The wet synthesis and quantification of ligand-free sub-nanometric Au clusters in solid matrices.

© The Royal Society of Chemistry. The synthesis of ligand-free sub-nanometric metal clusters on a large scale suffers typically from very low yields (15% yields, as unambiguously determined using a very simple and extremely sensitive analytical reaction test.

A promising camptothecin derivative: Semisynthesis, antitumor activity and intestinal permeability.

Oral administration of camptothecin (Cm) derivatives and other antitumoral agents is being actively developed in order to improve the quality of life of patients with cancer. Though several lipophilic derivatives of CPT have shown interesting oral bioavailability in preclinical and clinical studies, only Topotecan has been approved for this route of administration. Semisynthesis, antitumor activity, biological inhibition mechanism, and in situ intestinal permeability of 9, 10-[1,3]-Dioxinocamptothecin (CDiox), an unexplored CPT derivative, have been studied in this paper. The hexacyclic analog was as effective as Topotecan and CPT in different tumor cell lines, showing an expected similar a…

Cluster and Periodic Calculations of the Ethene Protonation Reaction Catalyzed by theta-1 Zeolite: Influence of Method, Model Size, and Structural Constraints

The protonation of ethene by three different acid sites of theta-1 zeolite was theoretically studied to analyze the extent and relevance of the following aspects of heterogeneous catalysis: the local geometry of the Bronsted acid site in a particular zeolite, the size of the cluster used to model the catalyst, the degree of geometry relaxation around the active site, and the effects related to medium- and long-range interactions between the reaction site and its environment. It has been found that while the reaction energy is very sensitive to the local geometry of the site, the activation energy is mainly affected by the methodology used and by electrostatic effects on account of the carbo…

Cobalt Metal-Organic Framework Based on Layered Double Nanosheets for Enhanced Electrocatalytic Water Oxidation in Neutral Media

A new cobalt metal-organic framework (2D-Co-MOF) based on well-defined layered double cores that are strongly connected by intermolecular bonds has been developed. Its 3D structure is held together by π-π stacking interactions between the labile pyridine ligands of the nanosheets. In aqueous solution, the axial pyridine ligands are exchanged by water molecules, producing a delamination of the material, where the individual double nanosheets preserve their structure. The original 3D layered structure can be restored by a solvothermal process with pyridine, so that the material shows a "memory effect"during the delamination-pillarization process. Electrochemical activation of a 2D-Co-MOF@Nafi…

Steam catalytic cracking of naphtha over ZSM-5 zeolite for production of propene and ethene: Micro and macroscopic implications of the presence of steam

One option to produce more ethene and propene can be to crack naphtha type fractions in dedicated smaller FCC units. We present here the results obtained for high temperature steam catalytic cracking (SCC) of a representative naphtha product (n-heptane) with ZSM-5. It has been found that under those conditions the presence of steam produces an irreversible dealumination of the zeolite as well as a reversible deactivation due to the interaction of water with active sites with a negative effect on protolytic cracking. A kinetic decay model that takes into account the two phenomena has been developed. The apparent activation energy is lower in the presence of steam. It appears that whilst the …

Quantum-chemistry calculations of surface complex and orbital control in para/ortho toluene alkylation catalyzed by big pore zeolites

Summary By means of MNDO-PM3 semiempirical quantum-chemistry calculations, the mechanism for alkylation of toluene by methanol on two zeolite clusters with Al and Ga as T III has been studied. The process variables controlled through the hypersurface of the reaction were: the distances of methyl group to the cluster of zeolite and to the toluene molecule; and the distances of the hydrogen atom of the toluene to be transfered to the zeolite cluster and to the toluene. The energetic factor associated with the electronic interaction between the molecular orbitals (LUMO of the zeolite-methoxy and HOMO of toluene) have been calculated by a PMO analysis for two geometries: the transition state an…

Surface interaction of Ni/Mo oxides on ultrastable Y zeolites

The interactions of NiO, MoO 3 and their mixtures with the acid surface of an H-Y ultrastable zeolite have been studied on a series of samples. These samples were prepared by impregnation, calcination and reduction, (if necessary), of Ni and Mo salts, on an H-Y ultrastable zeolite (HYUS). By using i.r. spectroscopy and X-ray diffraction techniques it has been observed that MoO 3 interacts with most of the hydroxyl groups while NiO interacts only with those appearing at 3640 and 3550 cm −1 . In the samples containing both oxides a strong interaction between them is shown, while the acidity of the original HYUS is partially regenerated. The influence of the order of impregnation on the final …

Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope

[EN] Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type …

Increasing the stability of the Ge-containing extra-large pore ITQ-33 zeolite by post-synthetic acid treatments

[EN] Extra-large pore ITQ-33 zeolite (ITT, 18 x 10 x 10-rings) is a very promising catalyst for the catalytic cracking of gasoil but, unfortunately, this material shows a limited hydrothermal stability due to the large germanium content present in the ITQ-33 structure. Taking this into account, the Ge-containing ITQ-33 has been post synthetically modified using different acid procedures with the aim of studying the effect of these treatments on the overall hydrothermal stability of this extra-large pore zeolite. In this sense, the as-prepared ITQ-33 has been treated with different HCl solutions in ethanol (from 0.1 to 1 M), containing also tetraethylorthosilicate (TEOS) as silicon precursor…

Electrochemical monitoring of the oxidative coupling of alkynes catalyzed by triphenylphosphine gold complexes

Electrochemical monitoring of the oxidative coupling of alkynes in the homogeneous phase through catalytic cycles involving triphenylphosphine gold complexes and selectfluor as oxidant reveals that at least two gold species in +3 and +1 oxidation states are implicated. Electrochemically driven homocoupling of terminal alkynes using molecular oxygen as the oxidant can be performed using such catalysts. Keywords: Gold catalysis, Oxidative coupling of alkynes, Oxygen, Voltammetry

Stabilized Naked Sub-nanometric Cu Clusters within a Polymeric Film Catalyze C-N, C-C, C-O, C-S, and C-P Bond-Forming Reactions

[EN] Sub-nanometric Cu clusters formed by endogenous reduction of Cu salts and Cu nanoparticles are active and selective catalysts for C−N, C−C, C−O, C−S, and C−P bond-forming reactions. Sub-nanometric Cu clusters have also been generated within a polymeric film and stored with full stability for months. In this way, they are ready to be used on demand and maintain high activity (TONs up to 104 ) and selectivity for the above reactions. A potential mechanism for the formation of the sub-nanometric clusters and their electronic nature is presented.

Enantioselective epoxidation of olefins with molecular oxygen catalyzed by gold(III): A dual pathway for oxygen transfer

Abstract A chiral gold(III) complex has been prepared that performs the epoxidation of olefins in the presence of O 2 , PhIO, or bleach. Catalytic experiments with 18 O show that O 2 is activated on the catalyst and can be directly incorporated into the epoxide through a non-radical mechanism that probably involves formation of gold, oxo, or peroxo species. In addition to this, there is a parallel radical mechanism operating that yields α , β -unsaturated ketones and alcohols as subproducts. Electrochemical and UV–Vis experiments confirmed the occurrence of a Au(III)/Au(I) redox cycle during the catalytic epoxidation in a mechanism sustained by molecular oxygen.

Unexpected photochemistry and charge-transfer complexes of [CB(11)H(12)](-) carborane.

Although the [CB(11)H(12)](-) carborane does not exhibit an absorption band in UV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation.

The influence of branching isomerization on the product distribution obtained during cracking of n-heptane on acidic zeolites

Abstract The initial selectivities for the primary products occurring during the cracking of n-heptane on a rare-earth (RE)-HY ultrastable zeolite up to 470°C have been calculated. The activation energies for the cracking of n-heptane and its branched isomers in the fraction C4 + C3 have been obtained by molecular orbital calculations, and these values and the predicted product distribution have been compared with those obtained experimentally. It is concluded that the cracking of n-heptane on large-pore zeolites may take place by different parallel routes involving protolytic and β-cracking of n-heptane and β-cracking of the readily formed branched carbenium ions. The relative importance o…

Gold Redox Catalytic Cycles for the Oxidative Coupling of Alkynes

[EN] Au(I)/Au(III) catalytic cycles are catalytically competent to perform the oxidative coupling of alkynes in the homogeneous phase at room temperature and without any protecting atmosphere. Selectfluor as oxidant, wet acetonitrile as solvent, and sodium carbonate as base are the reagents of choice. Both aromatic and alkyl alkynes can be coupled, and mechanistic studies reveal that at least two gold species having different oxidation states are implicated in the key step of the coupling.

