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Direct methane functionalization and, in particular, the selective partial oxidation to methanol, remains an eminent challenge and a field of competitive research. The conversion of methane to methanol over transition-metal-containing zeolites using molecular oxygen is a promising and extensively studied process. Herein, we scrutinize some oft-cited assumptions in this topic—which include the labelling of the process as biomimetic, the debate regarding the industrial viability of direct methane-oxidation systems and the claim that methane is difficult to activate—and delineate the extent to which these are scientifically robust. We highlight both the merits and pitfalls of such statements and point out the hazards associated with their improper use. By examining these misconceptions, we build an outlook for future research, highlighting the need to optimize materials and process conditions for the stepwise approach and to further explore catalytic processes that explicitly employ strategies for the preservation of methanol. While converting methane to methanol is an attractive process, making a catalytic—and commercially viable—route has presented severe difficulties. Here van Bokhoven and co-workers discuss the successes, problems and misconceptions in the field, focusing on the reaction with molecular oxygen over zeolites.

The isothermal, low-temperature stepwise conversion of methane to methanol over copper-exchanged zeolites eliminates the time-consuming heating and cooling steps of the conventional high temperature activation approach. To better understand differences between the two approaches, a series of zeolites were screened, of which omega zeolite (MAZ) showed superior performance in both the isothermal and conventional approaches.

Methane is often flared due to the heavy economic burden of transportation, particularly at rural petroleum extraction sites. Directly converting methane to methanol is possible through a stepwise process with copper- exchanged zeolites. Factors affecting this conversion are not yet fully understood. Omega zeolite ( MAZ) can yield 197 mu mol per gram- zeolite, the highest reported thus far. Here we show that the synthesis and resulting morphology of the zeolite play an enormous role in the yield of methanol. High yields are only achieved when the zeolite has a longer stick- like bundled morphology ( 2- 4 mu m by 100 nm). When the zeolite forms small spherulitic aggregates, the methanol yield is severely diminished ( 60- 97 mu molmethanol per gram- zeolite). This difference originates from minute changes in the synthesis procedure, emphasizing the extreme sensitivity of zeolite properties towards synthesis conditions. This work shows that selecting a parent zeolite is crucial and is an opportunity for process optimization to achieve high and industrially- relevant methanol yields.

International audience; A family of Al-rich ZSM-5 zeolites with Si / Al = 8 ± 0.5 was prepared according to a biomass-mediated supramolecular approach. A combination of advanced characterisation techniques and periodic density functional theory (DFT) calculations unraveled the purity and stability of unexpected Al-enriched ZSM-5 structures, hence allowing to cross the frontier of Si / Al lower limit. In addition, these Al-rich ZSM-5 zeolites demonstrated high catalytic activity in n-hexane cracking and methanol conversion into hydrocarbons, being in line with the presence of numerous BrØnsted acid sites.

A study exploring the use of ionic liquid reactions based on imidazolium halides in molecular sieve synthesis has produced a novel zincoaluminophosphate material with an open DFO-type framework structure. This framework structure had only been observed previously in the magnesioaluminophosphate system (Mg-DAF-1) where decamethonium was used as the structure directing agent. The new Zn-DAF-1 material has been characterized using chemical and thermogravimetric analysis and ^(13)C, ^(19)F, ^(27)Al and ^(31)P MAS NMR techniques. Structure analysis (P6/mcc, a = 22.2244(1) Å, c = 42.3293(3) Å) using synchrotron powder diffraction data not only confirmed the framework structure, but also revealed the locations of the Al, P and Zn atoms in the framework, the N,N′-di-isopropyl-imidazolium (DIPI) ions in the pores, some fluoride ions associated with double 4-rings, and some water molecules and anions filling the remaining space. This level of structural detail had not been possible in the Mg-DAF-1 material. Four different locations for the DIPI cation were found in the two 12-ring channels and Zn was found to substitute for only one of the six crystallographically distinct Al sites to yield the approximate crystal chemical formula |(DIPI)_(17)(OH,F)_(11)(H2O)_(23)|[Zn_6Al_(126)P_(132)O_(528)]-DFO.

Using heavy-atom labeling in conjunction with electron microscopy, we here visualize the distribution of point defects, i.e. internal silanol groups, in silicalite-1 zeolites at the single crystal level., Chemical Communications, 55 (4), ISSN:1359-7345, ISSN:1364-548X

A literature survey reveals a prominent reduction in the concentration of Brønsted acid sites in hierarchically organized zeolites with increasing mesoporous or external surface area independent of the framework type or synthesis route; this suggests a common fundamental explanation. To determine the cause, nature, and impact of the underlying changes in aluminum speciation, this study combines a multitechnique analysis that integrates basic characterization, a detailed synchrotron XRD and multiple-quantum NMR spectroscopy assessment, and catalytic tests to correlate evolution of the properties with performance during successive steps in the preparation of hierarchical MFI-type zeolites by desilication. The findings, subsequently generalized to FAU- and BEA-type materials, identify the crucial impact of calcination on the protonic form, which is an integral step in the synthesis and regeneration of zeolite catalysts; on aluminum coordination; and the associated acidity trends.

Electron-diffraction data on the zeolites Silicalite-1 and ZSM-5 (both MFI framework type) were collected from individual grains of about 150×100×50 nm3 . Crystals were synthesized with tetrapropylammonium as structure-directing agent. The resolution extended to about 0.8 A for Silicalite-1 and about 0.9-1.0 A for ZSM-5 crystals. Analysis of several data sets showed that at the nanometre-scale, these zeolite crystals are single crystals and not intergrown.

Large ZSM-5 zeolite crystals synthesized in fluoride medium show an astonishing activity, stability as well as selectivity towards light olefins in the Methanol-To-Olefins (MTO) reaction. By proper control of the synthesis parameters, ZSM-5 single crystals of unprecedented high quality are produced. The absence of usually uncontrollable variables such as structural defects, external non selective surface acid sites and extra-framework aluminium (EFAl) species was evidenced by SEM, HRTEM, CO-FTIR, 27Al and 19F MAS-NMR, Rietveld structure refinement and N2- and Ar-gas sorption measurements. Interestingly, diffusivity evaluation of different probe molecules (toluene, benzene and neopentane) has been carried out with PFG-NMR, allowing casting light on an interesting structure-diffusion-activity relationship. A “levitation” effect could be experimentally demonstrated and its impact on catalysis is highlighted in a rationalization attempt: Maxwell-Boltzmann based diffusion models properly predict product distributions for this counter-intuitively outstanding Methanol-To-Propylene (MTP) catalyst.

Funding: Royal Society for provision of an industry fellowship and the EPSRC for funding (EP/K025112/1 and EP/L014475/1) (R.E.M.); Czech Science Foundation for (P106/12/G015) (J.Cˇ.); European Community under a Marie Curie Intra-European Fellowship (A.B.P.). Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure-directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8-rings all the way to extra-large pores consisting of 14-rings. Publisher PDF

Hydrolysis of germanosilicate zeolites with the IWW structure shows two different outcomes depending on the composition of the starting materials. Ge-rich IWW (Si/Ge=3.1) is disassembled into a layered material (IPC-5P), which can be reassembled into an almost pure silica IWW on treatment with diethoxydimethylsilane. Ge-poor IWW (Si/Ge=6.4) is not completely disassembled on hydrolysis, but retains some 3D connectivity. This structure can be reassembled into IWW by incorporation of Al to fill the defects left when the Ge is removed., Angewandte Chemie, 53 (27), ISSN:1521-3757, ISSN:0044-8249

Herein, the first comparison of the mechanisms of glucose-to-fructose isomerization in aqueous media enabled by homogeneous (CrCl3 and AlCl3 ) and heterogeneous catalysts (Sn-beta) by using isotopic-labeling studies is reported. A pronounced kinetic isotope effect (KIE) was observed if the deuterium label was at the C2 position, thus suggesting that a hydrogen shift from the C2 to C1 positions was the rate-limiting step with the three catalysts. (13) C and (1) H NMR spectroscopic investigations confirmed that an intra-hydride-transfer reaction pathway was the predominant reaction channel for all three catalysts in aqueous media. Furthermore, the deuterium atom in the labeled glucose could be mapped onto hydroxymethylfurfural and formic acid through reactions that followed the isomerization step in the presence of Brønsted acids. In all three catalysts, the active site appeared to be a bifunctional Lewis-acidic/Brønsted-basic site, based on a speciation model and first-principles calculations. For the first time, a mechanistic similarities between the homogeneous and heterogeneous catalysis of aldose-to-ketose isomerization is established and it is suggested that learning from homogeneous catalysis could assist in the development of improved heterogeneous catalysts.

A procedure to enable the use of the very open framework Zn-STA-1 as catalyst, based on in situ calcination in a water-free environment, has been developed. The material shows a remarkable performance in the m-xylene isomerization test reaction, comparable to that of USY zeolite. The reported experimental procedure avoids the collapse of the SAO structure upon calcination, which has prevented the use of this very open framework structure in catalytic applications, and provides a promising new microporous catalyst for processing bulky molecules.

