Prediction of Cu Zeolite NH3-SCR Activity from Variable Temperature 1H NMR Spectroscopy.

Selective catalytic reduction (SCR) of NOx by ammonia is one of the dominant pollution abatement technologies for near-zero NOx emission diesel engines. A crucial step in the reduction of NOx to N2 with Cu zeolite NH3-SCR catalysts is the generation of a multi-electron donating active site, implying the permanent or transient dimerization of Cu ions. Cu atom mobility has been implicated by computational chemistry as a key factor in this process. This report demonstrates how variable temperature 1H NMR reveals the Cu induced generation of sharp 1H resonances associated with a low concentration of sites on the zeolite. The onset temperature of the appearance of these signals was found to strongly correlate with the NH3-SCR activity and was observed for a range of catalysts covering multiple frameworks (CHA, AEI, AFX, ERI, ERI-CHA, ERI-OFF, *BEA), with different Si/Al ratios and different Cu contents. The results point towards universal applicability of variable temperature NMR to predict the activity of a Cu-zeolite SCR catalyst. The unique relationship of a spectroscopic feature with catalytic behavior for zeolites with different structures and chemical compositions is exceptional in heterogeneous catalysis.

Selective catalytic reduction of NOx with ammonia (NH3-SCR) over copper loaded LEV type zeolites synthesized with different templates.

LEV type zeolites were synthesized with four different structure-directing agents and converted to copper loaded NH3-SCR catalysts. The synthesis recipe was found to impact the respective Al population in the two topologically different framework sites in double and single 6-rings, resolvable by 27Al MAS NMR spectroscopy. Hydrothermal stability was found to be related to the silanol concentration, Si/Al ratio, particle size, crystal morphology, crystal defects, external surface area, and microporosity. Catalytic activity in NH3-SCR was dependent on preferential Al siting in the double 6-rings. Levinite synthesized using adamantylamine showed the strongest preference for Al atoms sitting in double 6-ring sites, and showed the highest catalytic turnover frequency. Unfortunately, because of the large crystal size, copper loading of this sample was limited to 0.6 wt% while other samples could be loaded with copper up to 3.3 wt%. An optimum combination of hydrothermal stability and catalytic activity was obtained with N,N'-bis-dimethylpentanediyldiammonium dibromide as structure-directing agent.

In Situ Solid-State (13)C NMR Observation of Pore Mouth Catalysis in Etherification of ß-Citronellene with Ethanol on Zeolite Beta.

The reaction mechanism of etherification of ß-citronellene with ethanol in liquid phase over acid zeolite beta is revealed by in situ solid-state (13)C NMR spectroscopy. Comparison of (13)C Hahn-echo and (1)H-(13)C cross-polarization NMR characteristics is used to discriminate between molecules freely moving in liquid phase outside the zeolite and molecules adsorbed inside zeolite pores and in pore mouths. In the absence of ethanol, ß-citronellene molecules enter zeolite pores and react to isomers. In the presence of ethanol, the concentration of ß-citronellene inside zeolite pores is very low because of preferential adsorption of ethanol. The etherification reaction proceeds by adsorption of ß-citronellene molecule from the external liquid phase in a pore opening where it reacts with ethanol from inside the pore. By competitive adsorption, ethanol prevents the undesired side reaction of ß-citronellene isomerization inside zeolite pores. ß-citronellene etherification on zeolite beta is suppressed by bulky base molecules (2,4,6-collidine and 2,6-ditertiarybutylpyridine) that do not enter the zeolite pores confirming the involvement of easily accessible acid sites in pore openings. The use of in situ solid-state NMR to probe the transition from intracrystalline catalysis to pore mouth catalysis depending on reaction conditions is demonstrated for the first time. The study further highlights the potential of this NMR approach for investigations of adsorption of multicomponent mixtures in general.

Co3-xFexO4 inverse opals with tunable catalytic activity for high-performance overall water splitting.

The development of earth-abundant and high-performance bifunctional catalysts for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in alkaline electrolytes is required to efficiently produce hydrogen by electrochemical water splitting, but remains a challenge. We have fabricated mesoporous cobalt iron oxide inverse opals (m-CFO IO) with different mole ratios of cobalt and iron by a wet chemical method using polystyrene beads as a hard template, followed by calcination in air. The performance of the m-CFO IO as OER and HER electrocatalysts was investigated. The as-prepared catalyst with equal concentrations of Fe and Co exhibits remarkable OER and HER performances with low overpotentials of 261 and 157 mV to attain 10 mA cm-2 and small Tafel slopes of 63 and 56 mV dec-1, respectively. An alkaline water electrolyzer with a two-electrode configuration achieves 10 mA cm-2 at 1.55 V with excellent long-term stability, outperforming the combination of noble metal IrO2 and Pt/C benchmark catalysts. The superior catalytic performance is ascribed to the synergistic effects of particle size, crystallinity, oxygen efficiency, a large number of active sites, and the large specific surface area of the porous inverse opal structure.

