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

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

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

Synthesis of High Surface Area—Group 13—Metal Oxides via Atomic Layer Deposition on Mesoporous Silica

The atomic layer deposition of gallium and indium oxide was investigated on mesoporous silica powder and compared to the related aluminum oxide process. The respective oxide (GaOx, InOx) was deposited using sequential dosing of trimethylgallium or trimethylindium and water at 150 °C. In-situ thermogravimetry provided direct insight into the growth rates and deposition behavior. The highly amorphous and well-dispersed nature of the oxides was shown by XRD and STEM EDX-mappings. N2 sorption analysis revealed that both ALD processes resulted in high specific surface areas while maintaining the pore structure. The stoichiometry of GaOx and InOx was suggested by thermogravimetry and confirmed by XPS. FTIR and solid-state NMR were conducted to investigate the ligand deposition behavior and thermogravimetric data helped estimate the layer thicknesses. Finally, this study provides a deeper understanding of ALD on powder substrates and enables the precise synthesis of high surface area metal oxides for catalytic applications.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat

Atomic Layer Deposition of ZnO on Mesoporous Silica: Insights into Growth Behavior of ZnO via In-Situ Thermogravimetric Analysis

ZnO is a remarkable material with many applications in electronics and catalysis. Atomic layer deposition (ALD) of ZnO on flat substrates is an industrially applied and well-known process. Various studies describe the growth of ZnO layers on flat substrates. However, the growth characteristics and reaction mechanisms of atomic layer deposition of ZnO on mesoporous powders have not been well studied. This study investigates the ZnO ALD process based on diethylzinc (DEZn) and water with silica powder as substrate. In-situ thermogravimetric analysis gives direct access to the growth rates and reaction mechanisms of this process. Ex-situ analytics, e.g., N2 sorption analysis, XRD, XRF, HRTEM, and STEM-EDX mapping, confirm deposition of homogenous and thin films of ZnO on SiO2. In summary, this study offers new insights into the fundamentals of an ALD process on high surface area powders.TU Berlin, Open-Access-Mittel – 202

Towards Experimental Handbooks in Catalysis

The “Seven Pillars” of oxidation catalysis proposed by Robert K. Grasselli represent an early example of phenomenological descriptors in the field of heterogeneous catalysis. Major advances in the theoretical description of catalytic reactions have been achieved in recent years and new catalysts are predicted today by using computational methods. To tackle the immense complexity of high-performance systems in reactions where selectivity is a major issue, analysis of scientific data by artificial intelligence and data science provides new opportunities for achieving improved understanding. Modern data analytics require data of highest quality and sufficient diversity. Existing data, however, frequently do not comply with these constraints. Therefore, new concepts of data generation and management are needed. Herein we present a basic approach in defining best practice procedures of measuring consistent data sets in heterogeneous catalysis using “handbooks”. Selective oxidation of short-chain alkanes over mixed metal oxide catalysts was selected as an example.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat

Synthesis of High Surface Area—Group 13—Metal Oxides via Atomic Layer Deposition on Mesoporous Silica

The atomic layer deposition of gallium and indium oxide was investigated on mesoporous silica powder and compared to the related aluminum oxide process. The respective oxide (GaOx, InOx) was deposited using sequential dosing of trimethylgallium or trimethylindium and water at 150 °C. In-situ thermogravimetry provided direct insight into the growth rates and deposition behavior. The highly amorphous and well-dispersed nature of the oxides was shown by XRD and STEM EDX-mappings. N2 sorption analysis revealed that both ALD processes resulted in high specific surface areas while maintaining the pore structure. The stoichiometry of GaOx and InOx was suggested by thermogravimetry and confirmed by XPS. FTIR and solid-state NMR were conducted to investigate the ligand deposition behavior and thermogravimetric data helped estimate the layer thicknesses. Finally, this study provides a deeper understanding of ALD on powder substrates and enables the precise synthesis of high surface area metal oxides for catalytic applications

