Nanosized Anatase TiO2 Single Crystals with Tunable Exposed (001) Facets for Enhanced Energy Conversion Efficiency of Dye‐Sensitized Solar Cells

This paper reports the synthesis of nanosized TiO₂ single crystals with different percentages of exposed (001) facets in the presence of HF solution. Various characterizations are conducted to understand the correlation between particle morphology, exposed (001) facets and photo‐conversion efficiency of the nanosized anatase TiO₂ single crystals. An enhancement in dye‐sensitized solar cells (DSSCs) overall conversion efficiency is observed for the photoanode consisting of nanosized TiO₂ single crystals with higher percentage of exposed (001) facets, increasing from 7.47%, 8.14% to 8.49% for the TiO₂ single crystals with ca. 10%, 38%, and 80% percentage of exposed (001) facets. Experimentally confirmed by dark current potential and open‐circuit voltage decay scans, such highly exposed (001) facets are not only favorable for more dye adsorption but also effectively retard the charge recombination process in DSSCs.     

Nitrogen doped anatase TiO2 sheets with dominant {001} facets for enhancing visible-light photocatalytic activity

The photocatalytic activity of TiO₂ can be mainly improved from three approaches: (1) enhancing surface energy; (2) increasing availability of visible light and (3) improving the separation efficiency of photo-induced electrons and holes. Here, we report a one-step route to obtain nitrogen (N) doped TiO₂ sheets with dominant {001} facets by a hydrothermal process. The XRD patterns confirm the better crystallinity. XPS spectrums show nitrogen acting as interstitial N or an O–Ti–N structure in TiO₂ sheets. Compared with that of TiO₂ sheets, the N doped TiO₂ sheets not only absorb visible light, but also have a large percentage of high reactive {001} facets, so the photocatalytic activities are greatly enhanced, as confirmed by the decomposition of methylene orange.     

Shape‐ and Size‐Controlled Synthesis of Uniform Anatase TiO2 Nanocuboids Enclosed by Active {100} and {001} Facets

Uniform anatase TiO₂ nanocuboids enclosed by active {100} and {001} facets over a wide size range (60–830 nm in length) with controllable aspect ratios were solvothermally synthesized through hydrolysis of titanium tetraisopropoxide (TTIP) using acetic acid (HAc) as the solvent and the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF₄]) as the capping agent. The size and aspect ratio of the anatase TiO₂ nanocuboids can be readily adjusted by changing the composition parameters including the contents of [bmim][BF₄], water, and HAc in the quaternary solution system. It was revealed that [bmim][BF₄] played an important role in stabilizing both the {100} and {001} facets of the anatase TiO₂ nanocuboids. On the one hand, [bmim][BF₄] acted as a fluoride source to release F^? ions for stabilizing the {001} facets; on the other hand, the [bmim]⁺ ions acted as effective capping ions to preferentially stabilize the {100} facets. The obtained near‐monodisperse anatase TiO₂ nanocuboids exhibited an interesting self‐assembly behavior during deposition. These single‐crystalline anatase nanocuboids showed extremely high crystalline phase stability, retaining the pure phase of anatase as well as the morphology even after being calcined at 900 °C. Moreover, the anatase nanocuboids exhibited considerably enhanced photocatalytic activity owing the wholly exposed active {100} and {001} facets.     

TiO2 Microspheres with Controllable Surface Area and Porosity for Enhanced Light Harvesting and Electrolyte Diffusion in Dye‐Sensitized Solar Cells

An optimized configuration of TiO₂ microspheres in photoanodes is of great importance to prepare highly efficient dye‐sensitized solar cells (DSSCs). In this work, TiO₂ microspheres with tunable diameter, pore size, and porosity are synthesized by subtly adjusting the synthesizing conditions, including ratios of deionized water, ammonia, and ethanol, respectively. TiO₂ microspheres are obtained with large pore sizes and a high porosity without sacrificing specific surface areas. In addition, the effect of their porosity and pore size on the performance of DSSCs is investigated. As confirmed by the dye‐loading ability and electrolyte diffusion resistance, the large mesopores and the high porosity of the TiO₂ microspheres can improve dye adsorption and facilitate electrolyte diffusion, giving rise to a high light‐harvesting and electron collection efficiency. Consequently, the highest photocurrent of 19.21 mA cm^?2 and a power conversion efficiency of 9.98% are obtained by using the TiO₂ microspheres with the highest porosity, compared with a 9.29% efficiency demonstrated by the lowest porosity (an improvement of 7.4%). By modifying the interconnection and the external pores of the microspheres photoanode, a high efficiency of 11.67% is achieved for a DSSC based on the most potent TiO₂ microspheres.     

Evaluating the Critical Thickness of TiO2 Layer on Insulating Mesoporous Templates for Efficient Current Collection in Dye‐Sensitized Solar Cells

In this paper, a way of utilizing thin and conformal overlayer of titanium dioxide on an insulating mesoporous template as a photoanode for dye‐sensitized solar cells is presented. Different thicknesses of TiO₂ ranging from 1 to 15 nm are deposited on the surface of the template by atomic layer deposition. This systematic study helps unraveling the minimum critical thickness of the TiO₂ overlayer required to transport the photogenerated electrons efficiently. A merely 6‐nm‐thick TiO₂ film on a 3‐μm mesoporous insulating substrate is shown to transport 8 mA/cm² of photocurrent density along with ≈900 mV of open‐circuit potential when using our standard donor‐π‐acceptor sensitizer and Co(bipyridine) redox mediator.     

Effectively Utilizing NIR Light Using Direct Electron Injection from Up‐Conversion Nanoparticles to the TiO2 Photoanode in Dye‐Sensitized Solar Cells

TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures are prepared in situ on the TiO₂ photoanode of dye‐sensitized solar cells (DSCs). Transmission electron microscopy (TEM) and high‐resolution (HR)‐TEM confirm the formation of TiO₂/NaYF₄:Yb³⁺,Er³⁺ nano‐heterostructures. The up‐converted fluorescence spectrum of the photoanode containing the nano‐heterostructure confirms electron injection from NaYF₄:Yb³⁺,Er³⁺ to the condution band (CB) of TiO₂. When using a photoanode containing the nano‐heterostructure in a DSC, the overall efficiency (η) of the device is 17% higher than that of a device without the up‐conversion nanoparticles (UCNPs) and 13% higher than that of a device containing mixed TiO₂ and UCNPs. Nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ and TiO₂/NaYF₄:Yb³⁺,Ho³⁺ can also be prepared in situ on TiO₂ photoanodes. The overall efficiency of the device containing TiO₂/NaYF₄:Yb³⁺,Ho³⁺ nano‐heterostructures is 15% higher than the control device without UCNPs. When nano‐heterostructures of TiO₂/NaYF₄:Yb³⁺,Tm³⁺ are used, the open‐circuit voltage (V_oc) and the short‐circuit current density (J_sc) are all slightly decreased. The effect of the different UCNPs results from the different energy levels of Er³⁺, Tm³⁺, and Ho³⁺. These results demonstrate that utilizing the UCNPs with the apporpriate energy levels can lead to effective electron injection from the UCNPs to the CB of TiO₂, effectively improving the photocurrent and overall efficiency of DSCs while using NIR light.