A nonenzymatic route for xylose isomerization in an aqueous medium using zeolite Sn-beta as a catalyst is demonstrated. Xylulose and lyxose are the primary and secondary products. The maximum yield to xylulose is 27%, with an 11% yield to lyxose at ∼60% xylose conversion at 100 °C. When the Sn-beta zeolite is combined with a Bronsted acid catalyst, furfural forms in a single pot from xylose in an aqueous medium at much lower temperatures than typically employed for this reaction.

Three bulky organic cations, benzylmethylpyrrolidinium (BMP), (S,S)-2-hydroxymethyl-1-benzyl-1-methylpyrrolidinium (BML) and benzylmethylhexamethyleniminium (BMH), were used in combination with the small cation tetramethylammonium (TMA) in the synthesis of zeolite materials. Two of them are distinguished by the number of carbon atoms forming the cyclic amine, which varies from 4 in BMP to 6 in BMH. In addition, a –CH2–OH group has been introduced in the carbon atom belonging to the amine ring next to the nitrogen atom, to originate a chiral molecule, BML, the third SDA used in this work. It has been found that the combination of the small TMA with those three bulkier SDAs, promotes the crystallization of zeolite structures that contain cages and channels. BMP leads to the crystallization of the 10-ring zeolite ferrierite, where TMA is located inside the ferrierite cage. If the size of the N-cyclic amine moiety increases, the resulting cation cannot be accommodated in the relatively narrow 10-ring channels of ferrierite, and in these cases the zeolite MCM-22 crystallizes. This zeolite contains large cages whose cross section is delimited by a 12-ring, where both BMH and BML can be easily accommodated. In this system, cage-like, chlatrasil type structures often co-crystallize with the open structures, evidencing that an appropriate balance between TMA and the bulky SDA is required to achieve the crystallization of open-frameworks. When BMP is used, mixtures of structurally related ferrierite and cage-like RUB-10 are obtained if an excess of TMA is present in the synthesis gel, while MCM-22 crystallizes together with the structurally related cage-like MTN phase.

The skeletal isomerization of n-butenes to isobutene has been carried out over ferrierite catalysts (Si/Al ~ 15) containing different acid sites distribution and different amount of defects. The zeolite crystals were synthesized under hydrothermal conditions in fluoride medium in the absence of alkaline cations by using suitable combinations of structure directing agents. Template-driven low density of acid sites in 10-membered-ring channels enhances the isobutene selectivity and decreases catalyst deactivation. The presence of high amount of silanol groups and Lewis acid sites increases the yields of by-products and catalysts decay., MICINN (CTQ2006-06282) CSIC (JAE-doc contract)

We report on the systematic exploration of zeolite synthesis using a combination of organic molecules of different size. The effect of changing the co-structure directing agent, co-SDA, (tetramethylammonium or quinuclidine) and its replacement by sodium cations, when used together with the bulky organic cation 1-benzyl-1-methylpyrrolidinium (bmp) is analyzed and compared with preparations where bmp is replaced by the related cation (S)-1-benzyl-2-hydroxymethyl-1-methylpyrrolidinium (bmprol). The tendency to direct the synthesis to ferrierite or ferrierite-like materials depending on the particular combination of bulky organic cation and co-SDA is discussed. The catalytic activity of some of the materials synthesized was tested in the isomerization of m-xylene.

Analysis of the structure of the zeolite ferrierite (framework type FER) synthesized using a combination of tetramethylammonium (TMA) and pyrrolidine as organic structure-directing agents (|((CH3)4N) 0.4((CH2)4NH)3.6H 1.7|[Si33.9Al2.1O72]) has revealed that TMA ions reside exclusively in the [58668 2] cavities of the FER framework, whereas pyrrolidine species are found in both the [586682] cavities and the main 10-ring channel. A similar, but not identical, arrangement of pyrrolidine molecules was found for a sample synthesized with pyrrolidine as the only SDA (|((CH2)4NH)4.2H2.2|[Si 33.8Al2.2O72])). A comparison of the two structures shows the influence of TMA on the location of pyrrolidine and the framework Al. Pyrrolidine species establish stronger interactions with the zeolitic framework than does TMA, suggesting a different ability of the amine to exert an influence on the aluminum distribution of the zeolite. These findings have implications in the catalytic performance of the samples. © 2013 American Chemical Society., A.B.P. acknowledges the support of the European Community under a Marie Curie Intra-European Fellowship for Career Development. L.G.H. acknowledges the Spanish Ministry of Economy for a Juan de la Cierva contract. The Spanish Ministry of Economy has funded this work (project MAT2012–31127) .