Formation, dynamics, and long-term stability of Mn- and Fe-promoted Rh/SiO2 catalysts in CO hydrogenation

The conversion of syngas (CO/H2) to ethanol (StE) is one promising example to generate a high-value fuel and key intermediate for various base chemicals, preferably from non-fossil carbon resources. Rh-Based catalysts demonstrated the highest selectivities towards C2+ oxygenates and ethanol, in particular. However, the accomplished yields still must be increased, and the catalyst's stability must be improved for industrial application. One primary strategy to improve C2+ oxygenate yields over Rh is the addition of one or several promoters. Specifically, Mn and Fe are among the most frequently used metals to improve rhodium's catalytic performance in binary and ternary systems. To date, experimental studies primarily focused on increasing the C2+ oxygenate yields, but long-term catalytic investigations are only rarely reported. Consequently, Mn and Fe's specific role as promoter and their influence on the long-term and thermal stability of supported Rh catalysts are not clarified as yet. A holistic view of atomistic promoter effects and their impact on the stability and dynamics of Rh-based catalysts under reaction conditions is thereby highly desired. Herein, we report a comprehensive study about the stability and dynamics of Mn- and Fe-promoted Rh/SiO2 catalysts at industrially relevant high-pressure conditions (54 bar). For this purpose, unpromoted Rh/SiO2, single-promoted RhMn/SiO2 and RhFe/SiO2, and complex multi-promoted RhMnFe/SiO2 catalysts were systematically investigated in four different states: calcined, reduced, after a long-term catalytic study (>22 days on stream), and after a high temperature stability investigation (T = 243–320 °C). The thorough analysis of each catalyst in the different states with integral and local characterization methods led to specific structural models before and after long-term catalytic investigations. These structural models provide a detailed view on compositions, electronic properties, and morphologies of promoted Rh/SiO2 catalysts and serve as a basis for improved catalyst design strategies and more sophisticated computational modeling efforts.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"TU Berlin, Open-Access-Mittel – 202

Design of an active and stable catalyst for dry reforming of methane via molecular layer deposition

The dry reforming of methane (DRM) has been proposed as an efficient way to convert two greenhouse gases, namely CO2 and CH4 to syngas. However, most catalysts reported in the literature suffer from strong deactivation during the reforming reaction. The deactivation is caused by strong sintering of catalytically active nanoparticles and the formation of filamentous carbon. Herein a new synthesis procedure based on molecular layer deposition (MLD) is established to stabilize DRM catalysts under reaction conditions. Deactivation of a Ni/SiO2 reference catalyst was prevented by forming a defined porous net-like over-layer, which prevents the sintering and detachment of Ni nanoparticles by filamentous carbon. The MLD approach was further compared to the formation of an overlayer by atomic layer deposition (ALD), demonstrating the advantages of MLD forming hybrid organic-inorganic alucone layers over classical alumina ALD.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat

Toolbox for atomic layer deposition process development on high surface area powders

Atomic layer deposition (ALD) is an industrially applied technique for thin film deposition. The vast majority of processes target flat substrates rather than powders. For ALD on powders, new processes are needed, as different reaction conditions are required. Here, two setups are described in detail, which enhance the ALD process development for powders. The first setup described is capable of directly measuring the vapor pressure of a given precursor by a capacitance diaphragm gauge. Promising precursors can be pre-selected, and suitable precursor saturation temperatures can be determined. The second setup consists of four parallel reactors with individual temperature zones to screen the optimal ALD temperature window in a time efficient way. Identifying the precursor saturation temperature beforehand and subsequently performing the first ALD half cycle in the parallel setup at four different reactor temperatures simultaneously will drastically reduce process development times. Validation of both setups is shown for the well-known ALD precursors, trimethylaluminum to deposit aluminum oxide and diethyl zinc to deposit zinc oxide, both on amorphous silica powder.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat