Synergistic Effect of Rutile and Brookite TiO2 for Photocatalytic Formic Acid Dehydrogenation.

Solar energy is an ideal clean and inexhaustible energy source. Solar-driven formic acid (FA) dehydrogenation is one of the promising strategies to address safety and cost issues related to the storage, transport, and distribution of hydrogen energy. For FA dehydrogenation, the O-H and C-H cleavages are the key steps, and developing a photocatalyst with the ability to break these two bonds is critical. In this work, both density functional theory (DFT) calculation and experimental results confirmed the positive synergistic effect between brookite and rutile TiO2 for O-H and C-H cleavage in HCOOH. Further, brookite TiO2 is beneficial to the generation of the •OH radical and significantly promotes C-H cleavage in formate. Under optimized conditions, the H2 production efficiency of FA dehydrogenation can reach up to 30.4 µmol·mg-1·h-1, which is the highest value compared with similar reported TiO2-based systems and over 1.7 times the reported highest value of Au0.75Pd0.25/TiO2 photocatalysts. More importantly, after more than 42 days (>500 h) of irradiation, the system still demonstrated high H2 production activity, indicating the potential for practical application. This work provides a valuable strategy to improve both the efficiency and stability of photocatalytic FA dehydrogenation under mild conditions.

The photocatalytic wastewater hydrogen production process with superior performance to the overall water splitting.

The utilization of a cost-free sacrificial agent is a novel approach to significantly enhance the efficiency of photocatalytic hydrogen (H2) production by water splitting. Wastewater contains various organic pollutants, which have the potential to be used as hole sacrificial agents to promote H2 production. Our studies on different pollutants reveals that not all pollutants can effectively promote H2 production. However, when using the same pollutants, not all photocatalysts achieved a higher H2 evolution rate than pure water. Only when the primary oxidizing active species of the photocatalyst are •OH radicals, which are generated by photogenerated holes, and when the pollutants are easily attacked and degraded by •OH radicals, can the production of H2 be effectively promoted. It is noteworthy that the porous brookite TiO2 photocatalyst exhibits a significantly higher H2 evolution rate in Reactive Red X-3B and Congo Red, reaching as high as 26.46 mmol⋅g-1⋅h-1 and 32.85 mmol⋅g-1 ⋅h-1, respectively, which is 2-3 times greater than that observed in pure water and is 10 times greater than most reported studies. The great significance of this work lies in the potential for efficient H2 production through the utilization of wastewater.

Rutile TiO2 single crystals delivering enhanced photocatalytic oxygen evolution performance.

Owing to their scientific and technological importance, the development of highly efficient photocatalytic water oxidation systems with rapid photogenerated charge separation and high surface catalytic activity is highly desirable for the storage and conversion of solar energy. A promising candidate is rutile phase titanium dioxide (TiO2), which has been widely studied over half a century. Specifically, oriented single-crystalline TiO2 surfaces with high oxidative reactivity would be most desirable, but achieving these structures has been limited by the availability of synthetic techniques. In this study, a facile and green synthetic approach was developed for the first time to synthesize rutile TiO2 single crystals with regulable reductive and oxidative facets. Glycolic acid (GA) and sodium fluoride (NaF) are used as the crucial and effective phase and facet controlling agents, respectively. The selective adsorption of F- ions on the facets of rutile TiO2 crystals not only plays a key role in driving the nucleation and preferential growth of the crystals with desired facets but also significantly affects their photocatalytic gas evolution reactivity. With heat treatment, the highly stable F--free rutile TiO2 single crystals with a high percentage of oxidative facets exhibit a superior photocatalytic gas evolution rate (≈116 µmol h-1 per 0.005 g catalyst), 8.5 times higher than that of previous F--containing samples.

Considerations for a More Accurate Evaluation Method for Photocatalytic Water Splitting.

Over the past decades, various photocatalysts have been developed and great progress has been achieved in the field of solar-driven photocatalytic water splitting. However, the lack of an accurate and comprehensive evaluation method greatly hinders the meaningful comparison between different systems and becomes a serious impediment for the development of photocatalysts. Although many researchers are aware of this, there has been little work in this area. In this Viewpoint, we first analyze the insufficiencies of the existing evaluation methods and then make preliminary suggestions, aiming to stimulate discussion in the research community and hopefully lead to a widely accepted and authoritative evaluation system to assess photocatalyst performance.

