ABSTRACT
Photocatalytic H2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta2O5/SrZrO3 heterostructure with Ru and Cu (RuO2/CuxO/Ta2O5/SrZrO3) using solid-state chemistry methods to achieve a high H2 production of 5164 µmol g-1 h-1 under simulated solar light, 39 times higher than that produced using SrZrO3. The heterostructure performance is compared with other Ta2O5/SrZrO3 heterostructure compositions loaded with RuO2, CuxO, or Pt. CuxO is used to showcase the usage of less costly cocatalysts to produce H2. The photocatalytic activity toward H2 by the RuO2/CuxO/Ta2O5/SrZrO3 heterostructure remains the highest, followed by RuO2/Ta2O5/SrZrO3 > CuxO/Ta2O5/SrZrO3 > Pt/Ta2O5/SrZrO3 > Ta2O5/SrZrO3 > SrZrO3. Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO2 or CuxO) and are even higher for the binary catalyst (RuO2/CuxO). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta2O5/SrZrO3, improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO3-based heterostructures for photocatalytic H2 production by solar water splitting.
ABSTRACT
Strontium titanate (STO) is a well-known oxide used in a wide variety of applications due to its excellent stability and optoelectronic properties. However, its integration in photoelectrocatalytic devices is limited by the lack of fast and scalable methods to produce robust films at a low temperature and atmospheric pressure. Herein, we report an atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) approach for the synthesis of STO crystalline films and their applications for photoelectrochemical solar energy conversion. The film crystallinity, which plays a determinant role in the photoelectrochemical performance, was linked to the selected strontium precursor and injection method. Through thermal stability studies of the precursors [Sr(dpm), Sr(ipo), Sr(acac), and Ti(ipo)] and analysis of the solution droplet size, it was demonstrated that the closer thermal decomposition behavior and superior miscibility of the Sr(dpm) and Ti(ipo) precursors led to more homogeneous and crystalline films with the highest photoelectrochemical performance (16.5 µA cm-2 at 1.23 V vs RHE under 100 mW cm-2), which can be further improved by a factor of 3.4 using thermal annealing at 500 °C. Evidence of the impact of a strontium precursor on the properties of STO films is provided through thermogravimetric analysis, X-ray diffraction, energy-dispersive system, UV-vis, X-ray photoelectron spectroscopy, HIM-SIMS, and photoelectrochemical analysis.
ABSTRACT
Porous composite coatings, made of a carbon nanotube (CNT)-TiO2 core-shell structure, were synthesized by the hybrid CVD-ALD process. The resulting TiO2 shell features an anatase crystalline structure that covers uniformly the surface of the CNTs. These composite coatings were investigated as photoanodes for the photo-electrochemical (PEC) water splitting reaction. The CNT-TiO2 core-shell configuration outperforms the bare TiO2 films obtained using the same process regardless of the deposited anatase thickness. The improvement factor, exceeding 400% in photocurrent featuring a core-shell structure, was attributed to the enhancement of the interface area with the electrolyte and the electrons fast withdrawal. The estimation of the photo-electrochemically effective surface area reveals that the strong absorption properties of CNT severely limit the light penetration depth in the CNT-TiO2 system.
