RESUMEN
Amines supported on porous solid materials have a high CO2 adsorption capacity and low regeneration temperature. However, the high amine load on such substrates and the substrate itself may lead to substantial pressure drop across the reactor. Herein, we compare the CO2 adsorption capacity and pressure drop of fumed silica powder to 3D-printed monolithic fumed silica structures, both functionalized by polyethylenimine (PEI), and find a drastically reduced pressure drop for 3D-printed substrates (0.01 bar vs. 0.76 bar) in the sorption bed with equal CO2 adsorption capacity. Furthermore, the effect of 3D-printing nozzle diameter and PEI loading on the adsorption capacity are investigated and the highest capacities (2.0 mmol/g at 25 °C with 5000 ppm CO2) are achieved with 0.4 mm nozzle size and 34 wt% PEI loading. These high capacities are achieved since the 3D printing and subsequent sintering (700 °C) of monolithic samples does not compromise the surface area of the fumed silica. Finally, the comparison between 3D-printed monoliths and extruded granulate of varying diameter reveals that the ordered channel system of 3D-printed structures is superior to randomly oriented granulate in terms of CO2 adsorption capacity.
RESUMEN
TiO2 and WO3 are two of the most important, industrially relevant earth-abundant oxides. Although both materials show complementary functionality and are promising candidates for similar types of applications such as catalysis, sensor technology, and energy conversion, their chemical stability in reactive environments differs remarkably. In this study, anodic barrier oxides are grown on solid-solution W xTi1- x alloy precursors covering a wide compositional range (0 ≤ x ≤ 1) with the goal of creating functional oxides with tailored stability. A strong Ti-cation enrichment in the surface region of the grown W xTi1- xO n layer is observed, which can be controlled by both the anodizing conditions and precursor composition. For Ti concentrations above 50 at. %, a continuous nanometer-thick TiO2 protective coating is achieved on top of a homogeneous W xTi1- xO n film as evidenced by X-ray photoelectron spectroscopy and transmission electron microscopy analyses. A comprehensive electrochemical assessment demonstrates a very stable passivation of the surface in both acidic and alkaline environments. This increase in chemical stability correlates directly with the presence of this protective TiO2 film. The results of this work provide insights into the oxidation behavior of W1- xTi x alloys, but more importantly demonstrate how controlled oxidation of self-passivating alloys can lead to oxide alloys with thin, protective surface layers that otherwise would require more sophisticated deposition methods.
RESUMEN
In this work, we demonstrate that buried junction photocathodes featuring an ALD TiO2 protective overlayer can be readily characterized using a variation of the dual working electrode (DWE) technique, where the second working electrode (WE2) is spatially isolated from the hydrogen-evolving active area. The measurement of the surface potential during operation enables the operando deconvolution of the photovoltaic and electrocatalytic performance of these photocathodes, by reconstructing J-ΔV curves (reminiscent of photovoltaic J-V curves) from the 3-electrode water splitting data. Our method provides a clearer understanding of the photocathode degradation mechanism during stability tests, including loss of the catalyst from the surface, which is only possible in our isolated WE2 configuration. A pn+Si/TiO2 photocathode was first investigated as a well behaved model system, and then the technique was applied to an emerging material system based on Cu2O/Ga2O3, where we uncovered an intrinsic instability of the Cu2O/Ga2O3 junction (loss of photovoltage) during long term stability measurements.
RESUMEN
Protective overlayers for light absorbers in photoelectrochemical water-splitting devices have gained considerable attention in recent years. They stabilize light absorbers which would normally be prone to chemical side reactions leading to degradation of the absorber. Atomic layer deposition (ALD) enables conformal and reproducible ultrathin protective layer growth even on highly structured substrates. One of the most widely investigated protective layers is amorphous TiO2, deposited by ALD at a relatively low temperature (120-150 °C). We have deposited protective layers from tetrakis(dimethylamido)titanium(IV) at two different temperatures and investigated their chemical composition as well as optical and electrochemical properties. Our main findings reveal a change in the flat band potential with thickness, reaching a stable value of about -50 to -100 mV versus reversible hydrogen electrode for films >30 nm, with doping densities of â¼1020 cm3. Practical thicknesses to achieve pinhole-free films are evaluated and discussed.