Correction: Effect of aspect ratios of rutile TiO2 nanorods on overall photocatalytic water splitting performance.

Correction for 'Effect of aspect ratios of rutile TiO2 nanorods on overall photocatalytic water splitting performance' by Bing Fu et al., Nanoscale, 2020, DOI: 10.1039/c9nr10870j.

Effect of aspect ratios of rutile TiO2 nanorods on overall photocatalytic water splitting performance.

The spatial separation of reduction and oxidation reaction sites on the different facets of a semiconductor is an ideal and promising route for overall photocatalytic water splitting due to efficient charge carrier separation. Rutile TiO2 has separate oxidation and reduction crystal facets and can be used to achieve direct splitting of pure water under ultraviolet (UV) light irradiation. In order to improve the rate of water oxidation reaction, the ratio of different crystal facets of rutile should be regulated controllably. However, the preparation of rutile TiO2 architecture has been limited by the availability of synthetic techniques. In this study, rutile TiO2 nanorods with various aspect ratios were accurately prepared in the presence of Cl- anions and H+ cations, which were found to play a crucial role in forming the morphology of rutile TiO2 nanorods. In addition, the mechanism involving the growth of rutile TiO2 nanorods with different aspect ratios is proposed. Rutile TiO2 nanorods with a high proportion of oxidative (111) facets provided higher overall water splitting reactivity.

Comparative study of in vitro effects of different nanoparticles at non-cytotoxic concentration on the adherens junction of human vascular endothelial cells.

BACKGROUND: Effects of different nanoparticles (NPs) exposure at acutely non-cytotoxic concentrations are particularly worthy to figure out, compare, and elucidate. OBJECTIVE: To investigate and compare the effect of a small library of NPs at non-cytotoxic concentration on the adherens junction of human umbilical vein endothelial cells (HUVECs), obtaining new insights of NPs safety evaluation. MATERIALS AND METHODS: The HUVECs layer was exposed to NPs including gold (Au), platinum (Pt), silica (SiO2), titanium dioxide (TiO2), ferric oxide (Fe2O3), oxidized multi-walled carbon nanotubes, with different surface chemistry and size distribution. Cellular uptake of NPs was observed by transmission electron microscopy. and the cytotoxicity was determined by Cell Counting Kit-8 assay. The NP-induced variation of intracellular reactive oxygen species (ROS) and catalase (CAT) activity was measured using the probe of 2'7'-dichlorodihydr fluorescein diacetate and a CAT analysis kit, respectively. The level of VE-cadherin of HUVECs was analyzed by Western blot, and the loss of adherens junction was observed with laser confocal microscopy. RESULTS: The acutely non-cytotoxic concentrations of different NPs were determined and applied to HUVECs. The NPs increased the level of intracellular ROS and the activity of CAT to different degrees, depending on the characteristics. At the same time, the HUVECs lost their adherens junction protein VE-cadherin and gaps were formed between the cells. The NP-induced oxidative stress and gap formation could be rescued by the supplementary N-acetylcysteine in the incubation. CONCLUSION: The increase of intracellular ROS and CAT activity was one common effect of NPs, even at the non-cytotoxic concentration, and the degree was dependent on the composition, surface chemistry, and size distribution of the NP. The effect led to the gap formation between the cells, while could be rescued by the antioxidant. Therefore, the variation of adherens junction between endothelial cells was suggested to evaluate for NPs when used as therapeutics and diagnostics.

Effects of bulk and surface defects on the photocatalytic performance of size-controlled TiO2 nanoparticles.

