Monolithic metal-organic frameworks towards applications in industrial catalysis: a review

Journal of the Society of Chemical IndustryVolume 57, Issue 33 p. 759-766 Article The application of catalysis in industry. Jubilee memorial lecture, 1937-1938 E. B. Maxted, E. B. MaxtedSearch for more papers by this author E. B. Maxted, E. B. MaxtedSearch for more papers by this author First published: 13 August 1938 https://doi.org/10.1002/jctb.5000573302Citations: 5AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume57, Issue3313 August 1938Pages 759-766 RelatedInformation

Guiding the design of practical MTW zeolite catalysts: An integrated experimental-theoretical perspective

Advances and Applications of Catalysis in Industry: From Nanocatalysis to Environmental Sustainability

Iron oxide nanoparticles are iron-based nanomaterials that are, to date, successfully used in various areas of industry and everyday life. The sustainability of iron is a factor which leads to wide variety of research of the iron oxide roles in industrial catalysis and biomedicine. An industrial catalysis and biomedical applications are here connected, because these two groups of applications demand very similar preparation of materials: shape of the particles and their size, the particular and, as uniform as possible, particle porosity. Further, commonly used synthesis methods are outlined, in order to be able to select the preferred synthesis method according to final desired application of the nanoparticles.

Hydrotalcite-based materials, characterized by their unique composition are integral to diverse applications in heterogeneous catalysis and beyond. Renowned for their catalytic prowess, these compounds serve as versatile bases for organic reactions, support structures for metal catalysts, and facilitators in organic transformations and water treatment. This comprehensive book introduces readers to hydrotalcite-like compounds, with ten chapters exploring variations in metal ion ratios and interlayer anions, and their impact on properties crucial for industrial applications (ranging from industrial catalysis to medicine). Key Features Detailed exploration of hydrotalcite and hydrotalcite-like compounds Recent trends and applications in industrial catalysis, organic synthesis, and environmental remediation Hydrotalcite synthesis including methods like coprecipitation, sol-gel processing, and advanced techniques Contributions from leading researchers in the field with references Comprehensive overview for each topic suitable for both academics and industry professionals With its exhaustive coverage of hydrotalcite-based materials and their multifaceted applications, this book promises to be an indispensable resource for anyone who wants to understand the utilization of hydrotalcites for advanced catalytic processes.

Biomimetic metal-organic frameworks mediated hybrid multi-enzyme mimic for tandem catalysis

Contribution to catalytic cracking in the petroleum industry

Serious environment and safety issues by the wide application of inorganic mineral acids have attracted worldwide attention from fundamental science and application point of view. Under such circumstances, the development of the solid acid catalysts is a very hot topic currently. The ideal solid acid catalysts possess appropriate Bronsted and Lewis acidic nature, good porosity, high stability and unique morphology. Among them, the morphological nanostructure of catalysts is one of the important factors that can have a profound influence on their catalytic performance. Compared with a number of other supports of the solid acid catalysts, the silica-based materials are considered as promising candidates because of their diverse composition, physicochemical property and morphology as well as excellent porosity property. Among them, mesoporous silica-based materials possess lager pore compared with the microporous silica materials (e.g., ZSM-5, H-beta, etc.). They enable to catalyze reactions efficiently involving bulky substrates and/or products, and facilitate mass transfer. Meanwhile, the larger pore favors the dispersion of the active sites and hinders the accumulation of coke on the surface to avoid pore blocking. As a result, one of the important strategies to prepare novel solid acid catalysts is to immobilize the active sites on mesoporous silica materials. The as-prepared mesoporous silica-based solid acid catalysts have shown great potential for application in the field of environment, energy and industrial catalysis. In this paper, the latest progress on the morphology-controlled preparation of mesoporous silica−based materials and their applications in catalysis are summarized. In the case of the silica-based materials, it can be dated back to the early 1990s, and Mobil Company synthesized various M41S materials firstly (MCM-41, MCM-48 and MCM-50) by using the alkyl quaternary ammonium salt cationic surfactant as the template agent. Compared with the amorphous silica materials, M41S possess ordered mesoporous structure, uniform pore size (2‒5 nm), large pore volume and BET surface area (1000 m2 g-1). Subsequently, various SBA materials (such as SBA-15 and SBA-16) with large pore size were prepared successfully. It has attracted wide attention to functionalize the silica materials by incorporating the active sites and maintaining the morphological structure. With the development of silica-based materials, periodic mesoporous organosilicas (PMO) were synthesized by surfactant-directed sol-gel method, which opened a new pathway to prepare functional mesoporous silica materials. Up to now, a number of functionalized organosilica materials have been reported and exhibited great potential in the fields of catalysis, sensing, chromatography analysis, metal adsorption and bio-pharmacy etc. Herein, the mesoporous silica-based solid acid catalysts by the morphology-controlled preparation of functionalized organosilicas showed highly ordered, tubular or hollow spherical nanostructure by P123-directed sol-gel co-condensation. The as-prepared mesoporous silica-based solid acid catalysts possessed hydrophobic surface, excellent porosity property and strong Bronsted acidic nature. Moreover, the catalysts with well-defined morphology exhibited high catalytic performance for synthesis of the biomass-derived platform molecules or high value-added chemicals. Owing to the accelerated diffusion, transmission and improved accessibility of substrates to active sites, the mesoporous silica-based solid acid catalysts with hollow nanosphere morphology showed the highest activity compared with the tubular or ordered analogues. On the other hand, the covalent bond between active sites and silica framework can avoid the leaching issue of the solid acid catalysts. In addition, the hydrophobic character of alkyl-containing organosilica can reduce acid sites deactivation associated with adsorption of polar byproducts, which can improve the stability of as-prepared catalysts. To summarize, this review aims to provide important reference value for development of novel solid acid catalysts.