The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…

Structural incorporation of nitrogen into zeolites, and alpos: ab initio molecular orbital calculations on stability and basicity

Ab initio molecular orbital calculations (HF/6-31G*) are used to obtain thermodynamical information on the possibility to form NH-bridging or NH2-terminal groups in amorphous and crystalline materials containing Si–O–Si and Al–O–P structures, such as for instance, zeolites and aluminophosphates. We have employed dimeric model clusters Si–O–Si and Al–O–P which contain NH2-terminal groups or an oxygen atom substituted by a NH bridging unit. The Bronsted basicity and the softness–hardness of these structures have been determined using the proton affinity and the HOMO energy, respectively. The obtained results indicate that for both Si–O–Si and Al–O–P linkages and from a thermodynamic standpoin…

A New Aluminosilicate Molecular Sieve with a System of Pores between Those of ZSM-5 and Beta Zeolite

[EN] A new aluminosilicate zeolite (ITQ-39) has been synthesized. This is an extensively faulted structure with very small domains that makes the structure elucidation very difficult. However, a combination of adsorption spectroscopy and reactivity studies with selected probe molecules suggests that the pore structure of ITQ-39 is related to that of Beta zeolite, with a three-directional channel system with large pores (12-MR), but with an effective pore diameter between those of Beta and ZSM-5, or a three-directional channel system with interconnected large (12-MR) and medium pores (10-MR). The pore topology of ITQ-39 is very attractive for catalysis and shows excellent results for the pre…

Nanolayered Cobalt-Molybdenum Sulfides as Highly Chemo- and Regioselective Catalysts for the Hydrogenation of Quinoline Derivatives

[EN] Herein, a general protocol for the preparation of a broad range of valuable N-heterocyclic products by hydrogenation of quinolines and related N-heteroarenes is described. Interestingly, the catalytic hydrogenation of the N-heteroarene ring is chemoselectively performed when other facile reducible functional groups, including alkenes, ketones, cyanides, carboxylic acids, esters, and amides, are present. The key to successful catalysis relies on the use of a nanolayered cobalt-molybdenum sulfide catalyst hydrothermally synthesized from earth-abundant metal precursors. This heterogeneous system displays a tunable composition of phases that allows for catalyst regeneration. Its catalytic …

Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43

[EN] The formation of mesopores in microporous zeolites is generally performed by postsynthesis acid, basic, and steam treatments. The hierarchical pore systems thus formed allow better adsorption, diffusion, and reactivity of these materials. By combining organic and inorganic structure-directing agents and high-throughput methodologies, we were able to synthesize a zeolite with a hierarchical system of micropores and mesopores, with channel openings delimited by 28 tetrahedral atoms. Its complex crystalline structure was solved with the use of automated diffraction tomography.

Synthesis of a novel zeolite through a pressure-induced reconstructive phase transition process

et al.

Xylene isomerization and aromatic alkylation in zeolites NU-87, SSZ-33, β, and ZSM-5: molecular dynamics and catalytic studies

The unique pore topology of zeolite NU-87, with 10-membered ring (MR) channels intersected by perpendicular 12-MR cavities, can offer new opportunities for alkylaromatics isomerization, as well as for aromatics alkylation. The catalytic performance has been studied for meta-xylene isomerization and disproportionation, as well as toluene alkylation with methanol, ethanol, propanol, and isopropanol. Product distribution was interpreted on the basis of pore topology and compared to zeolites with 12-MR (β), 10- and 12-MR (SSZ-33), and 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for the location of bulky intermediates and/or products, and also traps the molecules, allowing…

Synthesis of hyacinth, vanilla, and blossom orange fragrances: the benefit of using zeolites and delaminated zeolites as catalysts

The synthesis of phenylacetaldehyde glycerol acetals, 2-benzyl-4-hydroxymethyl-1,3-dioxolane (1), 2-benzyl-5-hydroxy-1,3-dioxane (2), and vanillin propylene glycol acetal (2-(4-hydroxy-3-methoxyphenyl)-4-methyl-1,3-dioxolane) (3) which are flavoring compounds with hyacinth and vanilla scent fragrances, have been carried out successfully by acetalization of phenylacetaldehyde and vanillin with glycerol and propylene glycol, respectively, using toluene as solvent and zeolite catalysts whose adsorption properties have been optimized. However, in the case of a larger size acetal such as 2-acetonaphthone propylene glycol acetal (4) with blossom orange scent, geometrical constraints make the diff…

Ionic Hydrogel Based on Chitosan Cross-Linked with 6-Phosphogluconic Trisodium Salt as a Drug Delivery System.

