Recent advances in non-metal doped titania for solar-driven photocatalytic/photoelectrochemical water-splitting

Photocatalytic (PC) / Photoelectrochemical (PEC) water splitting under solar light irradiation is considered as a prospective technique to support the sustainable and renewable H_(2) economy and to reach the ultime goal of carbon neutral. TiO_(2) based photocatalysts with high chemical stability and excellent photocatalytic properties have great potential for solar-to-H_(2) conversion. To conquer the challenges of the large band-gap and rapid recombination of photo generated electron-holepairs in TiO_(2), non-metal doping turns out to be economic, facile, and effective on boosting the visible light activity. The localized defect states such as oxygen vacancy and Ti^(3+) generated by non-metal doping are located in the band-gap of TiO_(2), which result in the reduction of band-gap, thus a red-shift of the absorption edge. The hetero doping atoms such as B^(3+), I^(7+), S^(4+)/S^(6+), P^(5+) can also act as electron donors or trap sites which facilitate the charge carrier separation and suppress the recombination of electron-hole pairs. In this comprehensive review, we present the most recent advances on non-metal doped TiO_(2) photocatalysts in terms of fundamental aspects, origin of visible light activity and the PC / PEC behaviours for water splitting. In particular, the characteristics of different non-metal elements (N, C, B, S, P, Halogens) as dopants are discussed in details focusing on the synthesis approaches, characterization as well as the efficiency of PC and PEC water splitting. The present review aims at guiding the readers who want quick access to helpful information about how to efficiently improve the performance of photocatalysts by simple doping strategies and could stimulate new intuitive into the new doping strategies.

Anomalous metastable hcp Ni nanocatalyst induced by non-metal N doping enables promoted ammonia borane dehydrogenation

Developing high-performing non-noble transition metal catalysts for H_(2) evolution from chemical hydrogen storage materials is of great significance for the hydrogen economy system, yet challenging. Herein,we present for the first time that anomalous metastable hexagonal close-packed Ni nanoparticles induced by heteroatom N doping encapsulated in carbon(N-hcp-Ni/C) can exhibit admirable catalytic performance for ammonia borane(AB) dehydrogenation, prominently outperforming conventional fcc Ni counterpart with similar morphology and favorably presenting the state-of-the-art level.Comprehensive experimental and theoretical studies unravel that unusual hcp phase engineering of Ni together with N doping could induce charge redistribution and modulate electronic structure, thereby facilitating H_(2)O adsorption and expediting H_(2)O dissociation(rate-determining step). As a result, AB dehydrogenation can be substantially boosted with the assistance of N-hcp-Ni/C. Our proposed strategy highlights that unconventional crystal phase engineering coupled with non-metal heteroatom doping is a promising avenue to construct advanced transition metal catalysts for future renewable energy technologies.

Modelling and Dynamic Characteristics for a Non-metal Pressurized Reservoir with Variable Volume

With the increasing demand to reduce emissions and save energy,hydraulic reservoirs require new architecture to optimize their weight,space,and volume.Conventional open reservoirs are large,heavy,and easily polluted,and threaten the operation of hydraulic systems.A closed reservoir provides the advantages of small volume and light weight,compared to open reservoirs.In this study,a non-metallic pressure reservoir with variable volume is designed and manufactured for closed-circuit hydraulic systems.The reservoir housing is made of rubber,and the Mooney-Rivlin model is chosen based on the rubber strain properties.The FEA simulation for the reservoir is performed using ANSYS Workbench to obtain the structural stiffness.The major contribution is the establishment of mathematical models for this reservoir,including the volume equation changing with height,flow equation,and force balance equation,to explore the output characteristics of this reservoir.Based on these results,simulation models were built to analyze the output characteristics of the reservoir.Moreover,the test rig of a conventional hydraulic system was transformed into a closed-circuit asymmetric hydraulic system for the reservoir,and preliminary verification experiments were conducted on it.The results demonstrate that the designed reservoir can absorb and discharge oil and supercharge pump inlet to benefit system operation.The changes in the volume and pressure with displacements under different volume ratios and frequencies were obtained,which verified the accuracy of the mathematical models.Owing to its lightweight design and small volume,the reservoir can replace conventional open reservoirs,and this lays a foundation for future theoretical research on this reservoir.