Selective and reversible ammonia gas detection with nanoporous film functionalized silicon photonic micro-ring resonator.

Portable, low cost and real-time gas sensors have a considerable potential in various biomedical and industrial applications. For such applications, nano-photonic gas sensors based on standard silicon fabrication technology offer attractive opportunities. Deposition of high surface area nano-porous coatings on silicon photonic sensors is a means to achieve selective, highly sensitive and multiplexed gas detection on an optical chip. Here we demonstrate selective and reversible ammonia gas detection with functionalized silicon-on-insulator optical micro-ring resonators. The micro-ring resonators are coated with acidic nano-porous aluminosilicate films for specific ammonia sensing, which results in a reversible response to NH(3)with selectivity relative to CO(2). The ammonia detection limit is estimated at about 5 ppm. The detectors reach a steady response to NH(3) within 30 and return to their base level within 60 to 90 seconds. The work opens perspectives on development of nano-photonic sensors for real-time, non-invasive, low cost and light weight biomedical and industrial sensing applications.

In situ monitoring of atomic layer deposition in nanoporous thin films using ellipsometric porosimetry.

Ellipsometric porosimetry (EP) is a handy technique to characterize the porosity and pore size distribution of porous thin films with pore diameters in the range from below 1 nm up to 50 nm and for the characterization of porous low-k films especially. Atomic layer deposition (ALD) can be used to functionalize porous films and membranes, e.g., for the development of filtration and sensor devices and catalytic surfaces. In this work we report on the implementation of the EP technique onto an ALD reactor. This combination allowed us to employ EP for monitoring the modification of a porous thin film through ALD without removing the sample from the deposition setup. The potential of in situ EP for providing information about the effect of ALD coating on the accessible porosity, the pore radius distribution, the thickness, and mechanical properties of a porous film is demonstrated in the ALD of TiO(2) in a mesoporous silica film.

Tailoring nanoporous materials by atomic layer deposition.

Atomic layer deposition (ALD) is a cyclic process which relies on sequential self-terminating reactions between gas phase precursor molecules and a solid surface. The self-limiting nature of the chemical reactions ensures precise film thickness control and excellent step coverage, even on 3D structures with large aspect ratios. At present, ALD is mainly used in the microelectronics industry, e.g. for growing gate oxides. The excellent conformality that can be achieved with ALD also renders it a promising candidate for coating porous structures, e.g. for functionalization of large surface area substrates for catalysis, fuel cells, batteries, supercapacitors, filtration devices, sensors, membranes etc. This tutorial review focuses on the application of ALD for catalyst design. Examples are discussed where ALD of TiO(2) is used for tailoring the interior surface of nanoporous films with pore sizes of 4-6 nm, resulting in photocatalytic activity. In still narrower pores, the ability to deposit chemical elements can be exploited to generate catalytic sites. In zeolites, ALD of aluminium species enables the generation of acid catalytic activity.

HSIL-Based Synthesis of Ultracrystalline K,Na-JBW, a Zeolite Exhibiting Exceptional Framework Ordering and Flexibility.

A reproducible synthesis strategy for ultracrystalline K,Na-aluminosilicate JBW zeolite is reported. The synthesis uses a Na-based hydrated silicate ionic liquid (HSIL) as a silicon source and gibbsite as the aluminum source. 27Al and 23Na NMR spectra exhibit crystalline second-order quadrupole patterns in the hydrated as well as dehydrated states and distinct resonances for different T-sites demonstrating an exceptional degree of order of the elements of the JBW framework, observed for the first time in a zeolite. Detailed structural analysis via NMR crystallography, combining powder X-ray diffraction and solid-state NMR of all elements (27Al, 29Si, 23Na, 39K, and 1H), reveals remarkable de- and rehydration behavior of the JBW framework, transforming from its as-made hydrated structure via a modified anhydrous state into a different rehydrated symmetry while showing astonishing flexibility for a semicondensed aluminosilicate. Its crystallinity, exceptional degree of ordering of the T atoms and sodium cations, and the fully documented structure qualify this defect-free K,Na-aluminosilicate JBW zeolite as a suitable model system for developing NMR modeling methods.

Spherical core-shell alumina support particles for model platinum catalysts.