[EN] In this work, 6-phosphogluconic trisodium salt (6-PG(-)Na(+)) is introduced as a new aqueous and nontoxic cross-linking agent to obtain ionic hydrogels. Here, it is shown the formation of hydrogels based on chitosan cross-linked with 6-PG(-)Na(+). This formulation is obtained by ionic interaction of cationic groups of polymer with anionic groups of the cross linker. These hydrogels are nontoxic, do not cause dermal irritation, are easy to extend, and have an adequate adhesion force to be applied as polymeric film over the skin. This AWN formulation exhibits a first order release kinetic and can be applied as drug vehicle for topical administration or as wound dressing for wound healing…

Structure-reactivity relationship for aromatics transalkylation and isomerization process with TNU-9, MCM-22 and ZSM-5 zeolites, and their industrial implications

[EN] TNU-9 is a medium pore zeolite with a complex tridimensional channel system. Its catalytic properties have been studied in some reactions that involve the BTX fraction, such as benzene and toluene alkylation with methanol, ethanol or isopropanol. These reactions use in practice medium pore zeolites such as ZSM-5 (MFI) or MCM-22 (MWW), and the selectivities obtained with TNU-9 are compared and analyzed from the point of view of the zeolite structure and pore topology, as well as from its possible industrial application. For benzene alkylation to give ethylbenzene (EB), TNU-9 is an active and selective catalyst with selectivities to EB much higher than ZSM-5 and close to those of the ind…

Isomerization and disproportionation of m-xylene in a zeolite with 9- and 10-membered ring pores: Molecular dynamics and catalytic studies

The unique pore topology of zeolite ITQ-13 with 9-membered ring (MR) channels intersected by perpendicular 10-MR channels and larger void space with 10-MR cross-sections was studied for meta-xylene isomerization and disproportionation. Product distribution was interpreted on the basis of pore topology and compared with zeolites with 12-MR (β), 10-MR, and intersecting 12-MR cavities (NU-87), as well as 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for bulky intermediates and/or products and also provides room for molecules to drive consecutive reactions toward thermodynamic equilibrium. Channels, on the other hand, allow diffusion without trapping if their free diameters…

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixed-valence digold (I, III) acetylide compl…

Synthesis of Densely Packaged, Ultrasmall Pt02Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature

The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal c…

Unexpected photochemistry and charge-transfer complexes of [CB11H12]2 carborane

Although the [CB11H12]¯carborane does not exhibit an absorption band inUV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation. Galletero Pedroche, M.Sales, Sales.Galletero@uv.es

A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet-like crystal morphology, large surface area, fully four-coordinated Al species, and abundant acidic sites. Methanol-to-propylene (MTP) tests reveal that the Al-ITH zeo…

IM-5 zeolite for steam catalytic cracking of naphtha to produce propene and ethene. An alternative to ZSM-5 zeolite

Steam catalytic cracking of naphtha in smaller FCC units can be considered an option to produce more ethene and propene. These units will operate at high reaction temperatures and in the presence of steam. The profitability of these units could be improved with the use of new catalysts with higher activity and hydrothermal stability, without compromising the selectivity to light olefins. We have explored the possibilities of IM-5 zeolite for high temperature steam catalytic cracking (SCC) of a naphtha, as an alternative to commonly used ZSM-5 zeolite. So, we compare the catalytic activity, the effect of operating variables of the process and the yields of interest products between the two z…

Identification of Bioactive Compounds in Polar and Nonpolar Extracts of Araujia sericifera

Abstract Araujia sericifera is a native perennial, climbing laticiferous shrub from South America that is currently naturalized in many other countries. Previous data describe promising properties for A. sericifera, but no systematic study of its bioactive compounds and possible medicinal applications has been conducted to date. In the present study, aerial parts of A. sericifera (leaves, stems, and fruits) were explored by combining GC-MS and NMR spectroscopy analysis for both nonpolar (hexane) and polar (methanol) extracts. The hexanic extracts contained high amounts of pentacyclic triterpenes including two new metabolites, 3-tigloyl germanicol (18) and 3-tigloyl lupeol (19). The methanol…

