The relationships among the macroscopic compositional parameters of a Cu-exchanged SSZ-13 zeolite catalyst, the types and numbers of Cu active sites, and activity for the selective catalytic reduction (SCR) of NOx with NH3 are established through experimental interrogation and computational analysis of materials across the catalyst composition space. Density functional theory, stochastic models, and experimental characterizations demonstrate that within the synthesis protocols applied here and across Si:Al ratios, the volumetric density of six-membered-rings (6MR) containing two Al (2Al sites) is consistent with a random Al siting in the SSZ-13 lattice subject to Lowenstein’s rule. Further, exchanged CuII ions first populate these 2Al sites before populating remaining unpaired, or 1Al, sites as CuIIOH. These sites are distinguished and enumerated ex situ through vibrational and X-ray absorption spectroscopies (XAS) and chemical titrations. In situ and operando XAS follow Cu oxidation state and coordinatio...

Catalysis in a Cage: Condition-Dependent Speciation and Dynamics of Exchanged Cu Cations in SSZ-13 Zeolites

Subnanometric metal species (single atoms and clusters) have been demonstrated to be unique compared with their nanoparticulate counterparts. However, the poor stabilization of subnanometric metal species towards sintering at high temperature (>500 °C) under oxidative or reductive reaction conditions limits their catalytic application. Zeolites can serve as an ideal support to stabilize subnanometric metal catalysts, but it is challenging to localize subnanometric metal species on specific sites and modulate their reactivity. We have achieved a very high preference for localization of highly stable subnanometric Pt and PtSn clusters in the sinusoidal channels of purely siliceous MFI zeolite, as revealed by atomically resolved electron microscopy combining high-angle annular dark-field and integrated differential phase contrast imaging techniques. These catalysts show very high stability, selectivity and activity for the industrially important dehydrogenation of propane to form propylene. This stabilization strategy could be extended to other crystalline porous materials. Subnanometre Pt clusters show high catalytic activity, but can sinter and so reduce reactivity. Here, authors localize Pt clusters in one zeolite channel, preventing sintering and allowing highly stable and selective catalytic propane dehydrogenation.

/pdf/regioselective-generation-and-reactivity-control-of-22rb6x84dk.pdf

Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis

This study investigated the effects of desilication of ZSM-5 zeolite on its catalytic properties in catalytic fast pyrolysis (CFP) of lignocellulosic biomass. A series of mesoporous ZSM-5 zeolites were prepared by desilication of a conventional microporous ZSM-5 zeolite with NaOH solutions of varying concentrations (0.1–0.5 M). The creation of mesopores improved the diffusion property of the desilicated ZSM-5 zeolites and their catalytic activity for cracking bulky oxygenates (e.g., syringols derived from the lignin component of biomass). Consequently, the desilicated zeolites produced more aromatic hydrocarbons (carbon yields of 26.2–30.2%) and less coke (39.9–41.2%) in CFP of beech wood than the parent microporous ZSM-5 (23.2% aromatics and 44.4% coke). The highest aromatic yield (30.2%) and lowest coke yield (39.9%) were obtained in CFP of beech wood with mildly desilicated zeolite treated with 0.3 M NaOH solution. However, desilication with a greater concentration, 0.5 M NaOH, decreased the aromatic yield to 26.2% due to a considerable loss of microporosity in the severely desilicated zeolite. The results indicate that carefully controlled desilication of zeolite can improve the conversion of lignocellulose to valuable aromatic hydrocarbons and decrease the formation of undesired coke, thus improving the product distribution in CFP of lignocellulose.

Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions

As the conversion of methanol to olefins (MTO) over a zeolite catalyst is conducted on acid sites derived from framework aluminum (AlF), it is possible to enhance the catalytic performance by altering the siting of AlF if one knows the catalytic behavior of specified AlF located at certain sites. In this work, two series of H-ZSM-5 zeolites, viz., S-HZ-m and T-HZ-m, were synthesized with silica sol and tetraethyl orthosilicate, respectively, as the silicon source. Both series of H-ZSM-5 zeolites exhibit similar acidity, morphology, and textual properties. However, they are quite different with respect to AlF siting, as determined by UV–vis–DRS of Co(II) ions and 27Al MAS NMR; AlF of S-HZ-m is enriched in the sinusoidal and straight channels, whereas AlF of T-HZ-m is concentrated in the channel intersections. When they are used as the catalyst in MTO, T-HZ-m gives higher selectivity to ethene and aromatics and a larger hydrogen transfer index (HTI) than S-HZ-m, whereas S-HZ-m exhibits higher selectivity to...