Defects are one of the crucial factors influencing the photocatalytic activities of TiO2 nanoparticles (NPs), as they directly affect the charge separation efficiencies. However, we found that the effect of bulk or surface defects on the photocatalytic performance of TiO2 is totally different. Here, we controllably synthesized four kinds of uniform TiO2 NPs, which were used to investigate how the bulk and surface defects influenced the photoactivities of samples with different particle sizes. Through XPS and EPR analysis, bulk and surface defects were observed in all the TiO2 samples and their amounts had been reduced after the calcination process. The reduction of bulk and surface defects enhanced the photoactivities of TiO2 NPs with diameters >10 nm, but the situation was inverse for those samples with diameters <10 nm. Therefore, we demonstrated that bulk defects play a dominate role in the change in photoactivity in particles larger than 10 nm, while surface defects are more important than bulk defects for particles less than 10 nm.

Facile Synthesis of Hollow TiO2 Single Nanocrystals with Improved Photocatalytic and Photoelectrochemical Activities.

Diverse titanium dioxide (TiO2 ) nanostructures have attracted considerable attention owing to their broad applications in photocatalytic and photoelectrochemical fields. Herein, TiO2 hollow single nanocrystals are reported for the first time by using TiO2 nanopowders as the raw material and hydrofluoric acid as a capping and etching agent through a simple hydrothermal treatment. The influence of experimental parameters such as the concentration of HF, the amount of TiO2 nanoparticles, the reaction time, and temperature was investigated systematically. The obtained hollow single nanocrystals exhibited enhanced photoelectrochemical and photocatalytic performances attributed to their good crystallinity, suppressed charge recombination, and increased active sites. The current study will provide new insights into the nanostructured engineering of anatase TiO2 as well as opportunities for the controllable synthesis of hollow single nanocrystals.

[Bulk heterojunction solar cell based on porphyrin compounds].

Three kinds of porphyrins which can abbreviate as TPP, TPPCu and TMPPFeCl were synthesized by one-step method with mixed solvents. Then these porphyrin materials were used as donors to fabricate organic solar cells with PCBM as accepter by the solution processing of spin-coating method. The structure is ITO/porphyrin : PCBM/Al. The photovoltaic characterizations of these devices were investigated. The device based on TPP : PCBM shows the best performance with an open circuit voltage (V(OC)) of 0.52 V, a short circuit current (J(SC)) of 0.98 mA x cm(-2), and fill factor (FF) of 30.1%. Then the influence of different weight ratio of TPP : PCBM was researched. The best weight ratio of TPP : PCBM is 1 : 1. Increasing or decreasing the quatity of TPP would make J(SC) and V(OC) of the device deterioration and have little effect on the FF.

Hierarchical TiO2 nanospheres with dominant {001} facets: facile synthesis, growth mechanism, and photocatalytic activity.

Hierarchical TiO(2) nanospheres with controlled surface morphologies and dominant {001} facets were directly synthesized from Ti powder by a facile, one-pot, hydrothermal method. The obtained hierarchical TiO(2) nanospheres have a uniform size of 400-500 nm and remarkable 78 % fraction of {001} facets. The influence of the reaction temperature, amount of HF, and reaction time on the morphology and the exposed facets was systematically studied. A possible growth mechanism speculates that Ti powder first dissolves in HF solution, and then flowerlike TiO(2) nanostructures are formed by assembly of TiO(2) nanocrystals. Because of the high concentration of HF in the early stage, these TiO(2) nanostructures were etched, and hollow structures formed on the surface. After the F(-) ions were effectively absorbed on the crystal surfaces, {001} facets appear and grow steadily. At the same time, the {101} facets also grow and meet the {101} facets from adjacent truncated tetragonal pyramids, causing coalescence of these facets and formation of nanospheres with dominant {001} facets. With further extension of the reaction time, single-crystal {001} facets of hierarchical TiO(2) nanospheres are dissolved and TiO(2) nanospheres with dominant {101} facets are obtained. The photocatalytic activities of the hierarchical TiO(2) nanospheres were evaluated and found to be closely related to the exposed {001} facets. Owing to the special hierarchical architecture and high percentage of exposed {001} facets, the TiO(2) nanospheres exhibit much enhanced photocatalytic efficiency (almost fourfold) compared to P25 TiO(2) as a benchmark material. This study provides new insight into crystal-facet engineering of anatase TiO(2) nanostructures with high percentage of {001} facets as well as opportunities for controllable synthesis of 3D hierarchical nanostructures.