Quantitative EPR study of Mn(II)salen oxidation within zeolite Y

Confined Pt-1(1+) Water Clusters in a MOF Catalyze the Low-Temperature Water-Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

[EN] The synthesis and reactivity of single metal atoms in a low-valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Herein, we show a gram-scale wet synthesis of Pt-1(1+) stabilized in a confined space by a crystallographically well-defined first water sphere, and with a second coordination sphere linked to a metal-organic framework (MOF) through electrostatic and H-bonding interactions. The role of the water cluster is not only isolating and stabilizing the Pt atoms, but also regulating the charge of the metal and the adsorption of reactants. This is shown for the low-temperature water-gas shift reaction (WGSR: CO + H2O CO2 + H…

Catalytic cracking of n-alkane naphtha: The impact of olefin addition and active sites differentiation

An extended dual kinetic model allows to fit the n-heptane cracking results working in a wide range of reaction conditions. The duality of the model is provided by the contribution of monomolecular and bimolecular cracking mechanisms. It takes into account the role played by the olefins formed on the global cracking or added within the feed. Furthermore by means of this model and the kinetic parameters obtained when cracking n-heptane on ZSM-5, it has been observed that, while some characterization techniques show a homogeneous zeolite surface from the point of view of the active sites, rigorous kinetic experiments point to the possibility that the reactant sees a heterogeneous surface with…

Partial Reduction and Selective Transfer of Hydrogen Chloride on Catalytic Gold Nanoparticles

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim HCl in solution accepts electron density from Au NPs and partially reduces at room temperature, as occurs with other simple diatomic molecules, such as O2 and H2. The activation can be run catalytically in the presence of alkynes to give exclusively E-vinyl chlorides, after the regio- and stereoselective transfer of HCl. Based also on this method, vinyl chloride monomer (VCM) can be produced in a milder and greener way than current industrial processes.

Theta-1 zeolite catalyst for increasing the yield of propene when cracking olefins and its potential integration with an olefin metathesis unit

[EN] There is a need for on-purpose propene production technologies beyond energy-intensive steam cracking. Hexene is a compound with limited value that can be found in several streams in the refinery and can readily crack on zeolites at lower temperatures and shorter contact times than those used for cracking alkanes. Cracking over ZSM-5 zeolite yields high selectivity to light olefins. These results are improved by Theta-1 zeolite, which can yield a remarkable propene molar selectivity of 180% (90 wt%) at 90% conversion, close to the maximum thermodynamic yield. Moreover, crystal engineering allowed its TOF to increase by more than 50%. Based on these results we also identified some prosp…

Quantum chemistry calculations on the effect of electron confinement upon the frontier molecular orbitals of ethylene and benzene in sodalite. Implications on reactivity

Abstract Quantum chemistry calculations using HF / STO-3G, CEP-41G, and 3-21G basis sets have been carried out in order to study the effect of the electron confinement of ethylene and benzene in the microporous environment existing in a sodalite cage. The electron confinement produces an increase of 1.06 and 1.31 eV at the 3-21G level in the energy of the HOMO of ethylene and benzene, respectively, when placed in the centre of the cavity with respect to the HOMO energy in the gas phase. There is an increase in the energy of the HOMO when the molecules approach the walls of the zeolite.

Stabilization of ZSM-5 zeolite catalysts for steam catalytic cracking of naphtha for production of propene and ethene

In order to increase ethene and propene, naphtha steam catalytic cracking has been considered. The cracking of C 5-C 12 n-alkanes with ZSM-5 has been studied in absence and in presence of steam and the influence of the operation variables was studied. Irreversible catalyst deactivation by dealumination also occurs in the reactor when the cracking is carried out in the presence of steam. To diminish steam deactivation, the influence of zeolite Si/Al framework and a postsynthesis treatment by phosphorous have been studied and optimized. Much more stable catalyst can be achieved that result in an increase in activity without penalty for production of ethene and propene.