Conversion of Methanol to Olefins over H-ZSM-5 Zeolite: Reaction Pathway Is Related to the Framework Aluminum Siting

The purpose of this paper is to derive optimal spline algorithms for the enlargement or reduction of digital images by arbitrary (noninteger) scaling factors. In our formulation, the original and rescaled signals are each represented by an interpolating polynomial spline of degree n with step size one and /spl Delta/, respectively. The change of scale is achieved by determining the spline with step size /spl Delta/ that provides the closest approximation of the original signal in the L/sub 2/-norm. We show that this approximation can be computed in three steps: (i) a digital prefilter that provides the B-spline coefficients of the input signal, (ii) a resampling using an expansion formula with a modified sampling kernel that depends explicitly on /spl Delta/, and (iii) a digital postfilter that maps the result back into the signal domain. We provide explicit formulas for n=0, 1, and 3 and propose solutions for the efficient implementation of these algorithms. We consider image processing examples and show that the present method compares favorably with standard interpolation techniques. Finally, we discuss some properties of this approach and its connection with the classical technique of bandlimiting a signal, which provides the asymptotic limit of our algorithm as the order of the spline tends to infinity. >

Enlargement or reduction of digital images with minimum loss of information

The effects of the organic structure-directing agents (OSDAs) and Na cations for the synthesis of ZSM-5 on the location of Al atom in the framework as well as the acidic and catalytic properties were investigated. To achieve these purposes, ZSM-5 zeolites were synthesized by using four kinds of OSDAs including tetrapropylammonium hydroxide cations, dipropylamine, cyclohexylamine, and hexamethylenimine with or without Na cations. In situ FT-IR spectroscopy using CO as probe molecule was applied to the evaluation of the acid property of the ZSM-5 zeolites. The location of Al atoms was examined by high resolution 27Al MAS and MQMAS NMR techniques. The constraint index (CI) has also been used to estimate the distribution of acid sites in the micropores. The location of acid sites was investigated based on the difference in the transition-state shape-selectivity through the cracking of n-hexane and 3-methylpentane. Furthermore, the cracking of various types of paraffins and the conversion of aromatic compounds...

Control of the Al Distribution in the Framework of ZSM-5 Zeolite and Its Evaluation by Solid-State NMR Technique and Catalytic Properties

The effects of external surface and acid properties of desilicated H-type ZSM-5 zeolites (H-ZSM-5) on their catalytic performance in hexane cracking were investigated. H-ZSM-5 with two different crystallite sizes of 100 nm and 1 μm were treated with NaOH solution of different concentrations. The external surface area (SEXT) was increased with an increase in the NaOH concentration, because of the formation of mesopores inside the H-ZSM-5 crystallites as a result of desilication. The increase in the SEXT of the H-ZSM-5 catalysts contributed to mitigating the catalyst deactivation during the hexane cracking. Although the amount of coke deposited on the alkali-treated H-ZSM-5 was larger than that on the parent H-ZSM-5, the micropore volume of the alkali-treated H-ZSM-5 decreased less due to coke deposition than that of the parent. The deactivation rate and the decrease in the micropore volume of the small-sized H-ZSM-5 catalysts were smaller than those of the large-sized catalysts, because they had shorter average diffusion path lengths. Thus the activity of the alkali-treated H-ZSM-5, especially small-sized one is less sensitive to coke deposition. Lewis acid sites (LASs) were generated by treating with NaOH of high concentrations. The selectivities to benzene, toluene and xylene (BTX) in the hexane cracking were increased with an increase in the LASs amount at high reaction temperatures (≥873 K). The LASs on the alkali-treated H-ZSM-5 were selectively removed by acid treatment. The resultant H-ZSM-5 exhibited a slightly lower hexane conversion and a lower selectivity to BTX but a small amount of coke compared to the parent and alkali-treated H-ZSM-5 catalysts, suggesting that LASs on alkali-treated H-ZSM-5 accelerated the dehydrogenation including hydride transfer and aromatization, forming BTX, which would be precursors of coke.

Effect of desilication of H-ZSM-5 by alkali treatment on catalytic performance in hexane cracking

Facile control of crystallite size of ZSM-5 catalyst for cracking of hexane

Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols

The use of pentaerythritol in combination with the Na cation in the synthesis of ZSM-5 led to a unique Al distribution in the MFI framework; Al atoms were preferentially located at straight and sinusoidal channels, not the intersection.

Hiroshi Mochizuki

Papers

Control of the Al Distribution in the Framework of ZSM-5 Zeolite and Its Evaluation by Solid-State NMR Technique and Catalytic Properties

Effect of desilication of H-ZSM-5 by alkali treatment on catalytic performance in hexane cracking

Facile control of crystallite size of ZSM-5 catalyst for cracking of hexane

Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols

Unique Al Distribution in the MFI Framework and Its Impact on Catalytic Properties