Soluble copper phthalocyanine applied for organic solar cells.

A soluble derivative of copper phthalocyanine, that is 2,9,16,23-tetra carboxyl copper phthalocyanine (CuTCPc), is synthesized in this paper. The applications of CuTCPc as donor and interlayer materials in solar cell devices are investigated. The results demonstrate that when CuTCPc is used as a donor material, the performance of the device ITO/CuTCPc/PCBM/Al shows an open circuit voltage (V(OC)) of 0.54 V, a short circuit current (J(SC)) of 0.825 mA/cm2, a fill factor (FF) of 32.3% and the power conversion efficiency (nu) of 0.14%. When CuTCPc acts as an interlayer, the performance of the device ITO/CuTCPc/P3HT:PCBM/Al is improved: J(SC) increases to 3.12 mA/cm2, V(OC) increases to 0.59 V, FF increases to 33.8%, and the corresponding nu is 0.62%.

Preparation of porous titania film and its application in solar cells.

Polymer/nanocrystal bulk heterojunction photovoltaic cells have attracted substantial interest because the hybrid active layer combines the advantages of inorganic materials and polymers. In this work, a porous TiO2 was prepared via the sol-gel method with a polyethylene glycol 2000 (PEG2000) template. A kind of polymer/inorganic solar cell based on poly (3-hexylthiophene) (P3HT)/TiO2 was fabricated on the indium-tin-oxide (ITO) glass substrate and the structure of device was ITO/TiO2/P3HT/Au. The device showed the performance with a short circuit current (J(SC)) of 1.29 mA/cm2, an open circuit voltage (V(OC)) of 0.55 V and a fill factor (FF) of 28.7%.

Fabrication and characteristics of three-dimensional flower-like titanate nanostructures.

A novel and facile approach has been developed to fabricate three-dimension (3D) flower-like titanate nanostructures from Ti powders. The synthesized flower-like titanate nanostructures were composed of many thin nanoribbons and have an ultrahigh specific surface area of 572.3 m2/g. After high temperature heat treatment, the flower-like titanate nanostructures were totally transformed into corresponding anatase TiO2 nanostructures without destroying their 3D hierarchical structural motif. The flower-like TiO2 nanostructures exhibited high photocatalytic activity for photodecomposition of methyl blue, and they could possibly be further used in photovoltaic cell, sensors, Li-ion batteries, and so on.

Flower-like TiO2 nanostructures with exposed {001} facets: facile synthesis and enhanced photocatalysis.

Flower-like TiO(2) nanostructures with exposed {001} facets were synthesized by a low-temperature hydrothermal process from Ti powders for the first time, and they exhibited enhanced photocatalytic degradation of methylene blue dye under ultraviolet light irradiation.

Anatase TiO(2) single crystals with exposed {001} and {110} facets: facile synthesis and enhanced photocatalysis.

Anatase TiO(2) single crystals with exposed {001} and {110} facets have been successfully synthesized using a modified hydrothermal technique in the presence of hydrogen peroxide and hydrofluoric acid solution; these single crystals exhibited enhanced photocatalytic activities for degradation of Methylene Blue dye under ultraviolet light irradiation.

The adsorption of L-phenylalanine on oxidized single-walled carbon nanotubes.

A simple and green approach was proceeded to obtain a stable single-walled carbon nanotubes (SWNTs)/L-phenylalanine (Phe) solution. The oxidized SWNTs (OSWNT) were used in this work. The scanning electron microscopy (SEM), High-resolution transmission electron microscopy (HRTEM), Raman spectrometer, Fourier transform-infrared resonance (FT-IR), Ultraviolet-visible (UV-vis) spectroscopy, Thermogravimetric analysis (TGA) and High performance liquid chromatography (HPLC) were joined together to investigate the interaction between OSWNT and Phe. The OSWNT became soluble in the water and formed a stable solution since the Phe was adsorbed. The absorbed amount of Phe on the OSWNT is around 33 wt%. Adsorption of the Phe was mainly carried out on the OSWNT with smaller diameters. The Phe molecules were absorbed on the OSWNT by conjunct interaction of the pi-pi stacking, hydrogen bond and part of covalent bond.