Anionic Ligand Assisted Synthesis of 3‑D Hollow TiO₂ Architecture with Enhanced Photoelectrochemical Performance

Hollow structured materials have shown great advantages for use in photoelectrochemical devices. However, their poor charge transport limits overall device performance. Here, we report a unique 3-D hollow architecture of TiO₂ that greatly improves charge transport properties. We found that citric acid (CA) plays crucial roles in the formation of the 3-D hollow architecture. First, CA controls the hydrolysis rate of Ti ions and facilitates surface hydrolysis on templates during hydrothermal synthesis. Second, CA suppresses the growth of the carbon template at the initial reaction stage, resulting in the formation of comparatively small hollow fibers. More importantly, a prolonged hydrothermal reaction with CA enables a hollow sphere to grow into entangled hollow fibers via biomimetic swallowing growth. To demonstrate advantages of the 3-D hollow architecture for photoelectrochemical devices, we evaluated its photoelectrochemical performance, specifically the electrolyte diffusion and electron dynamics, by employing dye-sensitized solar cells as a model device. A systemic analysis reveals that the 3-D hollow architecture greatly improves both the electrolyte diffusion and electron transport compared to those of the nanoparticle and hollow sphere due to the elongated porous hollow morphology as well as the densely interconnected nanoparticles at the wall layer

1‑D Structured Flexible Supercapacitor Electrodes with Prominent Electronic/Ionic Transport Capabilities

A highly efficient 1-D flexible supercapacitor with a stainless steel mesh (SSM) substrate is demonstrated. Indium tin oxide (ITO) nanowires are prepared on the surface of the stainless steel fiber (SSF), and MnO₂ shell layers are coated onto the ITO/SSM electrode by means of electrodeposition. The ITO NWs, which grow radially on the SSF, are single-crystalline and conductive enough for use as a current collector for MnO₂-based supercapacitors. A flake-shaped, nanoporous, and uniform MnO₂ shell layer with a thickness of ∼130 nm and an average crystallite size of ∼2 nm is obtained by electrodeposition at a constant voltage. The effect of the electrode geometry on the supercapacitor properties was investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and a galvanostatic charge/discharge study. The electrodes with ITO NWs exhibit higher specific capacitance levels and good rate capability owing to the superior electronic/ionic transport capabilities resulting from the open pore structure. Moreover, the use of a porous mesh substrate (SSM) increases the specific capacitance to 667 F g^–1 at 5 mV s^–1. In addition, the electrode with ITO NWs and the SSM shows very stable cycle performance (no decrease in the specific capacitance after 5000 cycles)

Improved Quantum Efficiency of Highly Efficient Perovskite BaSnO₃‑Based Dye-Sensitized Solar Cells

Ternary oxides are potential candidates as an electron-transporting material that can replace TiO₂ in dye-sensitized solar cells (DSSCs), as their electronic/optical properties can be easily controlled by manipulating the composition and/or by doping. Here, we report a new highly efficient DSSC using perovskite BaSnO₃ (BSO) nanoparticles. In addition, the effects of a TiCl₄ treatment on the physical, chemical, and photovoltaic properties of the BSO-based DSSCs are investigated. The TiCl₄ treatment was found to form an ultrathin TiO₂ layer on the BSO surface, the thickness of which increases with the treatment time. The formation of the TiO₂ shell layer improved the charge-collection efficiency by enhancing the charge transport and suppressing the charge recombination. It was also found that the TiCl₄ treatment significantly reduces the amount of surface OH species, resulting in reduced dye adsorption and reduced light-harvesting efficiency. The trade-off effect between the charge-collection and light-harvesting efficiencies resulted in the highest quantum efficiency (<i>i</i>.<i>e</i>., short-circuit photocurrent density), leading to the highest conversion efficiency of 5.5% after a TiCl₄ treatment of 3 min (<i>cf</i>. 4.5% for bare BSO). The conversion efficiency could be increased further to 6.2% by increasing the thickness of the BSO film, which is one of the highest efficiencies from non-TiO₂-based DSSCs

Indium–Tin–Oxide Nanowire Array Based CdSe/CdS/TiO₂ One-Dimensional Heterojunction Photoelectrode for Enhanced Solar Hydrogen Production

For photoelectrochemical (PEC) hydrogen production, low charge transport efficiency of a photoelectrode is one of the key factors that largely limit PEC performance enhancement. Here, we report a tin-doped indium oxide (In₂O₃:Sn, ITO) nanowire array (NWs) based CdSe/CdS/TiO₂ multishelled heterojunction photoelectrode. This multishelled one-dimensional (1D) heterojunction photoelectrode shows superior charge transport efficiency due to the negligible carrier recombination in ITO NWs, leading to a greatly improved photocurrent density (∼16.2 mA/cm² at 1.0 V vs RHE). The ITO NWs with an average thickness of ∼12 μm are first grown on commercial ITO/glass substrate by a vapor–liquid–solid method. Subsequently, the TiO₂ and CdSe/CdS shell layers are deposited by an atomic layer deposition (ALD) and a chemical bath deposition method, respectively. The resultant CdSe/CdS/TiO₂/ITO NWs photoelectrode, compared to a planar structure with the same configuration, shows improved light absorption and much faster charge transport properties. More importantly, even though the CdSe/CdS/TiO₂/ITO NWs photoelectrode has lower CdSe/CdS loading (i.e., due to its lower surface area) than the mesoporous TiO₂ nanoparticle based photoelectrode, it shows 2.4 times higher saturation photocurrent density, which is attributed to the superior charge transport and better light absorption by the 1D ITO NWs