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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Dealuminated Beta zeolite reverses Ostwald ripening for durable copper nanoparticle catalysts

Science, Год журнала: 2023, Номер 383(6678), С. 94 - 101

Опубликована: Дек. 21, 2023

Copper nanoparticle-based catalysts have been extensively applied in industry, but the nanoparticles tend to sinter into larger ones chemical atmospheres, which is detrimental catalyst performance. In this work, we used dealuminated Beta zeolite support copper (Cu/Beta-deAl) and showed that these particles become smaller methanol vapor at 200°C, decreasing from ~5.6 ~2.4 nanometers diameter, opposite general sintering phenomenon. A reverse ripening process was discovered, whereby migratable sites activated by were trapped silanol nests species acted as new nucleation for formation of small nanoparticles. This feature reversed channel, resulting robust dimethyl oxalate hydrogenation performed with supported use industry.

Язык: Английский

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The Role of In Situ/Operando IR Spectroscopy in Unraveling Adsorbate-Induced Structural Changes in Heterogeneous Catalysis

Chemical Reviews, Год журнала: 2023, Номер 123(21), С. 12135 - 12169

Опубликована: Окт. 26, 2023

Heterogeneous catalysts undergo thermal- and/or adsorbate-induced dynamic changes under reaction conditions, which consequently modify their catalytic behavior. Hence, it is increasingly crucial to characterize the properties of a catalyst conditions through so-called "operando" approach. Operando IR spectroscopy probably one most ubiquitous and versatile characterization methods in field heterogeneous catalysis, but its potential identifying adsorbate- thermal-induced phenomena often overlooked favor other less accessible methods, such as XAS high-resolution microscopy. Without detracting from these techniques, while aware enormous value multitechnique approach, purpose this Review show that alone can provide relevant information field. This done by discussing few selected case studies our own research experience, belong categories both "single-site"- nanoparticle-based catalysts.

Язык: Английский

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Tandem catalytic approaches for CO2 enriched Fischer-Tropsch synthesis

Progress in Energy and Combustion Science, Год журнала: 2024, Номер 103, С. 101159 - 101159

Опубликована: Май 21, 2024

Язык: Английский

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Reactant-Induced Structural Evolution of Pt Catalysts Confined in Zeolite

JACS Au, Год журнала: 2024, Номер 4(2), С. 666 - 679

Опубликована: Фев. 6, 2024

Reactant-induced structural evolutions of heterogeneous metal catalysts are frequently observed in numerous catalytic systems, which can be associated with the formation or deactivation active sites. In this work, we will show transformation subnanometer Pt clusters pure-silica MFI zeolite structure presence CO, O2, and/or H2O and consequences Pt-zeolite materials derived from various treatment conditions. By applying appropriate pretreatment under a reactant atmosphere, precisely modulate size distribution species spanning single atoms to small nanoparticles (1–5 nm) matrix, resulting desirably stable for CO oxidation. We also incorporation Fe into framework greatly promotes stability against undesired sintering harsh conditions (up 650 °C moisture).

Язык: Английский

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Bridging the Gap between the X-ray Absorption Spectroscopy and the Computational Catalysis Communities in Heterogeneous Catalysis: A Perspective on the Current and Future Research Directions

ACS Catalysis, Год журнала: 2022, Номер 12(22), С. 13813 - 13830

Опубликована: Окт. 27, 2022

X-ray absorption spectroscopy (XAS) [extended fine structure (EXAFS) and near-edge (XANES)] is a key technique within the heterogeneous catalysis community to probe properties of active site(s) for diverse range catalytic materials. However, interpretation raw experimental data derive an atomistic picture catalyst requires modeling analysis; EXAFS are compared model, goodness fit parameter used judge best fit. This can often be nontrivial time-consuming; overcoming or improving these limitations remains central challenge community. Considering limitations, this Perspective highlights how recent developments in analysis software, increased availability reliable computational models, application science tools improve speed, accuracy, reliability interpretation. In particular, we emphasize advantages combining theory as unified that should treated standard (when applicable) identify sites not two separate complementary methods. Building on trends community, also present community-driven approach adopt FAIR Guiding Principles collection, analysis, dissemination, storage XAS data. Written with both audience mind, provide roadmap foster collaborations between communities.