Chromene derivatives are naturally occurring heterocyclic compounds used as cosmetic agents, food additives, and potential biodegradable agrochemicals. Normally, its synthesis is carried out with three component/substrates with a suitable base. Dendrimer with amine functionality has several applications in catalysis, more specifically, dendrimers having enriched amino groups with accessible void makes a significant impact in base catalysis. Moreover, polar periphery of the dendrimers may enhance the solubility of material in the reaction medium. Therefore, herein we report the base catalytic efficiency of magnetite nanoparticle supported polyamine dendrimer with enriched amine groups and peripheral carboxyl groups. Actually, magnetite supported polyamine dendrimer synthesis involves the synthesis of PAMAM G3 on magnetite nanoparticle core, followed by reduction of amide group with subsequent functionalization of carboxylic acid terminals. Further, it is used as versatile polyvalent base for the synthesis of chromene derivatives. The magnetite supported dendritic scaffold has accessible voids and polar periphery which enables them dispersible in the reaction medium. The recycle efficiency study confirms, the competency of the material to work in industrial catalysis.

Ionic liquids: applications in catalysis

Applied Organometallic Chemistry and Catalysis has two main objectives: to provide an overview of the influence of organometallic chemistry on homogeneous and heterogenous catalysis, and to provide an account of the principle commercial applications of homogeneous catalysis in industry. The first chapter provides some background to the subject, looking at the vital role that catalysis plays in the production of fuels and pharmaceuticals, amongst other things. The next chapter covers mechanistic organometallic chemistry. Chapter Three is related to hydroformylation and related reactions. The chapter that follows examines acetic acid and acetyl chemicals. The next two chapters look at nylon intermediates: buta- 1,3-diene hydrocyanation and olefin oligomerization and polymerization. The final chapter is about fine chemicals manufacture.