Enhancing visible-light photocatalytic activity of α-Bi_2O_3 via non-metal N and S doping

In recent years, some important research indicated that the visible-light activity of photocatalysts could be enhanced via incorporating p-block non-metal elements into the lattice. In this paper, we investigated the electronic structures of pure and different non-metal （C, N, S, F, Cl, and Br） doped α-Bi2O3 using first-principles calculations based on the density functional theory. The band structures, the electronic densities of states, and the effective masses of electrons and holes for doped α-Bi2O3 were obtained and analyzed. The N and S dopings narrowed the band gap and reduced the effective mass of the carriers, which are beneficial for the photocatalytic performance. The theoretical predication was further confirmed by the experimental results.

Growth,Dislocation and Morphology of Nd∶GdVO_4 Single Crystal

The neodymium ions doped gadolinium vanadate (Nd∶GdVO_4) single crystals were successfully grown by Czochralski method. Chemical etching technique was used to reveal the dislocation structure of the crystals. An average dislocation density of (100) plane is 600 pits/mm 2. The crystal-morphology can be used to determine crystal orientation accurately with simple optical method.

Main and Trace Element Contents of Tomatoes Grown in Austria

Tomatoes are one of the most popular and widespread kinds of vegetables on a global scale. Tomatoes of various varieties, sizes and shapes, were grown in 3 different greenhouses in Austria on solid substrates. After freeze drying, they were analyzed for main and trace elements by ICP-OES, ICP-MS, and combustion methods （for C, N）. Main inorganic cation was K, whereas contents of hazardous metals （e.g. Cd, Pb）, Rare Earth Elements, Si, and Ti were marginal. Due to high water contents, the contribution to the Recommended Daily Intake of essential elements is largely below 1/5 for 1 kg consumption. In spite of different varieties grown at the 3 sites, trends for concentrations versus fruit size could be noted for K, Ca, S, B, Cu, Fe, Zn and Si. Similarly, fruits with seeds ＋ jelly tended to contain more of almost all elements, but less of Li, Ca, Sr, and Ba, whereas P and B were equally distributed. No significant correlations between the concentrations found in tomato-fruits and the amount of soil mobilizable in 0.16 M acetic acid （exchangeable ＋ acid mobile） were found. A look into already published data from other countries reveals that element concentrations met in tomatoes presumably depend on climatic conditions and suitably adapted varieties than on the growing substrate.

Defect and Doping Co‑Engineered Non‑Metal Nanocarbon ORR Electrocatalyst

Exploring low-cost and earth-abundant oxygen reduction reaction(ORR)electrocatalyst is essential for fuel cells and metal–air batteries.Among them,non-metal nanocarbon with multiple advantages of low cost,abundance,high conductivity,good durability,and competitive activity has attracted intense interest in recent years.The enhanced ORR activities of the nanocarbons are normally thought to originate from heteroatom(e.g.,N,B,P,or S)doping or various induced defects.However,in practice,carbon-based materials usually contain both dopants and defects.In this regard,in terms of the co-engineering of heteroatom doping and defect inducing,we present an overview of recent advances in developing non-metal carbon-based electrocatalysts for the ORR.The characteristics,ORR performance,and the related mechanism of these functionalized nanocarbons by heteroatom doping,defect inducing,and in particular their synergistic promotion effect are emphatically analyzed and discussed.Finally,the current issues and perspectives in developing carbon-based electrocatalysts from both of heteroatom doping and defect engineering are proposed.This review will be beneficial for the rational design and manufacturing of highly efficient carbon-based materials for electrocatalysis.

