ZnO based heterojunctions and their application in environmental photocatalysis.

As an alternative to TiO2 photocatalysts, ZnO exhibits a large potential for photocatalytic (PC) applications in environmental treatments, such as degradation of wastewater, sterilization of drinking water, and air cleaning. However, the efficiency achieved with ZnO to date is far from that expected for commercialization, due to rapid charge recombination, photo-corrosion as well as poor utilization of solar energy. Fortunately, in recent years, a great number of breakthroughs have been achieved in PC performance (including activity and stability) of micro-/nano- structured ZnO by forming heterojunctions (HJs) with metal nanoparticles (NPs), carbon nanostructures and other semiconductors. In most cases, the improvement of PC performance was ascribed to the better charge separation at the interfaces between ZnO and the other components. Sometimes, the formation of hybrids is also in favor of visible light harvesting. This review summarizes recent advances in the fields of environmental photocatalysis by ZnO based HJs, and especially emphasizes their abilities in degradation of organic pollutants or harmful substances in water. We aim to reveal the mechanism underlying the enhanced PC performance by constructing HJs, and extend the potential of ZnO HJ photocatalysts for future trends, and practical, large-scale applications in environment-related fields.

One-Pot Hydrothermal Synthesis of FeMoO4 Nanocubes as an Anode Material for Lithium-Ion Batteries with Excellent Electrochemical Performance.

Metal molybdates nanostructures hold great promise as high-performance electrode materials for next-generation lithium-ion batteries. In this work, the facial design and synthesis of monodisperse FeMoO4 nanocubes with the edge lengths of about 100 nm have been successfully prepared and present as a novel anode material for highly efficient and reversible lithium storage. Well-defined single-crystalline FeMoO4 with high uniformity are first obtained as nanosheets and then self-aggregated into nanocubes. The morphology of the product is largely controlled by the experimental parameters, such as the reaction temperature and time, the ratio of reactant, the solution viscosity, etc. The molybdate nanostructure would effectively promote the insertion of lithium ions and withstand volume variation upon prolonged charge/discharge cycling. As a result, the FeMoO4 nanocubes exhibit high reversible capacities of 926 mAh g(-1) after 80 cycles at a current density of 100 mA g(-1) and remarkable rate performance, which indicate that the FeMoO4 nanocubes are promising materials for high-power lithium-ion battery applications.

[Study on the occurrence status of formamide in kaolinite-formamide intercalation system and the microstructure of its compounds by FTIR and XRD].

The objectives of this study are to investigate the possible occurrence status of formamide in the intercalation system, the founction of water and the molecular configurations and orientations of formamide inserted into the interlayer of kaolinite, by washing the products with acetone to eliminate the interferences due to the outersurface absorbed formamide molecules in FTIR spectrometry. The results show that the intercalated, absorbed and free formamide probably exist in the intercalation system. Free formamide is easily to be eliminated selectively by drying, whereas the absorbed formamide is removed only by washing with the proper eluting reagent. H2O also is inserted into the interlayer during the formamide molecules' intercalation, which is deintercalated after the compounds being dried. Intercalation caused blue shifts of the inner surface OH stretching bands from 3 687 to 3 692 cm(-1), and deforming bands from 911 to 906 cm(-1), the bands at 3 651 cm(-1) disappeared with a new band appearing at 3 539 cm(-1). The frequency of the Si-O bands of kaolinite was slightly shifted. These IR bands changes implied the breaking of the H-bonds between layers of kaolinite, and the formation of new H-bonds between the kaolinite and the inserting formamide molecules in the intercalation compounds. The formamide molecules intercalated were oriented with the C-N bond perpendicular or nearly perpendicular to the (001) surface of the kaolininte and formed 2 types of H-bonding with inner-surface hydroxyls and siloxane layer of the kaolinite respectively through NH2. A novel model was provided to analyse the microstructure of kaolinite-formamide intercalation compounds. The results show that computation data is in good agreement with experimental data.