Язык: Английский

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Screening Cu-Zeolites for Methane Activation Using Curriculum-Based Training

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1232 - 1242

Опубликована: Янв. 10, 2024

Machine learning (ML), when used synergistically with atomistic simulations, has recently emerged as a powerful tool for accelerated catalyst discovery. However, the application of these techniques been limited by lack interpretable and transferable ML models. In this work, we propose curriculum-based training (CBT) philosophy to systematically develop reactive machine potentials (rMLPs) high-throughput screening zeolite catalysts. Our CBT approach combines several different types calculations gradually teach model about relevant regions potential energy surface. The resulting rMLPs are accurate, transferable, interpretable. We further demonstrate effectiveness exhaustively thousands [CuOCu]2+ sites across hundreds Cu-zeolites industrially methane activation reaction. Specifically, large-scale analysis entire International Zeolite Association (IZA) database identifies set previously unexplored zeolites (i.e., MEI, ATN, EWO, CAS) that show highest ensemble-averaged rates [CuOCu]2+-catalyzed activation. believe can be generally applied other zeolite-catalyzed reactions and, subsequently, heterogeneous Thus, represents an important step toward overcoming long-standing barriers within computational catalysis community.

Язык: Английский

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Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals

ACS Nano, Год журнала: 2024, Номер 18(8), С. 6638 - 6649

Опубликована: Фев. 13, 2024

Strong metal–support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce encapsulation platinum (Pt) group metals by oxide supports through high temperature H2 reduction. However, demonstrations SMSI overlayers have largely been limited reducible oxides, such as TiO2 and Nb2O5. Here, we show that amorphous native surface plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced Pt following reduction a structure dependent manner. Reductive treatment at 300 °C induces formation an AlOx overlayer on clusters, leaving single-atom sites (Ptiso) exposed available for catalysis. The remaining Ptiso species possess more uniform local coordination environment than has observed other forms Al2O3, suggesting AlNCs presents well-defined anchoring individual atoms. This observation extends our understanding SMSIs providing evidence H2-induced can occur wider variety materials should stimulate expanded studies this effect include nonreducible oxides with oxygen defects presence disorder. It also suggests created manner, when combined properties Al nanocrystal core, may allow site-specific photocatalysis, dynamic control over light-driven reactivity these systems.

Язык: Английский

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Migration of zeolite-encapsulated subnanometre platinum clusters via reactive neural network potentials

Nanoscale, Год журнала: 2024, Номер 16(16), С. 8108 - 8118

Опубликована: Янв. 1, 2024

Pt atoms and small clusters move through the zeolite framework via distinct mechanisms, leading to complex size-dependent diffusivity.

Язык: Английский

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Generation of Subnanometer Metal Clusters in Silicoaluminate Zeolites as Bifunctional Catalysts

JACS Au, Год журнала: 2023, Номер 3(11), С. 3213 - 3226

Опубликована: Ноя. 2, 2023

Zeolite-encapsulated subnanometer metal catalysts are an emerging class of solid with superior performances in comparison to supported on open-structure carriers. Currently, there is no general synthesis methodology for the encapsulation different zeolite structures. In this work, we will show a method clusters (Pt, Pd, and Rh) within various silicoaluminate zeolites topologies (MFI, CHA, TON, MOR). The successful generation species relies introduction Sn, which can suppress migration during high-temperature oxidation–reduction treatments according advanced electron microscopy spectroscopy characterizations. advantage encapsulated Pt reflected direct coupling ethane benzene production ethylbenzene, acid sites work synergistic way.

Язык: Английский

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