Influence of processing parameters on the phase composition of ZrN-Si_3N_4 synthesized from zircon

The optimum parameters were determined for synthesizing ZrN-Si3N4 composite powder from zircon by carbothermal reduction-nitridation （CTRN） process. The samples were prepared by mixing the carbon black of an average particle size less than 30 μm and the zircon of 40 μm with C/ZrSiO4 mass ratios of 0.2, 0.3, 0.4, and 0.5. The prepared samples were subjected to the CTRN process at temperatures of 1673, 1723, 1753, and 1773 K for 6, 9, and 12 h. The CTRN process was conducted in an atmosphere-controlled tubular furnace in a nitrogen gas flow of 1.0 L/rain. All the products were examined by X-ray powder diffraction to determine the transformation. The results showed that the proper transformation of ZrN-Si3N4 occurred at 1773 K for 12 h with a C/ZrSiO4 mass ratio of 0.4.

Influence of cerium ions on the anatase-rutile phase transition of TiO_2 prepared by sol-gel auto-igniting synthesis

The anatase-rutile phase transformation of TiO_2 doped cerium up to 5 molpercent was studied by X-ray diffraction and X-ray photoelectron spectroscopy. The samples wereprepared by sol-gel auto-igniting synthesis process from a TiO(NO_3)_2-Ce(NO_3)_2-NH_4NO_3-citricacid complex compound system. The combusted amorphous powders were calcined at differenttemperatures. Significant structural changes were observed during the various stages of the phasetransformation. It was concluded that at low dopant contents, cerium ions were incorporated into theTiO_2 structure, and the anatase phase was stabilized; but at larger amounts, part of the dopantwas segregated on the surface of TiO_2 and the rutile formation was accelerated at elevatedcalcination temperature.

TiO_2 thin film photocatalyst

It is well known that the photocatalytic activity of TiO_2 thin filmsstrongly depends on the preparing methods and post-treatment conditions, since they have a decisiveinfluence on the chemical and physical properties of TiO_2 thin films. Therefore, it is necessary toelucidate the influence of the preparation process and post-treatment conditions on thephoto-catalytic activity and surface microstructures of the films. This review deals with thepreparation of TiO_2 thin film photo-catalysts by wet-chemical methods (such as sol-gel,-reversemicellar and liquid phase deposition) and the comparison of various preparation methods as well astheir advantage and disadvantage. Furthermore, it is discussed that the advancement ofphotocatalytic activity, super-hydrophilicity and bactericidal activity of TiO_2 thin filmphotocatalyst in recent years.

Preparation and characterization of the TiO_2-V_2O_5 photocatalyst with visible-light activity

Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline （PANI） by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 dusters during the calcination process was avoided because of the wrap of polyaniline. The surface mor- phology, the crystal phases, the structure, and the absorption spectra of （PANI）,/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FT-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue （MB） solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2： V2O5 = 10：1 presented the best photocatalytic activity.

Rapid communication Preparation of TiO_2 nanometer thin films with high photocatalytic activity by reverse micellar method

Two kinds of TiO_2 nanometer thin films were prepared on stainless steel bythe reverse micellar and sol-gel methods, respectively. The calcined TiO_ 2 thin films werecharacterized by X-ray diffraction (XRD), atomic force microscopy (AFM), BET surface area and X-rayphotoelectron spectroscopy (XPS). Photocatalytic activity was evaluated by photocatalyticdecoloration of methyl orange aqueous solution. The results showed that the TiO_2 thin filmsprepared by reverse micellar method (designated as RM-TiO_2 films) showed higher photocatalyticactivity than those by sol-gel method (designated as SG-TiO_2 films). This is attributed to the factthat the former is composed of smaller monodispersed spherical particles with a size of about 15 nmand possesses higher surface areas.

Effect of growth time on morphology and photovoltaic properties of ZnO nanowire array films

Single-crystalline ZnO nanowire arrays with different aspect ratios and nanowire densities were prepared by the hydrothermal growing method using polyethyleneimine （PEI） as a surfactant. PEI can only hinder the lateral growth of the ZnO nanowires, which is observed by high resolution transmission electron microscopy （HRTEM） analysis. Dye-sensitized solar cells were assembled by the ZnO nanowire arrays with different thicknesses, which can be controlled by the growing time and characterized using photocurrent-voltage measurements. Their photocurrent densities and energy allover conversion efficiencies increased with increasing ZnO nanowire lengths. Short-circuit current density of 4.31 mA.cm-2 and allover energy conversion efficiency of 0.87% were achieved with 12.9-μm-long ZnO nanowire arrays.