Machine Learning-Assisted Sensor Based on CsPbBr3@ZnO Nanocrystals for Identifying Methanol in Mixed Environments.

Methanol is a respiratory biomarker for pulmonary diseases, including COVID-19, and is a common chemical that may harm people if they are accidentally exposed to it. It is significant to effectively identify methanol in complex environments, yet few sensors can do so. In this work, the strategy of coating perovskites with metal oxides is proposed to synthesize core-shell CsPbBr3@ZnO nanocrystals. The CsPbBr3@ZnO sensor displays a response/recovery time of 3.27/3.11 s to 10 ppm methanol at room temperature, with a detection limit of 1 ppm. Using machine learning algorithms, the sensor can effectively identify methanol from an unknown gas mixture with 94% accuracy. Meanwhile, density functional theory is used to reveal the formation process of the core-shell structure and the target gas identification mechanism. The strong adsorption between CsPbBr3 and the ligand zinc acetylacetonate lays the foundation for the formation of the core-shell structure. The crystal structure, density of states, and band structure were influenced by different gases, which results in different response/recovery behaviors and makes it possible to identify methanol from mixed environments. Furthermore, due to the formation of type II band alignment, the gas response performance of the sensor is further improved under UV light irradiation.

Electrochemical and electronic properties of LiCoO2 cathode investigated by galvanostatic cycling and EIS.

The processes of extraction and insertion of lithium ions in LiCoO(2) cathode are investigated by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) at different potentials during the first charge/discharge cycle and at different temperatures after 10 charge/discharge cycles. The spectra exhibit three semicircles and a slightly inclined line that appear successively as the frequency decreases. An appropriate equivalent circuit is proposed to fit the experimental EIS data. Based on detailed analysis of the change in kinetic parameters obtained from simulating the experimental EIS data as functions of potential and temperature, the high-frequency, the middle-frequency, and the low-frequency semicircles can be attributed to the migration of the lithium ions through the SEI film, the electronic properties of the material and the charge transfer step, respectively. The slightly inclined line arises from the solid state diffusion process. The electrical conductivity of the layered LiCoO(2) changes dramatically at early delithiation as a result of a polaron-to-metal transition. In an electrolyte solution of 1 mol L(-1) LiPF(6)-EC (ethylene carbonate) :DMC (dimethyl carbonate), the activation energy of the ion jump (which is related to the migration of the lithium ions through the SEI film), the thermal activation energy of the electrical conductivity and the activation energy of the intercalation/deintercalation reaction are 37.7, 39.1 and 69.0 kJ mol(-1), respectively.

A p-p+ Homojunction-Enhanced Hole Transfer in Inverted Planar Perovskite Solar Cells.

Perovskite solar cells (PSCs) have triggered a research trend in solar energy devices in view of their high power conversion efficiency and ease of fabrication. However, more delicate strategies are still required to suppress carrier recombination at charge transfer interfaces, which is the necessary path to high-efficiency solar cells. Here, a p-p+ homojunction was constructed on basis of NiO film to enhance hole transfer in an inverted planar perovskite solar cell. The homojunction was generated by fabricating a NiO/Cu:NiO bilayer film. The density functional theory calculation demonstrated the charge density difference in the two layers, which could generate a space charge region and a band bending at the junction, and the result was further proved by energy level structure analysis of NiO and Cu:NiO films. The designed homojunction could accelerate the hole transfer and inhibit carrier recombination at the interface between hole transfer layer and perovskite layer. Finally, the inverted planar perovskite solar cell with p-p+ homojunction showed an efficiency of 18.30 % and a high fill factor of 0.81, which were much higher than the counterpart of the PSCs individually using NiO or Cu:NiO as hole transfer layer. This work developed a new structure of hole transport layer to enhance the performance of PSCs, and also provided new ideas for design of charge transfer films.

Hybridized Mechanical and Solar Energy-Driven Self-Powered Hydrogen Production.