The hydroformylation of alkenes catalyzed by dissolved rhodium complexes is not only one of the largest applications of homogeneous catalysis in industry, but also an established benchmark reaction for testing immobilization concepts for homogeneous catalysts. In recent years, ionic liquids (ILs) as non-aqueous solvents for liquid–liquid biphasic hydroformylation catalysis have been the subject of intensive study. Important features of ILs compared to the industrial aqueous–organic biphasic catalysis (Ruhrchemie–Rh ne–Poulenc process), are their much better solubility for higher alkenes and their compatibility with phosphite ligands, which readily decompose by hydrolysis in water. Despite these attractive features, we know of no largescale industrial application of ionic liquids in biphasic hydroformylation catalysis to date. Two important drawbacks of the biphasic ionic liquid systems are the relatively high amounts of expensive IL that are required and its intrinsically high viscosity, which leads to slow mass transport between the two liquid phases. To overcome these limitations, we, among others, have in recent years developed the supported ionic liquid phase (SILP) concept. SILP materials are prepared by dispersing a solution of the catalyst complex in an ionic liquid as a thin, physisorbed film on the large internal surface area of a porous solid material. Since the film thickness of the ionic liquid is within the nanometer range, diffusion problems are minimized by the extremely small diffusion distances. Excellent ionic liquid utilization is achieved; that is, the same catalytic performance can be achieved with a much smaller total IL amount compared to liquid–liquid biphasic systems. Because ionic liquids typically have extremely low vapor pressures, catalysis with SILP materials is particularly attractive in continuous gas-phase contact. During catalysis the immobilized catalytic ionic liquid film comes into contact solely with gaseous reactants and products. For the continuous gas-phase hydroformylation of pure 1-alkene feedstock, such as, propene and 1-butene, this concept has been demonstrated quite successfully with good catalytic activity (turnover frequencies (TOFs) up to 500 h 1 in the case of propene and 564 h 1 in the case of 1-butene) and excellent catalyst stability (up to 200 h time-on-stream in the case of propene and 120 h in the case of 1-butene) as was demonstrated using a Rh-SILP catalyst modified with the sulfonated phosphine ligand sulfoxantphos (1). The sulfoxantphos–rhodium catalyst is, however, unable to react with internal alkenes such as 2butenes in either hydroformylation or isomerization. Thus, to convert 1-butene and 2-butenes from a mixed technical C4 feedstock from steam-cracker into the desired linear pentanal, a different catalyst system is required. Rhodium–phosphite complexes are known to be capable of selective isomerization/hydroformylation activity, which converts internal alkenes in a classical monophase homogeneous catalysis into linear aldehydes with good to excellent selectivity. Most of these ligands, however, are highly airand moisture-sensitive, making it difficult to handle and use them in large quantities and a real challenge to recycle rhodium– phosphite systems. Herein, we show how the new diphosphite ligand 2 in form of a SILP catalyst system is applied in the continuous gas-phase hydroformylation of an industrial mixed C4 feedstock as illustrated in Scheme 1. Synthesizing 2 and using it in

Aspects of enzymatic catalysis in lipase-catalyzed reactions of organic synthesis are discussed in the review. The data on modern methods of protein engineering and enzyme modification allowing a broader range of used substrates are briefly summarized. The application of lipase in the preparation of pharmaceuticals and agrochemicals containing no inactive enantiomers and in the synthesis of secondary alcohol enantiomers and optically active amides is demonstrated. The subject of lipase involvement in the C-C bond formation in the Michael reaction is discussed. Data on the enzymatic synthesis of construction materials--polyesters, siloxanes, etc.--are presented. Examples demonstrating the application of lipase enzymatic catalysis in industry are given.

Rhodium catalyzed hydroformylation is one of the most important applications of homogeneous catalysis in industry[1]. The addition of CO and H2 to alkenes is a mild and clean method for the functionalization of hydrocarbons. The atom economy of the reaction can be 100% and the selectivity for the desired aldehyde can be very high. Most of the six million tons of aldehydes produced annually by this process is converted into plasticizers for polymers and detergent alcohols. Since the linear aldehydes are the desired products for these applications, a key issue in industrial hydroformylation is the control of regioselectivity. The generally accepted hydroformylation mechanism is shown in Scheme 1. The active catalyst is the five-coordinated complex A, which usually contains two phosphorus ligands. This catalyst consists of two isomeric structures in which the phosphine ligands coordinate in a diequatorial (e-e) and in an equatorial-apical (e-a) fashion. Bidentate ligands can give rise to either of these two complexes depending on their natural bite angle.

As one of the alternative metals to platinum, which supports a wide range of applications in chemistry and catalysis in industry, palladium increasingly receives attention because of its similar physicochemical properties. However, Pd is generally less expensive than Pt and has a richer natural reserve. Herein, some recently developed techniques for the preparation and characterization of Pd‐based bimetallic catalysts are reviewed. The impact on catalytic reactions of interest, including hydrogenation, dehydrogenation, hydrogenolysis, reforming, the oxygen reduction reaction, and hydrodesulfurization are also discussed. It is shown that the catalytic performance of Pd‐based bimetallic catalysts is strongly dependent on the geometric and electronic states of Pd, which can be significantly affected by blended foreign element(s). Rationalization of the structure–activity relationship can provide useful guidelines to the fine tuning of these important catalytic reactions.