Zn atoms have been incorporated into the STA-1 microporous framework (SAO framework type) for the first time. Pure Zn-containing STA-1 aluminophosphate has been obtained in the presence of either (S)-(-)-N-benzylpyrrolidine-2-methanol (BPM) or benzylpyrrolidine (BP) as structure-directing agent. Characterisation results have demonstrated that the organic molecules remain intact within the microporous framework after the hydrothermal treatment. The X-ray diffraction pattern has been indexed in the tetragonal space group I ̅4m2 (a = 13.7828(1) Å and c = 21.9444(4) Å). Chemical analysis and (31)P MAS NMR spectroscopy confirm the incorporation of ca. 4.5 Zn atoms per unit cell by isomorphous substitution of Al. This large-pore aluminophosphate has one of the lowest framework densities among the known zeolite structures, and is therefore of potential interest for applications in adsorption or catalytic processes involving bulky molecules.

A computational study is performed to rationalize the effect of the organic template molecules used in the synthesis of zeolites on their catalytic behaviour. Apart from being structure-directing, these molecules influence the location of heteroatoms. Molecules bearing acidic protons susceptible to forming H-bonds with framework oxygens show the strongest dopant-siting direction.

Fluorescence spectroscopy and a range of computer simulation techniques are used to study the structure directing effect of benzylpyrrolidine (BP) and (S)-(-)-N-benzylpyrrolidine-2-methanol (BPM) in the synthesis of nanoporous aluminophosphate frameworks with AFI (one-dimensional channels) and SAO (three-dimensional interconnected channels) topologies. We study the supramolecular chemistry of BP and BPM molecules in aqueous solution and compare it with the aggregation state of the molecules found when they are inside the AlPO nanopores after crystallization. The aggregation of the molecules within the structures can be explained by a combination of thermodynamic and kinetic effects. The former are given by the stability of the molecular species interacting with the oxide networks relative to their stability in solution; the latter depend on the aggregation behavior of the molecules in the synthesis gels prior to crystallization. Whereas BPM only forms one type of aggregate in solution, which has the appropriate conformation to match the empty channels of the forming nanoporous frameworks, BP forms aggregates with different molecular orientations, of which only one matches the framework interstices. This different supramolecular chemistry, together with the higher interaction of BPM with the oxide networks, makes BPM a better structure directing agent (SDA); it is also responsible for the higher incorporation of BPM as dimers in the frameworks, especially in the AFI structure, observed experimentally. The concentration of the SDA molecules in the gels, and so the density per volume of the SDAs, determines the exclusion zone from which the pores and/or cavities of the framework will arise, and so the porous network of the formed material. A clear relationship between the SDA density in solution and in the framework is observed, thus enabling an eventual control of the material density by adjusting the SDA concentration in the gels. The topological instability intrinsic to these open framework structures is compensated by a high host-guest interaction energy; the SAO topology is further stabilized by doping with Zn. Our computational results account for and rationalize all the effects observed experimentally, providing a complete picture of the mode of structure direction of these aromatic molecules in the synthesis of nanoporous aluminophosphates.

A synthesis strategy to tailor the acid sites location in ferrierite crystals has been developed. The zeolite catalysts were synthesised in fluoride medium using different combinations of organic structure directing agents (SDAs) in the absence of inorganic cations. Therefore, the negative charge associated to the incorporation of aluminium to the framework was compensated exclusively by the positive charge of the organic SDAs. In this way, Al sitting in the zeolite framework was driven by the specific location of the different SDA molecules within the zeolite void volume. Following this synthesis strategy, it has been found that the distribution of strongly acidic hydroxyl groups in the proton form of the zeolites obtained after removal of the organic templates was dependent on the combination of organic molecules used as SDAs. Moreover, the catalytic activity of the zeolites in m-xylene and 1-butene isomerisation increased as the relative population of strong Brönsted acid groups in sterically constrained sites inside the ferrierite cavity decreased., This work has been financially supported by the MICINN (project CTQ2006-06282).

1-benzyl-1-methyl-pyrrolidium and a chiral related molecule have been used together with several cage-forming organic molecules like TMA, TEA and quinuclidine, as well as with sodium cations, as structure directing agents (SDA) to crystallize different zeolite materials. Ferrierite, ferrierite-related layered compounds, ZSM-12 and MCM-22 were obtained from highly concentrated synthesis gels in fluoride medium. It has been found that the nature of the zeolite phase obtained is influenced by the specific combination of bulky and cage-forming cations and the synthesis temperature. Computational studies have been used to rationalize the experimental results, in terms of the relative trend for each SDA to occupy specific sites within each zeolite structure. Examples are provided on the influence of the synthesis procedure on the acidity and catalytic activity of the different synthesized materials in acid-catalyzed reactions.