Photoelectrochemical hydrogen generation is a promising approach to address the environmental pollution and energy crisis. In this work, we present a hybridized mechanical and solar energy-driven self-powered hydrogen production system. A rotatory disc-shaped triboelectric nanogenerator was employed to harvest mechanical energy from water and functions as a sufficient external power source. WO3/BiVO4 heterojunction photoanode was synthesized in a PEC water-splitting cell to produce H2. After transformation and rectification, the peak current reaches 0.1 mA at the rotation speed of 60 rpm. In this case, the H2 evolution process only occurs with sunlight irradiation. When the rotation speed is over 130 rpm, the peak photocurrent and peak dark current have nearly equal value. Direct electrolysis of water is almost simultaneous with photoelectrocatalysis of water. It is worth noting that the hydrogen production rate increases to 5.45 and 7.27 µL min-1 without or with light illumination at 160 rpm. The corresponding energy conversion efficiency is calculated to be 2.43% and 2.59%, respectively. All the results demonstrate such a self-powered system can successfully achieve the PEC hydrogen generation, exhibiting promising possibility of energy conversion.

[FTIR and XRD analysis studies of intercalation of kaolinite with benzamide].

Benzamide was intercalated into kaolinite by replacing DMSO pre-intercalated. Pure kaolinite-benzamide intercalation compounds were obtained by washing resulting products with acetone. The analysis of XRD shows that the basal spacing of kaolinite-benzamide intercalation compounds increased to 1.437 nm from 0.717 nm of kaolinite. The analysis of FTIR shows that intercalation caused the shifts of the inner surface OH stretching bands from 3 696 and 3 657 cm(-1) of the raw kaolinite to 3 701 and 3 651 cm(-1) of the kaolinite-benzamide intercalation compounds, respectively, and the blue shift of C=O stretching bands from 1 659 cm(-1) of benzamdie to 1 640 cm(-1) of the kaolinite-benzamide intercalation compounds, and the NH vibrations at 3 368 and 3 172 cm(-1) of benzamdie shifted to 3 474 and 3 184 cm(-1), respectively. These changes in IR bands implied the breaking of the H-bonds between layers of kaolinite and the formation of new H-bonds between the inner-surface hydroxyls of the kaolinite and the benzamide in the intercalation compounds. The experimental results show that the intercalation reaction comes to equilibrium rapidly during 30 min, and the highest intercalation ratio occurs when the reaction temperature is 180 degrees C. Washed by acetone, the residual benzamide and that adsorbed on the surface of the resulting products could be eliminated without significant influence on the structure of the intercalation compounds.

A facile sol-gel synthesis of low-fusing titanium opaque porcelain using borate-silicate system and its bioactivity.

The titanium opaque porcelain was synthesized through sol-gel using borate-silicate system. The porcelain was characterized by DSC-TG, X-ray diffraction, N2 adsorption-desorption isotherms and scanning electron microscope tests. The results of DSC showed that the nitrates could be decomposed completely when the bioglass xerogel precursor was heat-treated at 760 ℃. The XRD results showed that the Na2Ca3Si6O16 was the major phase of the opaque porcelain. The synthesized opaque porcelain powders had an average particle size of about 5-25 µm with nanopores of around 50-70 nm on the surface. The BET average surface area of the porcelain was 12.67 m2/g, while the average pore diameters for adsorption and desorption were 9.73 and 10.16 nm, respectively. The flexure strength significantly increased from 47.4 MPa to 116.2 MPa with the sintering temperature increasing from 575 ℃ to 600 ℃. The XRD, FTIR and EDS results proved that hydroxyapatite had formed on the porcelain surface after incubation in simulated body fluid.

Cost-Performance Analysis of Perovskite Solar Modules.

Perovskite solar cells (PSCs) are promising candidates for the next generation of solar cells because they are easy to fabricate and have high power conversion efficiencies. However, there has been no detailed analysis of the cost of PSC modules. We selected two representative examples of PSCs and performed a cost analysis of their productions: one was a moderate-efficiency module produced from cheap materials, and the other was a high-efficiency module produced from expensive materials. The costs of both modules were found to be lower than those of other photovoltaic technologies. We used the calculated module costs to estimate the levelized cost of electricity (LCOE) of PSCs. The LCOE was calculated to be 3.5-4.9 US cents/kWh with an efficiency and lifetime of greater than 12% and 15 years respectively, below the cost of traditional energy sources.

