein, a rational structural model is proposed, distance-dependent investigated by combining theoretical simulations experiments, including density functional theory computation, aberration-corrected transmission electron microscopy, synchrotron-based X-ray absorption fine Monte Carlo experiments. A distance threshold around 5.3 Å between adjacent NiN4 CuN4 moieties revealed trigger effective electronic regulation boost CRR performance on both selectivity activity. universal macro-descriptor rigorously correlating intrinsic material features (e.g., metal loading thickness) established guide design synthesis advanced DACs. This study highlights significance identifying DACs, helps bridge gap experimental atomically dispersed highly correlated sites.

Язык: Английский

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Heteroatom‐Driven Coordination Fields Altering Single Cerium Atom Sites for Efficient Oxygen Reduction Reaction

Advanced Materials, Год журнала: 2023, Номер 35(28)

Опубликована: Апрель 4, 2023

For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, N co-doped hollow carbon substrate (Ce SAs/PSNC) for oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses half-wave potential 0.90 V, turnover frequency value 52.2 s

Язык: Английский

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Efficient Photoreduction of Diluted CO₂to Tunable Syngas by Ni−Co Dual Sites through d‐band Center Manipulation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 29, 2022

Photocatalytic conversion of CO2 into syngas is a promising way to address the energy and environmental challenges. Here we report integration Ni-Co dual sites on Ni doped Co3 O4 ultrathin nanosheets assembled double-hollow nanotube (Ni-Co3 NSDHN) for efficient photoreduction low-concentration . Quasi in situ spectra density functional theory calculations demonstrate that declining d-band center enables electrons accumulation dxz /dyz -2π* dz2 -5σ orbitals. As result, binding strength *CO weakened *H adsorption site modulated from metal an oxygen site. Remarkably, Ni-Co3 NSDHN exhibits superior diluted photoconversion activity controllable selectivity under irradiation visible light or even natural sunlight. A evolution rate 170.0 mmol g-1 h-1 with apparent quantum yield 3.7 % continuously adjustable CO/H2 ratios 1 : 10 are achieved.

Язык: Английский

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Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Small Methods, Год журнала: 2022, Номер 6(8)

Опубликована: Июнь 25, 2022

Abstract Single‐atom catalysts (SACs) provide well‐defined active sites with 100% atom utilization, and can be prepared using a wide range of support materials. Therefore, they are attracting global attention, especially in the fields energy conversion storage. To date, research has focused on transition‐metal precious‐metal‐based SACs. More recently, rare‐earth (RE)‐based SACs have emerged as new frontier photo/electrocatalysis owing to their unique electronic structure arising from spin‐orbit coupling 4f valence orbitals, unsaturated coordination environment, behavior charge‐transport bridges. However, systematic review role RE sites, catalytic mechanisms, synthetic methods for is lacking. this review, latest developments having applications summarized discussed. First, theoretical advantages briefly introduced, focusing roles orbitals coupled levels. In addition, most recent progress several important photo/electrocatalytic reactions corresponding mechanisms Further, strategies production reported. Finally, challenges development highlighted, along future directions perspectives.

Язык: Английский

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Synergistic Interactions of Neighboring Platinum and Iron Atoms Enhance Reverse Water–Gas Shift Reaction Performance

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2264 - 2270

Опубликована: Янв. 23, 2023

The limitations of conventional strategies in finely controlling the composition and structure demand new promotional effects for upgrading reverse water–gas shift (RWGS) catalysts enhanced fuel production. We report design synthesis a hetero-dual-site catalyst boosting RWGS performance by controllably loading Fe atoms at neighboring Pt atom on surface commercial CeO2. Fe–Pt/CeO2 exhibits remarkably high catalytic (TOFPt: 43,519 h–1) CO2 to CO conversion with ∼100% selectivity relatively low temperature 350 °C. Furthermore, retains over 80% activity after 200 h continuous operation. experimental computational investigations reveal "two-way synergistic effect", where can not only serve as promotors alter charge density but also be activated excess active hydrogen species generated atoms, enhancing stability.

Язык: Английский

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Recent Progress of Diatomic Catalysts: General Design Fundamentals and Diversified Catalytic Applications

Small, Год журнала: 2022, Номер 18(46)

Опубликована: Сен. 23, 2022

Abstract In recent years, some experiments and theoretical work have pointed out that diatomic catalysts not only retain the advantages of monoatomic catalysts, but also introduce a variety interactions, which exceed limit catalytic performance can be applied to many fields. Here, interaction between adjacent metal atoms in is elaborated: synergistic effect, spacing enhancement effect (geometric effect), electronic effect. With regard classification characterization various new are classified into four categories: heteronuclear/homonuclear, with/without carbon carriers, their measures introduced explained detail. aspect preparation widely used atomic layer deposition method, metal–organic framework derivative simple ball milling method introduced, with emphasis on formation mechanism catalysts. Finally, effective control strategies key applications electrocatalysis, photocatalysis, thermal catalysis, other fields given.

Язык: Английский

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