Recent Developments in the Synthesis of Supported Catalysts
About: This article is published in Chemical Reviews.The article was published on 2015-06-19 and is currently open access. It has received 892 citations till now.
Citations
More filters
TL;DR: This review provides an updated and critical survey of the ever-expanding material architectures and applications of hollow structures in all branches of catalysis, including bio-, electro-, and photocatalysis.
Abstract: Catalysis is at the core of almost every established and emerging chemical process and also plays a central role in the quest for novel technologies for the sustainable production and conversion of energy. Particularly since the early 2000s, a great surge of interest exists in the design and application of micro- and nanometer-sized materials with hollow interiors as solid catalysts. This review provides an updated and critical survey of the ever-expanding material architectures and applications of hollow structures in all branches of catalysis, including bio-, electro-, and photocatalysis. First, the main synthesis strategies toward hollow materials are succinctly summarized, with emphasis on the (regioselective) incorporation of various types of catalytic functionalities within their different subunits. The principles underlying the scientific and technological interest in hollow materials as solid catalysts, or catalyst carriers, are then comprehensively reviewed. Aspects covered include the stabilizat...
595 citations
TL;DR: Cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
Abstract: The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobalt-diamine-dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere. The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
537 citations
TL;DR: This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years.
Abstract: Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber–Bosch process of ammonia synthesis and later in the Fischer–Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their “greenness”. This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.
432 citations
TL;DR: This review aims to provide a comprehensive account of the most significant advances in the development of functionalised heterogeneous catalysts for efficient biomass upgrading by critically discussing the role of consequent properties on cascade reactions as well as on other vital processes within the bio-refinery.
Abstract: Efficient transformation of biomass to value-added chemicals and high-energy density fuels is pivotal for a more sustainable economy and carbon-neutral society. In this framework, developing potential cascade chemical processes using functionalised heterogeneous catalysts is essential because of their versatile roles towards viable biomass valorisation. Advances in materials science and catalysis have provided several innovative strategies for the design of new appealing catalytic materials with well-defined structures and special characteristics. Promising catalytic materials that have paved the way for exciting scientific breakthroughs in biomass upgrading are carbon materials, metal–organic frameworks, solid phase ionic liquids, and magnetic iron oxides. These fascinating catalysts offer unique possibilities to accommodate adequate amounts of acid–base and redox functional species, hence enabling various biomass conversion reactions in a one-pot way. This review therefore aims to provide a comprehensive account of the most significant advances in the development of functionalised heterogeneous catalysts for efficient biomass upgrading. In addition, this review highlights important progress ensued in tailoring the immobilisation of desirable functional groups on particular sites of the above-listed materials, while critically discussing the role of consequent properties on cascade reactions as well as on other vital processes within the bio-refinery. Current challenges and future opportunities towards a rational design of novel functionalised heterogeneous catalysts for sustainable biomass valorisation are also emphasized.
429 citations
TL;DR: A facile method is reported to prepare an efficient and robust Ru-M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH-universal HER, which exhibits outstanding HER performance at all pH levels.
Abstract: A challenging but pressing task to design and synthesize novel, efficient, and robust pH‐universal hydrogen evolution reaction (HER) electrocatalysts for scalable and sustainable hydrogen production through electrochemical water splitting. Herein, we report a facile method to prepare an efficient and robust Ru‐M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH‐universal HER. The RuNi/CQDs catalysts exhibit outstanding HER performance at all pH levels. The unexpected low overpotentials of 13, 58, and 18 mV shown by RuNi/CQDs allow a current density of 10 mA cm−2 in 1 m KOH, 0.5 m H2SO4, and 1 m PBS, respectively, for Ru loading at 5.93 μgRu cm−2. This performance is among the best catalytic activities reported for any platinum‐free electrocatalyst. Theoretical studies reveal that Ni doping results in a moderate weakening of the hydrogen bonding energy of nearby surface Ru atoms, which plays a critical role in improving the HER activity.
392 citations
References
More filters
TL;DR: Hydrogen Production by Water−Gas Shift Reaction 4056 4.1.