CNTs-Modified Nb3O7F Hybrid Nanocrystal towards Faster Carrier Migration, Lower Bandgap and Higher Photocatalytic Activity.

Novel semiconductor photocatalysts have been the research focus and received much attention in recent years. The key issues for novel semiconductor photocatalysts are to effectively harvest solar energy and enhance the separation efficiency of the electron-hole pairs. In this work, novel Nb3O7F/CNTs hybrid nanocomposites with enhanced photocatalytic activity have been successfully synthesized by a facile hydrothermal plus etching technique. The important finding is that appropriate pH values lead to the formation of Nb3O7F nanocrystal directly. A general strategy to introdue interaction between Nb3O7F and CNTs markedly enhances the photocatalytic activity of Nb3O7F. Comparatively, Nb3O7F/CNTs nanocomposites exhibit higher photodegradation efficiency and faster photodegradation rate in the solution of methylene blue (MB) under visible-light irradiation. The higher photocatalytic activity may be attributed to more exposed active sites, higher carrier migration and narrower bandgap because of good synergistic effect. The results here may inspire more engineering, new design and facile fabrication of novel photocatalysts with highly photocatalytic activity.

Low-Temperature Soft-Cover Deposition of Uniform Large-Scale Perovskite Films for High-Performance Solar Cells.

Large-scale high-quality perovskite thin films are crucial to produce high-performance perovskite solar cells. However, for perovskite films fabricated by solvent-rich processes, film uniformity can be prevented by convection during thermal evaporation of the solvent. Here, a scalable low-temperature soft-cover deposition (LT-SCD) method is presented, where the thermal convection-induced defects in perovskite films are eliminated through a strategy of surface tension relaxation. Compact, homogeneous, and convection-induced-defects-free perovskite films are obtained on an area of 12 cm2 , which enables a power conversion efficiency (PCE) of 15.5% on a solar cell with an area of 5 cm2 . This is the highest efficiency at this large cell area. A PCE of 15.3% is also obtained on a flexible perovskite solar cell deposited on the polyethylene terephthalate substrate owing to the advantage of presented low-temperature processing. Hence, the present LT-SCD technology provides a new non-spin-coating route to the deposition of large-area uniform perovskite films for both rigid and flexible perovskite devices.

Surface engineering of perovskite films for efficient solar cells.

It is critical to prepare smooth and dense perovskite films for the fabrication of high efficiency perovskite solar cells. However, solution casting process often results in films with pinhole formation and incomplete surface coverage. Herein, we demonstrate a fast and efficient vacuum deposition method to optimize the surface morphology of solution-based perovskite films. The obtained planar devices exhibit an average power conversion efficiency (PCE) of 13.42% with a standard deviation of ±2.15% and best efficiency of 15.57%. Furthermore, the devices also show excellent stability of over 30 days with a slight degradation <9% when stored under ambient conditions. We also investigated the effect of vacuum deposition thickness on the electron transportation and overall performance of the devices. This work provides a versatile approach to prepare high-quality perovskite films and paves a way for high-performance and stable perovskite photovoltaic devices.

Direct Synthesis of Few-Layer F-Doped Graphene Foam and Its Lithium/Potassium Storage Properties.

