State of the Art and Prospects in Metal–Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis

Chemical Reviews, Год журнала: 2019, Номер 120(2), С. 1438 - 1511

Опубликована: Июнь 27, 2019

Metal–organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability richness structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple selective heterogeneous interactions activations these MOF-based nanocatalysts. Pyrolysis MOF-nanoparticle composites forms highly N- P-doped graphitized MOF-derived that increasingly used as efficient catalysts especially electro- photocatalysis. This review first briefly summarizes this background MOF nanoparticle then comprehensively reviews fast-growing literature reported during last years. parts organic molecular reactions, electrocatalysis, photocatalysis, views prospects. Major challenges our society addressed using well-defined fields synthesis, energy, environment. In spite many achievements, enormous progress still necessary to improve understanding processes involved beyond proof-of-concept, particularly methane oxidation, hydrogen production, water splitting, CO2 reduction methanol, nitrogen fixation, depollution.

Язык: Английский

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Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts

Nature Catalysis, Год журнала: 2018, Номер 1(6), С. 385 - 397

Опубликована: Июнь 7, 2018

Язык: Английский

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Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(5), С. 2035 - 2044

Опубликована: Янв. 20, 2017

The selectivity control toward aldehyde in the aromatic alcohol oxidation remains a grand challenge using molecular oxygen under mild conditions. In this work, we designed and synthesized Pt/PCN-224(M) composites by integration of Pt nanocrystals porphyrinic metal–organic frameworks (MOFs), PCN-224(M). exhibit excellent catalytic performance photo-oxidation alcohols 1 atm O2 at ambient temperature, based on synergetic photothermal effect singlet production. Additionally, opposition to function Schottky junction, injection hot electrons from plasmonic into PCN-224(M) would lower electron density surface, which thus is tailorable for optimized via competition between junction altering light intensity. To best our knowledge, not only an unprecedented report oxygen-engaged selective aldehydes but also first MOFs.

Язык: Английский

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Carbon Materials as Catalyst Supports and Catalysts in the Transformation of Biomass to Fuels and Chemicals

ACS Catalysis, Год журнала: 2014, Номер 4(10), С. 3393 - 3410

Опубликована: Авг. 25, 2014

Carbon plays a dual role as catalyst or support for chemical and enzymatic biomass transformation reactions due to its large specific surface area, high porosity, excellent electron conductivity, relative inertness. Advantageously, carbon materials can be prepared from residual biomass, an attractive property decreasing the so-called "carbon-footprint" of process. chemically functionalized and/or decorated with metallic nanoparticles enzymes impart improve novel catalytic activity. Sulfonated porous exhibit reactivity in diversified compared their nonporous counterparts. However, SO3H groups prevent incorporation hydrophobic molecules into bulk, thereby causing acid-catalyzed proceed only on surface. Metal catalysts supports have significant advantages over other oxide different types reactions. The future success biorefinery will require design new generation multifunctional catalysts, possibly derived emerging such graphene, nanotubes, monoliths, selective processing carbohydrates lignin. most achievable economical way is convert lignocellulosic directly, rather than pure cellulose, hemicellulose, lignin using catalysts.

Язык: Английский

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Bottom-up precise synthesis of stable platinum dimers on graphene

Nature Communications, Год журнала: 2017, Номер 8(1)

Опубликована: Окт. 16, 2017

Supported metal clusters containing only a few atoms are of great interest. Progress has been made in synthesis single-atom catalysts. However, precise dimers on high-surface area support remains grand challenge. Here, we show that Pt2 can be fabricated with bottom-up approach graphene using atomic layer deposition, through proper nucleation sites creation, Pt1 deposition and attaching secondary Pt atom selectively the preliminary one. Scanning transmission electron microscopy, x-ray absorption spectroscopy, theoretical calculations suggest likely oxidized form Pt2Ox. In hydrolytic dehydrogenation ammonia borane, exhibit high specific rate 2800 molH2 molPt-1 min-1 at room temperature, ~17- 45-fold higher than supported single nanoparticles, respectively. These findings open an avenue to fabrication atomically ultrafine for practical applications.

Язык: Английский

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Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities

ACS Catalysis, Год журнала: 2016, Номер 6(5), С. 2965 - 2981

Опубликована: Март 31, 2016

In this Perspective, we highlight the main challenges to be addressed in development of heterogeneous catalysts for direct functionalization methane. Along with our personal view on current developments field, outline mechanistic, engineering, and catalyst design issues that have hampered implementation new technologies possible paths overcome these problems.

Язык: Английский

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O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Chemical Reviews, Год журнала: 2017, Номер 118(5), С. 2816 - 2862

Опубликована: Ноя. 8, 2017

The activation of O2 on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies well-defined using variety techniques have given crucial insight into the mechanisms, energetics, dynamics adsorption dissociation. Here, trends in transition are discussed, various states described terms both electronic structure geometry. mechanism dissociation also reviewed, including importance spin transition. reactivity O toward reactant molecules briefly discussed context catalysis. surface generally correlates with strength O, tendency to oxidize, heat formation oxide. Periodic can be rationalized attractive repulsive interactions d-band, such that inert metals tend feature full d band low energy has large spatial overlap adsorbate states. More open or undercoordinated defect sites much more reactive than close-packed surfaces. Reactions between other species prevalent reactions species, particularly

Язык: Английский

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Water-Mediated Mars–Van Krevelen Mechanism for CO Oxidation on Ceria-Supported Single-Atom Pt₁ Catalyst

ACS Catalysis, Год журнала: 2016, Номер 7(1), С. 887 - 891

Опубликована: Дек. 21, 2016

In water-promoted CO oxidation, water was thought not to directly participate in CO2 production. Here we report that via a water-mediated Mars–van Krevelen (MvK) mechanism, can contribute about 50% of production on single-atom Pt1/CeO2 catalyst. The origin is the facile reaction with hydroxyl from dissociated yield carboxyl intermediate, which dehydrogenates subsequently help lattice generate and water. MvK type found here provides new insights promotion role heterogeneous catalysis.

Язык: Английский

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Hydroxyapatite: A review of syntheses, structure and applications in heterogeneous catalysis

Coordination Chemistry Reviews, Год журнала: 2017, Номер 347, С. 48 - 76

Опубликована: Июнь 16, 2017

Язык: Английский

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Base-Free Aerobic Oxidation of 5-Hydroxymethyl-furfural to 2,5-Furandicarboxylic Acid in Water Catalyzed by Functionalized Carbon Nanotube-Supported Au–Pd Alloy Nanoparticles

ACS Catalysis, Год журнала: 2014, Номер 4(7), С. 2175 - 2185

Опубликована: Май 26, 2014

The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound in cellulose transformation, into 2,5-furandicarboxylic acid (FDCA), promising renewable alternative to petroleum-derived terephthalic acid, is one the most attractive reactions for establishing biomass-based sustainable chemical processes. Supported Au catalysts have shown encouraging performance this reaction, but need an excess amount base additives makes process less green and cost-effective. Here, we report stable efficient carbon nanotube (CNT)-supported Au–Pd alloy catalyst HMF FDCA water without any bases. functionalization CNT surfaces crucial formation. We clarified that containing more carbonyl/quinone carboxyl groups favors formation by enhancing adsorption reactant reaction intermediates. Significant synergistic effects exist between Pd base-free through three tandem steps. present work provides understanding support-enhanced effect alloying supported Au-based bimetallic catalysts, knowledge may help develop relatively complicated organic compounds with different functional water.

Язык: Английский

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