γ- and δ-alumina are popular catalyst support materials. Using a hydrothermal synthesis method starting from aluminum nitrate and urea in diluted solution, spherical core-shell particles with a uniform particle size of about 1 µm were synthesized. Upon calcination at 1000 °C, the particles adopted a core-shell structure with a γ-alumina core and δ-alumina shell as evidenced by 2D and 3D electron microscopy and 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The spherical alumina particles were loaded with Pt nanoparticles with an average size below 1 nm using the strong electrostatic adsorption method. Electron microscopy and energy dispersive X-ray spectroscopy revealed a homogeneous platinum dispersion over the alumina surface. These platinum loaded alumina spheres were used as a model catalyst for bifunctional catalysis. Physical mixtures of Pt/alumina spheres and spherical zeolite particles are equivalent to catalysts with platinum deposited on the zeolite itself facilitating the investigation of the catalyst components individually. The spherical alumina particles are very convenient supports for obtaining a homogeneous distribution of highly dispersed platinum nanoparticles. Obtaining such a small Pt particle size is challenging on other support materials such as zeolites. The here reported and well-characterized Pt/alumina spheres can be combined with any zeolite and used as a bifunctional model catalyst. This is an interesting strategy for the examination of the acid catalytic function without the interference of the supported platinum metal on the investigated acid material.

Bifunctional earth-abundant phosphate/phosphide catalysts prepared via atomic layer deposition for electrocatalytic water splitting.

The development of active and stable earth-abundant catalysts for hydrogen and oxygen evolution is one of the requirements for successful production of solar fuels. Atomic Layer Deposition (ALD) is a proven technique for conformal coating of structured (photo)electrode surfaces with such electrocatalyst materials. Here, we show that ALD can be used for the deposition of iron and cobalt phosphate electrocatalysts. A PE-ALD process was developed to obtain cobalt phosphate films without the need for a phosphidation step. The cobalt phosphate material acts as a bifunctional catalyst, able to also perform hydrogen evolution after either a thermal or electrochemical reduction step.

Low-temperature activation of carbon black by selective photocatalytic oxidation.

Carbon black is chemically modified by selective photocatalytic oxidation, removing amorphous carbon and functionalizing the graphitic fraction to produce porous, graphitized carbon black, commonly used as an adsorbent in chromatography. In contrast to pyrolytic treatments, this photocatalytic modification proceeds under mild reaction conditions using oxygen, nitric oxide, water vapor and a titanium dioxide photocatalyst at 150 °C. The photo-oxidation can be performed both with the photocatalyst in close proximity (contact mode) or physically separated from the carbon. Structural analysis of remotely photo-oxidized carbon black reveals increased hydrophilic properties as compared to pyrolysis at 700 °C in a N2 atmosphere. Carbon black photo-oxidation selectively mineralizes sp3-hybridized carbon, leading to enhanced graphitization. This results in an overall improved structural ordering by enriching carbon black with sp2-hybridized graphitic carbon showing decreased interplanar distance, accompanied by a twofold increase in the specific surface area. In addition, the photo-oxidized material is activated by the presence of oxygen functionalities on the graphitic carbon fraction, further enhancing the adsorptive properties.

EU-7 zeolite: a synthetic BIK type zeolite with high hydrothermal stability.

EU-7 zeolite with Si/Al ratio of 15 is identified as a BIK type zeolite. The framework charge is compensated with Cs+ cations located in 8-ring channels at regular distances. Even partially exchanged, Cu-loaded EU-7 is active in NH3-SCR and withstands hydrothermal aging at 900 °C needed for application in diesel particulate filters.

Resolving Interparticle Heterogeneities in Composition and Hydrogenation Performance between Individual Supported Silver on Silica Catalysts.

Supported metal nanoparticle catalysts are commonly obtained through deposition of metal precursors onto the support using incipient wetness impregnation. Typically, empirical relations between metal nanoparticle structure and catalytic performance are inferred from ensemble averaged data in combination with high-resolution electron microscopy. This approach clearly underestimates the importance of heterogeneities present in a supported metal catalyst batch. Here we show for the first time how incipient wetness impregnation leads to 10-fold variations in silver loading between individual submillimeter-sized silica support granules. This heterogeneity has a profound impact on the catalytic performance, with 100-fold variations in hydrogenation performance at the same level. In a straightforward fashion, optical microscopy interlinks single support particle level catalytic measurements to structural and compositional information. These detailed correlations reveal the optimal silver loading. A thorough consideration of catalyst heterogeneity and the impact thereof on the catalytic performance is indispensable in the development of catalysts.

Synthesis of uniformly dispersed anatase nanoparticles inside mesoporous silica thin films via controlled breakup and crystallization of amorphous TiO2 deposited using atomic layer deposition.

Amorphous titanium dioxide was introduced into the pores of mesoporous silica thin films with 75% porosity and 12 nm average pore diameter via Atomic Layer Deposition (ALD) using alternating pulses of tetrakis(dimethylamino)titanium and water. Calcination provoked fragmentation of the deposited amorphous TiO2 phase and its crystallization into anatase nanoparticles inside the nanoporous film. The narrow particle size distribution of 4 ± 2 nm and the uniform dispersion of the particles over the mesoporous silica support were uniquely revealed using electron tomography. These anatase nanoparticle bearing films showed photocatalytic activity in methylene blue degradation. This new synthesis procedure of the anatase nanophase in mesoporous silica films using ALD is a convenient fabrication method of photocatalytic coatings amenable to application on very small as well as very large surfaces.