Heteroatom-doped graphene is considered a potential electrode materials for lithium-ion batteries (LIBs). However, potassium-ion batteries (PIBs) systems are possible alternatives due to the comparatively higher abundance. Here, a practical solid-state method is described for the preparation of few-layer F-doped graphene foam (FFGF) with thickness of about 4 nm and high surface area (874 m(2)g(-1)). As anode material for LIBs, FFGF exhibits 800 mAh·g(-1) after 50 cycles at a current density of 100 mA·g(-1) and 555 mAh·g(-1) after 100 cycles at 200 mA·g(-1) as well as remarkable rate capability. FFGF also shows 165.9 mAh·g(-1) at 500 mA·g(-1) for 200 cycles for PIBs. Research suggests that the multiple synergistic effects of the F-modification, high surface area, and mesoporous membrane structures endow the ions and electrons throughout the electrode matrix with fast transportation as well as offering sufficient active sites for lithium and potassium storage, resulting in excellent electrochemical performance. Furthermore, the insights obtained will be of benefit to the design of reasonable electrode materials for alkali metal ion batteries.

One-pot hydrothermal synthesis of Nitrogen-doped graphene as high-performance anode materials for lithium ion batteries.

Nitrogen-doped (N-doped) graphene has been prepared by a simple one-step hydrothermal approach using hexamethylenetetramine (HMTA) as single carbon and nitrogen source. In this hydrothermal process, HMTA pyrolyzes at high temperature and the N-doped graphene subsequently self-assembles on the surface of MgO particles (formed by the Mg powder reacting with H2O) during which graphene synthesis and nitrogen doping are simultaneously achieved. The as-synthesized graphene with incorporation of nitrogen groups possesses unique structure including thin layer thickness, high surface area, mesopores and vacancies. These structural features and their synergistic effects could not only improve ions and electrons transportation with nanometer-scale diffusion distances but also promote the penetration of electrolyte. The N-doped graphene exhibits high reversible capacity, superior rate capability as well as long-term cycling stability, which demonstrate that the N-doped graphene with great potential to be an efficient electrode material. The experimental results provide a new hydrothermal route to synthesize N-doped graphene with potential application for advanced energy storage, as well as useful information to design new graphene materials.

Improving the photovoltaic performance of perovskite solar cells with acetate.

In an all-solid-state perovskite solar cell, methylammonium lead halide film is in charge of generating photo-excited electrons, thus its quality can directly influence the final photovoltaic performance of the solar cell. This paper accentuates a very simple chemical approach to improving the quality of a perovskite film with a suitable amount of acetic acid. With introduction of acetate ions, a homogeneous, continual and hole-free perovskite film comprised of high-crystallinity grains is obtained. UV-visible spectra, steady-state and time-resolved photoluminescence (PL) spectra reveal that the obtained perovskite film under the optimized conditions shows a higher light absorption, more efficient electron transport, and faster electron extraction to the adjoining electron transport layer. The features result in the optimized perovskite film can provide an improved short-circuit current. The corresponding solar cells with a planar configuration achieves an improved power conversion efficiency of 13.80%, and the highest power conversion efficiency in the photovoltaic measurements is up to 14.71%. The results not only provide a simple approach to optimizing perovskite films but also present a novel angle of view on fabricating high-performance perovskite solar cells.

Surface modifications and Nano-composite coatings to improve the bonding strength of titanium-porcelain.

Surface modifications of Ti and nano-composite coatings were employed to simultaneously improve the surface roughness, corrosion resistance and chemical bonding between porclain-Ti. The specimens were studied by field-emission scanning electron microscopy, surface roughness, differential scanning calorimetry, Fourier transform infrared spectroscopy, corrosion resistance and bonding strength tests. The SEM results showed that hybrid structures with micro-stripes, nano-pores and nano-protuberances were prepared by surface modification of Ti, which significantly enhanced the surface roughness and corrosion resistance of Ti. Porous nano-composite coatings were synthesized on Ti anodized with pre-treatment in 40% HF acid. TiO2 nanoparticles were added into the hybrid coating to increase the solid phase content of the sols and avoid the formation of microcracks. With the TiO2 content increasing from 45 wt% to 60 wt%, the quantities of the microcracks on the coating surface gradually decreased. The optimal TiO2 content for the nanocomposite coatings is 60 wt% in this research. Compared to the uncoated group, the bonding strength of the coated groups showed a bonding strength improvement of 23.96%. The cytotoxicity of the 4# coating group was ranked as zero, which corresponds to non-cytotoxicity.