Abstract: 1.0. Introduction 4044 2.0. Biomass Chemistry and Growth Rates 4047 2.1. Lignocellulose and Starch-Based Plants 4047 2.2. Triglyceride-Producing Plants 4049 2.3. Algae 4050 2.4. Terpenes and Rubber-Producing Plants 4052 3.0. Biomass Gasification 4052 3.1. Gasification Chemistry 4052 3.2. Gasification Reactors 4054 3.3. Supercritical Gasification 4054 3.4. Solar Gasification 4055 3.5. Gas Conditioning 4055 4.0. Syn-Gas Utilization 4056 4.1. Hydrogen Production by Water−Gas Shift Reaction 4056
7,067 citations
TL;DR: In this article, the rate of penetration into a small cylindrical capillary of radius $r$ was shown to be: ρ(r}^{2}+4\ensuremath{\epsilon}r)
Abstract: Penetration of Liquids into Cylindrical Capillaries.---The rate of penetration into a small capillary of radius $r$ is shown to be: $\frac{\mathrm{dl}}{\mathrm{dt}}=\frac{P({r}^{2}+4\ensuremath{\epsilon}r)}{8\ensuremath{\eta}l}$, where $P$ is the driving pressure, $\ensuremath{\epsilon}$ the coefficient of slip and $\ensuremath{\eta}$ the viscosity. By integrating this expression, the distance penetrated by a liquid flowing under capillary pressure alone into a horizontal capillary or one with small internal surface is found to be the square root of ($\frac{\ensuremath{\gamma}\mathrm{rt}\ifmmode\cdot\else\textperiodcentered\fi{}cos\ensuremath{\theta}}{2\ensuremath{\eta}}$), where $\ensuremath{\gamma}$ is the surface tension and $\ensuremath{\theta}$ the angle of contact. The quantity ($\frac{\ensuremath{\gamma}cos\ensuremath{\theta}}{2\ensuremath{\eta}}$) is called the coefficient of penetrance or the penetrativity of the liquid.Penetration of Liquids into a Porous Body.---(1) Theory. If a porous body behaves as an assemblage of very small cylindrical capillaries, the volume which penetrates in a time $t$ would be proportional to the square root of ($\frac{\ensuremath{\gamma}t}{\ensuremath{\eta}}$). (2) Experiments with mercury, water and other liquids completely verify the theoretical deductions.Dynamic capillary method of measuring surface tension is described. It possesses certain advantages on the static method of capillary rise.
5,658 citations
TL;DR: In conclusion, MOFs as Host Matrices or Nanometric Reaction Cavities should not be considered as a source of concern in the determination of MOFs’ properties in relation to other materials.
Abstract: 2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636
3,106 citations
TL;DR: The literature treating mechanisms of catalyst deactivation is reviewed in this paper, which can be classified into six distinct types: (i) poisoning, (ii) fouling, (iii) thermal degradation, (iv) vapor compound formation accompanied by transport, (v) vapor solid and/or solid solid reactions, and (vi) attrition/crushing.
Abstract: The literature treating mechanisms of catalyst deactivation is reviewed. Intrinsic mechanisms of catalyst deactivation are many; nevertheless, they can be classified into six distinct types: (i) poisoning, (ii) fouling, (iii) thermal degradation, (iv) vapor compound formation accompanied by transport, (v) vapor-solid and/or solid-solid reactions, and (vi) attrition/crushing. As (i), (iv), and (v) are chemical in nature and (ii) and (v) are mechanical, the causes of deactivation are basically three-fold: chemical, mechanical and thermal. Each of these six mechanisms is defined and its features are illustrated by data and examples from the literature. The status of knowledge and needs for further work are also summarized for each type of deactivation mechanism. The development during the past two decades of more sophisticated surface spectroscopies and powerful computer technologies provides opportunities for obtaining substantially better understanding of deactivation mechanisms and building this understanding into comprehensive mathematical models that will enable more effective design and optimization of processes involving deactivating catalysts. © 2001 Elsevier Science B.V. All rights reserved.
2,526 citations
TL;DR: In this paper, an overall picture of shaped metal particles is presented, with a particular focus on solution-based syntheses for the noble metals, emphasizing key factors that result in anisotropic, nonspherical growth such as crystallographically selective adsorbates and seeding processes.
Abstract: Colloidal metal nanoparticles are emerging as key materials for catalysis, plasmonics, sensing, and spectroscopy. Within these applications, control of nanoparticle shape lends increasing functionality and selectivity. Shape-controlled nanocrystals possess well-defined surfaces and morphologies because their nucleation and growth are controlled at the atomic level. An overall picture of shaped metal particles is presented, with a particular focus on solution-based syntheses for the noble metals. General strategies for synthetic control are discussed, emphasizing key factors that result in anisotropic, nonspherical growth such as crystallographically selective adsorbates and seeding processes.
2,203 citations