Pd/TiO2 coatings with template-controlled mesopore structure as highly active hydrogenation catalyst
(2015)
Micro-structured reactors offer excellent mass and heat transport capabilities and can therefore sustain very high reaction rates and space–time-yields also for highly exothermic catalytic reactions. However, such high rates cannot be reached when the reactors are coated or filled with conventional catalysts powders. We present a strategy for the direct synthesis of highly active wall-coated supported catalysts via co-deposition of a pore template (here micelles formed from PEO-b-PPO-b-PEO) and a precursors for the metal oxide (TiCl4) along with a compatible precursor for the active metal (PdCl2). The obtained catalytic coatings possess a template-controlled open pore structure and excellent mechanical stability. Moreover, the active metal is highly dispersed and well-distributed across the coating also at high Pd loadings. The corresponding high activity along with rapid mass transfer enabled by the open pore system results in the best space–time-yields in the gas-phase hydrogenation of butadiene reported so far in literature for a supported catalyst.
Micro structured reactors are attractive candidates for further process intensification in heterogeneous catalysis. However, they require catalytic coatings with significantly improved space-time yields compared to traditional supported catalysts. We report the facile synthesis of homogeneous nanocrystalline Pt coatings with hierarchical pore structure by electrochemical dealloying of amorphous sputter-deposited platinum silicide layers. Thickness, porosity and surface composition of the catalysts can be controlled by the dealloying procedure. XPS analysis indicates that the catalyst surface is primarily composed of metallic Pt. Catalytic tests in gas-phase hydrogenation of butadiene reveal the typical activity, selectivity and activation energy of nanocrystalline platinum. However, space time yields are about 13 to 200 times higher than values reported for Pt-based catalysts in literature. The highly open metallic pore structure prevents heat and mass transport limitations allowing for very fast reactions and reasonable stability at elevated temperatures.
Organosilanes are used routinely to functionalize various support materials for further modifications. Nevertheless, reliable quantitative information about surface functional group densities after layer formation is rarely available. Here, we present the analysis of thin organic nanolayers made from nitrogen containing silane molecules on naturally oxidized silicon wafers with reference-free total reflection X-ray fluorescence (TXRF) and X-ray photoelectron spectroscopy (XPS). An areic density of 2−4 silane molecules per nm2 was calculated from the layer’s nitrogen mass deposition per area unit obtained by reference-free TXRF. Complementary energy and angle-resolved XPS (ER/ARXPS) in the Si 2p core-level region was used to analyze the outermost surface region of the organic (silane layer)−inorganic (silicon wafer) interface. Different coexisting silicon species as silicon, native silicon oxide, and silane were identified and quantified. As a result of the presented proof-of-concept, absolute and traceable values for the areic density of silanes containing nitrogen as intrinsic marker are obtained by calibration of the XPS methods with reference-free TXRF. Furthermore, ER/AR-XPS is shown to facilitate the determination of areic densities in (mono)layers made from silanes having no heteroatomic marker other than silicon. After calibration with reference-free TXRF, these areic densities of silane molecules can be determined when using the XPS component intensity of the silane’s silicon atom.
The preparation of aminated monolayers with a controlled density of functional groups on silica surfaces through a simple vapor deposition process employing different ratios of two suitable monoalkoxysilanes, (3-aminopropyl)diisopropylethoxysilane (APDIPES) and (3-cyanopropyl)dimethylmethoxysilane (CPDMMS), and advances in the reliable quantification of such tailored surfaces are presented here. The one-step codeposition process was carried out with binary silane mixtures, rendering possible the control over a wide range of densities in a single step. In particular, APDIPES constitutes the functional silane and CPDMMS the inert component. The procedure requires only small amounts of silanes, several ratios can be produced in a single batch, the deposition can be carried out within a few hours and a dry atmosphere can easily be employed, limiting self-condensation of the silanes. Characterization of the ratio of silanes actually bound to the surface can then be performed in a facile manner through contact angle measurements using the Cassie equation. The reliable estimation of the number of surface functional groups was approached with a dual-mode BODIPY-type fluorescence label, which allows quantification by fluorescence and XPS on one and the same sample. We found that fluorescence and XPS signals correlate over at least 1 order of magnitude, allowing for a direct linking of quantitative fluorescence analysis to XPS quantification. Employment of synchrotron-based methods (XPS; reference-free total reflection X-ray fluorescence, TXRF) made the traceable quantification of surface functional groups possible, providing an absolute reference for quantitative fluorescence measurements through a traceable measurement chain.