Crystalline Membranes

In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer

Synthesis of Porous Inorganic Membranes

Here we will attempt a brief overview of recent synthetic efforts for micropore and lower-end mesopore membranes. We will not address the very important classes of nonporous membranes, such as dense metals and solid electrolytes with applications in H_2 and O_2 separations, or meso- and macroporous membranes, which find applications in food processing and water treatment. Microporous materials provide high permselectivities for molecules encountered in the chemical-processing industry but suffer from low intrinsic permeabilities. Therefore, in order to bring microporous membrane materials to commercial applications, functional composites with small effective thicknesses (in the micron or submicron range) must be developed. For example, to achieve economical membrane-reactor sizes, fluxes as high as 0.1 mol/(m^2 s) are desirable. Approaches to microporous membranes include modification of mesoporous membranes by sol-gel and chemical-vapor-deposition (CVD) techniques, carbonization of polymers to form molecular-sieve carbon, and polycrystalline-film growth of zeolites and other molecular sieves

Zeolite membranes - a review and comparison with MOFs

The latest developments in zeolite membranes are reviewed, with an emphasis on the synthesis techniques, including seed assembly and secondary growth methods. This review also discusses the current industrial applications of zeolite membranes, the feasibility of their use in membrane reactors and their hydrothermal stability. Finally, zeolite membranes are compared with metal–organic framework (MOF) membranes and the latest advancements in MOF and mixed matrix membranes are highlighted

Interplay between hydrophilicity and surface barriers on water transport in zeolite membranes

A comprehensive understanding of molecular transport within nanoporous materials remains elusive in a broad variety of engineering and biomedical applications. Here, experiments and atomistic simulations are synergically used to elucidate the non-trivial interplay between nanopore hydrophilicity and surface barriers on the overall water transport through zeolite crystals. At these nanometre-length scales, these results highlight the dominating effect of surface imperfections with reduced permeability on the overall water transport. A simple diffusion resistance model is shown to be sufficient to capture the effects of both intracrystalline and surface diffusion resistances, thus properly linking simulation to experimental evidence. This work suggests that future experimental work should focus on eliminating/overcoming these surface imperfections, which promise an order of magnitude improvement in permeability.MITOR ProjectNANO-BRIDGE (PRIN 2012, grant number 2012LHPSJC)NANOSTEP (Fondazione CRT, Torino) projectsScuola Interpolitecnica di Dottorato—SCUDOISCRA initiative (CINECA award)Center for Clean Water and Clean Energy at MIT and KFUP

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis.

Commonly used methods to assess crystallinity, micro-/mesoporosity, Brønsted acid site density and distribution (in micro- vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two-dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro- and mesoporosity, and micropore reaction rates

Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization

Single-unit-cell Sn-MFI, with the detectable Sn uniformly distributed and exclusively located at framework sites, is reported for the first time. The direct, single-step, synthesis is based on repetitive branching caused by rotational intergrowths of single-unit-cell lamellae. The self-pillared, meso- and microporous zeolite is an active and selective catalyst for sugar isomerization. High yields for the conversion of glucose into fructose and lactose to lactulose are demonstrated

Pillared Sn-MWW Prepared by a Solid-State-Exchange Method and its Use as a Lewis Acid Catalyst

Pillared Sn-MWW (Sn-MWW(SP)-SSE) was prepared through a solid-state-exchange (SSE) route. The pillared structure was inherited from pillared B-MWW, and Sn was inserted in the framework by boron leaching and solid-state-exchange with tin tetrachloride pentahydrate. The Sn-MWW(SP)-SSE with framework Sn sites exhibits Lewis acidity and good catalytic performance for the Baeyer–Villiger oxidation, and mono- and disaccharide isomerizations

Challenges of and Insights into Acid-Catalyzed Transformations of Sugars

The selective transformation of hexose and pentose sugars to intermediate platform chemicals, such as furans, is an essential step in the conversion of cellulosic and hemicellulosic biomass to biofuels and biochemicals. Yet, many challenges in achieving commercially viable processes remain. In this feature article, we outline challenges that need to be overcome to enable these transformations. Then, we present the newly introduced acid-catalyzed isomerization of aldose sugars to ketose sugars via a class of solid Lewis acid catalysts (e.g., Sn-Beta, Ti-Beta). We elucidate mechanistic insights arising from subnanometer cooperativity and solvent effects that can be controlled to tune reaction pathways and selectivity and draw parallels between heterogeneous and homogeneous Lewis acid catalysts. Subsequently, we discuss fructose dehydration to 5-hydroxyl-methylfurfural (HMF) via homogeneous and heterogeneous Brønsted acid-catalyzed chemistry. We show how fundamental insights arising from the combination of kinetics, spectroscopy, and multiscale simulations rationalize the improved yield of HMF in water–organic cosolvents. The stability of heterogeneous Lewis acid catalysts under low pH enables tandem Brønsted and Lewis acid-catalyzed reactions in a single pot that overcomes equilibrium limitations and gives a high HMF yield starting from sugar raw materials. Additionally, we provide an overview of multicomponent adsorption of biomass derivatives from solution in microporous materials and discuss how structure–property relations can lead to superior micro- and micromesoporous carbon adsorbents for reactive adsorption toward high HMF yield. Finally, we provide an outlook for the field

A New Concept for the Fabrication of Hydrogen Selective Silica Membranes

It was proposed to investigate a new concept for the synthesis of molecular sieve hydrogen selective membranes. This concept is based on the use of exfoliated layered zeolite precursors in coating processes to make nanocomposite films with inorganic or polymeric matrices. We discovered that creating exfoliated zeolite layers was much more difficult than anticipated because the methods originally proposed (based on existing literature reports) were not successful in providing exfoliated layers while preserving their porous structure. Although the original goals of fabricating high-selectivity-high-flux membranes that are stable under conditions present in a water-gas-shift reactor and that are able to selectively permeate hydrogen over all other components of the mixtures present in these reactors were not accomplished fully, significant progress has been made as follows: (1) Proof-of-concept hydrogen-selective nanocomposite membranes have been fabricated; (2) Methods to exfoliate layered zeolite precursors preserving the layer structure were identified; and (3) Unexpectedly, membranes exhibiting high ideal selectivity for carbon dioxide over nitrogen at room temperature were produced. The findings listed above provide confidence that the proposed novel concept can eventually be realized

Hierarchical materials: Background and perspectives

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