Minkee Choi

Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts.

Zeolites—microporous crystalline aluminosilicates—are widely used in petrochemistry and fine-chemical synthesis because strong acid sites within their uniform micropores enable size- and shape-selective catalysis. But the very presence of the micropores, with aperture diameters below 1 nm, often goes hand-in-hand with diffusion limitations that adversely affect catalytic activity. The problem can be overcome by reducing the thickness of the zeolite crystals, which reduces diffusion path lengths and thus improves molecular diffusion. This has been realized by synthesizing zeolite nanocrystals, by exfoliating layered zeolites, and by introducing mesopores in the microporous material through templating strategies or demetallation processes. But except for the exfoliation, none of these strategies has produced ‘ultrathin’ zeolites with thicknesses below 5 nm. Here we show that appropriately designed bifunctional surfactants can direct the formation of zeolite structures on the mesoporous and microporous length scales simultaneously and thus yield MFI (ZSM-5, one of the most important catalysts in the petrochemical industry) zeolite nanosheets that are only 2 nm thick, which corresponds to the b-axis dimension of a single MFI unit cell. The large number of acid sites on the external surface of these zeolites renders them highly active for the catalytic conversion of large organic molecules, and the reduced crystal thickness facilitates diffusion and thereby dramatically suppresses catalyst deactivation through coke deposition during methanol-to-gasoline conversion. We expect that our synthesis approach could be applied to other zeolites to improve their performance in a range of important catalytic applications.

Microporosity and connections between pores in SBA-15 mesostructured silicas as a function of the temperature of synthesis

Imaging of the platinum replica of the porous structure and low-pressure argon adsorption allowed us to elucidate the complicated porous structure of SBA-15. These techniques enabled us to draw a coherent picture of the evolution of the SBA-15 precursor mesophase as a function of the synthesis temperature. TEM of the platinum replicas has been unable to show bridges between the structural mesopores of SBA-15 synthesized at low temperature, whereas mesoporous bridges are clearly observed for samples formed at higher temperature. Argon adsorption has evidenced the ultramicroporosity of the materials formed at low temperature, as well as its evolution to secondary porosity with diameters greater than 1.5 nm under more severe hydrothermal treatment.

Pillared MFI zeolite nanosheets of a single-unit-cell thickness.

Zeolite MFI nanosheets of 2-nm thickness have been hydrothermally synthesized via cooperative assembly between silica and an organic surfactant, which is functionalized with a diquaternary ammonium group. The zeolite nanosheets have been further assembled into their ordered multilamellar mesostructure through hydrophobic interactions between the surfactant tails located outside the zeolite nanosheet. This assembly process involves successive transformations from an initially hexagonal mesophase to a multilamellar mesophase without crystallinity and then to a lamellar mesophase with a crystalline zeolite framework. The mesopore volume in the interlamellar space could be retained by supporting the zeolite nanosheets with silica pillars, as in pillared clays, even after surfactant removal by calcination. The mesopore diameters could be controlled according to the surfactant tail lengths. Due to the interlamellar structural coherence, the hierarchically mesoporous/microporous zeolite could exhibit small-angle X-ray diffraction peaks up to the fourth-order reflections corresponding to the interlayer distance. In addition, an Ar adsorption analysis and transmission electron microscopic investigation indicated that the pillars were highly likely to be built with an MFI structure. The present approach using a zeolite structure-directing functional group contained in a surfactant would be suitable for the synthesis of other related nanomorphous zeolites in the future.

Facile synthesis of high quality mesoporous SBA-15 with enhanced control of the porous network connectivity and wall thickness

Convenient and commercially viable synthesis conditions are described, providing efficient and reproducible control of pore connectivity and pore wall thickness for the synthesis of high quality SBA-15 mesoporous silica.

High Catalytic Activity of Palladium(II)‐Exchanged Mesoporous Sodalite and NaA Zeolite for Bulky Aryl Coupling Reactions: Reusability under Aerobic Conditions

Exchange for the better: Mesoporous sodalite and NaA zeolite exchanged with Pd(2+) exhibit remarkably high activity and reusability in C-C coupling reactions under aerobic atmosphere. It is proposed that the catalytic reactions are mediated by a molecular Pd(0) species generated in situ within the pores (see picture), which is oxidized back to Pd(2+) by O(2), preventing the formation of catalytically inactive Pd(0) agglomerates.

