Atomic layer deposition on porous powders with in situ gravimetric monitoring in a modular fixed bed reactor setup

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Review of Scientific Instruments 88, 074102 (2017) and may be found at https://doi.org/10.1063/1.4992023.A modular setup for Atomic Layer Deposition (ALD) on high-surface powder substrates in fixed bed reactors with a gravimetric in situ monitoring was developed. The design and operation are described in detail. An integrated magnetically suspended balance records mass changes during ALD. The highly versatile setup consists of three modular main units: a dosing unit, a reactor unit, and a downstream unit. The reactor unit includes the balance, a large fixed bed reactor, and a quartz crystal microbalance. The dosing unit is equipped with a complex manifold to deliver gases and gaseous reagents including three different ALD precursors, five oxidizing or reducing agents, and two purge gas lines. The system employs reactor temperatures and pressures in the range of 25-600 °C and 10−3 to 1 bar, respectively. Typically, powder batches between 100 mg and 50 g can be coated. The capabilities of the setup are demonstrated by coating mesoporous SiO2 powder with a thin AlOx (submono) layer using three cycles with trimethylaluminium and H2O. The self-limiting nature of the deposition has been verified with the in situ gravimetric monitoring and full saturation curves are presented. The process parameters were used for a scale-up in a large fixed bed reactor. The samples were analyzed with established analytics such as X-ray diffraction, N2 adsorption, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry.DFG, 53182490, EXC 314: Unifying Concepts in Catalysi

Enhancing of catalytic properties of vanadia via surface doping with phosphorus using atomic layer deposition

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Vac. Sci. Technol. A 34, 01A135 (2016) and may be found at https://doi.org/10.1116/1.4936390.Atomic layer deposition is mainly used to deposit thin films on flat substrates. Here, the authors deposit a submonolayer of phosphorus on V2O5 in the form of catalyst powder. The goal is to prepare a model catalyst related to the vanadyl pyrophosphate catalyst (VO)2P2O7 industrially used for the oxidation of n-butane to maleic anhydride. The oxidation state of vanadium in vanadyl pyrophosphate is 4+. In literature, it was shown that the surface of vanadyl pyrophosphate contains V5+ and is enriched in phosphorus under reaction conditions. On account of this, V2O5 with the oxidation state of 5+ for vanadium partially covered with phosphorus can be regarded as a suitable model catalyst. The catalytic performance of the model catalyst prepared via atomic layer deposition was measured and compared to the performance of catalysts prepared via incipient wetness impregnation and the original V2O5 substrate. It could be clearly shown that the dedicated deposition of phosphorus by atomic layer deposition enhances the catalytic performance of V2O5 by suppression of total oxidation reactions, thereby increasing the selectivity to maleic anhydride.DFG, 53182490, EXC 314: Unifying Concepts in Catalysi

Investigating the trimethylaluminium/water ALD process on mesoporous silica by in situ gravimetric monitoring

A low amount of AlOx was successfully deposited on an unordered, mesoporous SiO2 powder using 1–3 ALD (Atomic Layer Deposition) cycles of trimethylaluminium and water. The process was realized in a self-built ALD setup featuring a microbalanceand a fixed particle bed. The reactor temperature was varied between 75, 120, and 200 °C. The self-limiting nature of the deposition was verified by in situ gravimetric monitoring for all temperatures. The coated material was further analyzed by nitrogen sorption, inductively coupled plasma-optical emission spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, attenuated total reflection Fourier transformed infrared spectroscopy, and elemental analysis. The obtained mass gains correspond to average growth between 0.81–1.10 Å/cycle depending on substrate temperature. In addition, the different mass gains during the half-cycles in combination with the analyzed aluminum content after one, two, and three cycles indicate a change in the preferred surface reaction of the trimethylaluminium molecule from a predominately two-ligand exchange with hydroxyl groups to more single-ligand exchange with increasing cycle number. Nitrogen sorption isotherms demonstrate (1) homogeneously coated mesopores, (2) a decrease in surface area, and (3) a reduction of the pore size. The experiment is successfully repeated in a scale-up using a ten times higher substrate batch size.DFG, 325093850, Open Access Publizieren 2017 - 2018 / Technische Universität Berli