A Multisite Molecular Mechanism for Baeyer-Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant

The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO 2 (rutile). The tin active site has been modeled by means of a S…

Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

[EN] The search for simple, earth-abundant, cheap, and nontoxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated FeIII¿O sites on solids are able to dissociate and chemoselectively transfer H2 to acetylene in an industrial process. For that, a novel, robust, and highly crystalline metal¿organic framework (MOF), embedding FeIII¿OH2 single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structur…

Selective Introduction of Acid Sites in Different Confined Positions in ZSM-5 and Its Catalytic Implications

Controlling the location of acid sites in zeolites can have a great effect on catalysis. In this work we face the objective of directing the location of Al into the 10R channels of ZSM-5 by taking advantage of the structural preference of B to occupy certain positions at the channel intersections, as suggested by theoretical calculations. The synthesis of B-Al-ZSM-5 zeolites with variable Si/Al and Si/B ratios, followed by B removal in a postsynthesis treatment, produces ZSM-5 samples enriched in Al occupying positions at 10R channels. The location of the acid sites is determined on the basis of the product distribution of 1-hexene cracking as a test reaction. The higher selectivity to prop…

Predicting the activity of single isolated Lewis acid sites in solid catalysts.

An experimental study of the activity of Ti-, Zr- and Sn-beta catalysts in different types of oxidation reactions is combined with a quantum-chemical analysis of the electronic properties of the active sites and the adsorbed reactants. The differences observed in the catalytic behaviour of the three materials are explained in terms of the molecular orbital distribution of each system. The intrinsic Lewis acid strength of the isolated active site, the degree of back-donation from the catalyst to the empty orbitals of the organic reactant and the net atomic charges on selected atoms are proposed as predictors of reactivity.

Influence of layer structure preservation on the catalytic properties of the pillared zeolite MCM-36

MCM-36 is a catalytically active material made by swelling and subsequent pillaring of a layered zeolite precursor, MCM-22(P). However, the swelling procedures lead to significant destruction of layer structure and alteration of framework silicon/aluminum (Si/Al) ratio, which are likely to influence the acidity and catalytic activity of the final materials. We report a milder swelling and pillaring process to prevent such structural destruction. The resulting pillared materials show higher crystallinity and improved retention of the zeolitic layer structure when compared to the ones prepared by the previously reported methods involving more aggressive treatments. Implications of such struct…

Orbital-controlled reactions catalysed by zeolites: Electrophilic alkylation of aromatics

The role of orbital control in product selectivity during electrophilic aromatic alkylation catalysed by zeolites was studied both theoretically and experimentally. In order to discuss this, the alkylation of toluene and m-xylene by methanol was carried out on a series of large-pore zeolites (HY). The changes in the para to ortho ratio observed on changing the framework Si/Al ratio of the zeolites were related to ab initio molecular orbital calculations of the LUMO energy of structurally alike model clusters but containing different tetrahedral cations around the active site. The observed correlation is discussed in terms of the HSAB principle by taking into account the influence of the cat…

Book Review: Catalysis and Zeolites. Fundamentals and Applications. Edited by Jens Weitkamp and Lothar Puppe.

The benefit of multipore zeolites: Catalytic behaviour of zeolites with intersecting channels of different sizes for alkylation reactions

Abstract The catalytic behaviour of two multipore zeolites containing channels of different sizes, SSZ-33 (10 windows × 12 MR) and ITQ-22 (8 × 10 × 12 MR pores), for alkylation of benzene with ethanol and benzene with isopropanol or propylene, has been studied and compared to that of zeolites with intersecting channels of the same size, ZSM-5 (10 × 10 MR channels) and Beta (12 × 12 MR channels), which are industrially used for the above-mentioned process. For the alkylation of benzene with ethanol in gas phase, ITQ-22 behaves like the 10 MR ZSM-5 with respect to ethylbenzene selectivity, while the behaviour of SSZ-33 is close to that of a 12 MR zeolite such as Beta. For the alkylation of be…

Metal-Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces

ConspectusSince the advent of the first metal-organic frameworks (MOFs), we have witnessed an explosion of captivating architectures with exciting physicochemical properties and applications in a wide range of fields. This, in part, can be understood under the light of their rich host-guest chemistry and the possibility to use single-crystal X-ray diffraction (SC-XRD) as a basic characterization tool. Moreover, chemistry on preformed MOFs, applying recent developments in template-directed synthesis and postsynthetic methodologies (PSMs), has shown to be a powerful synthetic tool to (i) tailor MOFs channels of known topology via single-crystal to single-crystal (SC-SC) processes, (ii) impart…

CCDC 1587822: Experimental Crystal Structure Determination

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CSD 1409698: Experimental Crystal Structure Determination

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CCDC 1841425: Experimental Crystal Structure Determination

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