Mercaptosilane-Assisted Synthesis of Metal Clusters within Zeolites and Catalytic Consequences of Encapsulation

We report here a general synthetic strategy to encapsulate metal clusters within zeolites during their hydrothermal crystallization. Precursors to metal clusters are stabilized against their premature colloidal precipitation as hydroxides during zeolite crystallization using bifunctional (3-mercaptopropyl)trimethoxysilane ligands. Mercapto (-SH) groups in these ligands interact with cationic metal centers, while alkoxysilane moieties form covalent Si-O-Si or Si-O-Al linkages that promote zeolite nucleation around ligated metal precursors. These protocols led to the successful encapsulation of Pt, Pd, Ir, Rh, and Ag clusters within the NaA zeolite, for which small channel apertures (0.41 nm) preclude postsynthesis deposition of metal clusters. Sequential treatments in O(2) and H(2) formed small (approximately 1 nm) clusters with uniform diameter. Titration of exposed atoms with H(2) or O(2) gave metal dispersions that agree well with mean cluster sizes measured from electron microscopy and X-ray absorption spectroscopy, consistent with accessible cluster surfaces free of mercaptosilane residues. NaA micropore apertures restrict access to encapsulated clusters by reactants based on their molecular size. The ratio of the rates of hydrogenation of ethene and isobutene is much higher on clusters encapsulated within NaA than those dispersed on SiO(2), as also found for the relative rates of methanol and isobutanol oxidation. These data confirm the high encapsulation selectivity achieved by these synthetic protocols and the ability of NaA micropores to sieve reactants based on molecular size. Containment within small micropores also protects clusters against thermal sintering and prevents poisoning of active sites by organosulfur species, thus allowing alkene hydrogenation to persist even in the presence of thiophene. The bifunctional nature and remarkable specificity of the mercapto and alkoxysilane functions for metal and zeolite precursors, respectively, render these protocols extendable to diverse metal-zeolite systems useful as shape-selective catalysts in demanding chemical environments.

Mesoporous carbons with KOH activated framework and their hydrogen adsorption

The effects of KOH activation on pore structure of ordered mesoporous carbons were analyzed by transmission electron microscopy, powder X-ray diffraction and argon adsorption. The activation led to remarkable increases in micropore volume and BET surface area up to 1.0 mL g−1 and 2700 m2 g−1, at the expense of the mesostructural order. The resultant carbons with various microporosity and mesoporosity were tested for room-temperature adsorption of hydrogen under high pressure. The adsorption data were analyzed in correlation with the varied carbon pore structures. The results showed that the hydrogen adsorption capacity increased approximately linearly with respect to micropore volume, or BET surface area, reaching a 2.5-times higher value when fully activated. However, the adsorption capacity at 100 atm (0.75 wt%) was still far below the US DOE target of 6.5 wt%. The extrapolation of our results to the carbon structure with the highest possible surface area could lead to no more than 2.5 wt%. This result suggests that chemisorption or other chemical storage methods should be combined with physisorption if carbon materials are considered for hydrogen storage.

Palladium acetate immobilized in a hierarchical MFI zeolite-supported ionic liquid: a highly active and recyclable catalyst for Suzuki reaction in water

Palladium acetate was immobilized in thin ionic liquid layers on the mesopore wall of hierarchical MFI zeolite, and tested as a catalyst for Suzuki coupling reaction in water. The catalyst exhibited very high activity in the coupling of various aryl bromides with arylboronic acids. Moreover, the catalyst could be recycled without a significant loss of catalytic activity.

Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts.

Efficient microalgae harvesting by organo-building blocks of nanoclays

The synthesis of aminoclays with Mg2+ or Fe3+, placed in metal centers by sol–gel reaction with 3-aminopropyltriethoxysilane (APTES) as a precursor, is demonstrated, producing –(CH2)3NH2 organo-functional pendants which are covalent-bonding onto cationic metals. The protonated amine groups in aqueous solution lead the efficient sedimentation (harvesting) of microalgae biomass within approximately 5 min and 120 min for fresh and marine species, respectively. To our surprise, the aminoclays did not depend on microalgae species or media for microalgae harvesting. In particular, the harvesting efficiency (%) of microalgae was not decreased in a wide pH region. The harvesting mechanism can be explained by the sweep flocculation of microalgae, which is confirmed by measurement of zeta potential of aminoclay in aqueous solution where aminoclay shows a positively charged surface in a wide pH region. In order to reduce the cost of aminoclays and to make the harvesting procedures simple, the membrane process using aminoclay-coated cotton filter is introduced for the treatment of 1 L-scale microalgae stocks. It is successfully performed with three recycles using the same aminoclay-coated cotton filter after removing the harvested microalgae biomass. Conclusively, the aminoclay-based microalgae harvesting systems are a promising means of reducing the cost of downstream processes in microalgae-based biorefinery.