Effects of argon gas flow rate and guide shell on oxygen concentration in Czochralski silicon growth

φ200 mm silicon single crystals were grown in the φ450 mm hot zone of a Czochralski （CZ） furnace. By modifying the pattern and the velocity of the argon flow, the silicon single crystals with different oxygen concentrations were obtained. Through numerical simulation, the velocity of the argon gas flow was plotted for the first time. The experiment resuits were analyzed and the optimum condition of the argon flow with the lowest oxygen concentration was obtained.

Roles of crystal defects in the persistent luminescence of Eu^(2+), Dy^(3+) co-doped strontium aluminate based phosphors

The roles of different point defects in persistent luminescence of SrAl2O4：Eu,Dy phosphors were investigated. The research results showed that Dyer plays an important role in the persistent luminescence of SrA1EO4：Eu, Dy phosphors. It can serve as the electron trap of suitable depth for persistent luminescence. V~ does not serve as the electron trap of suitable depth, but its existence can increase the depth of electron traps. There is interaction between the Dy^3＋（ DySr ） and the Eu^2＋（Eu^x Sr ）, and only if the distance between the Dy^3＋（DySr） and the Eu^2＋ （Eu^x Sr） is close enough, the Dyer can work as an effective electron trap. The point defect of V＂ Sr can be hole trap, but the change of its density in crystal matrix does not arouse the obvious change of persistent luminescence.

Synthesis of Long Afterglow Phosphors MAl_2O_4∶Eu^(2+), Dy~ (3+)(M=Ca, Sr, Ba) by Microemulsion Method and Their Luminescent Properties

Long afterglow phosphors MAl2O4：Eu^2＋ , Dy^3＋ （M = Ca, Sr, Ba） were synthesized by microemulsion method, and their crystal structure and luminescent properties were compared and investigated. XRD patterns of samples indicate that phosphors CaAl2O4：Eu^2＋, Dy^3＋ and SrAl2O4 ： Eu^2＋, Dy^3＋ are with monoelinie crystal structure and phosphor BaAl2O4：Eu^2＋ , Dy^3＋ is with hexagonal crystal structure. The wide range of excitation spectrum of phosphors MAl2O4： Eu^2 ＋ , Dy^3＋ （M = Ca,Sr, Ba） indicates that the luminescent materials can he excited by light from ultraviolet ray to visible light and the maximum emission wavelength of phosphors MAl2O4：Eu^2＋ , Dy^3＋ （M = Ca, Sr, Ba） is found mainly at λem of 440 nm （M = Ca）, 520 nm （M = Sr） and 496 nm （M = Ba） respectively, the corresponding colors of emission light are blue, green and eyna-green respectively. The afterglow decay tendency of phosphors can he summarized as three processes： initial rapid decay, intermediate transitional decay and very long slow decay. Afterglow decay curves coincide with formula I = At^ - n, and the sequence of afterglow intensity and time is Sr 〉 Ca 〉 Ba.

Photocatalysts for Photocatalytic CO_(2)Reduction:A Review

Energy crisis and environmental pollution have become vitally severe challenges for the current society.During the circumstances of pursuing carbon peak and carbon neutrality,photocatalytic CO_(2) reduction will be an essential,necessary and even inevitable development requirement and trend.However,there are some bottlenecks that need to be addressed immediately,such as low quantum efficiency and narrow light absorption range for single photocatalysts.Therefore,efficient and stable visible light driving materials are the core challenge in the field of photocatalytic CO_(2) conversion.This paper reviewed the photocatalysts used for CO_(2) reduction classified as metal photocatalysts,non-metal photocatalysts,and MOFs photocatalysts,and the CO_(2) reduction capacity and mechanism of different photocatalysts were described.In the end,the problems to be solved and the future development of photocatalytic CO_(2) reduction were summarized.

Facile synthesis of La_2Mo_2O_9 nanoparticles via an EDTA complexing approach

A facile EDTA （ethylene diamine tetraacetic acid） complexing technique has been successfully employed to prepare La2Mo2O9 nanoparticles. The as-synthesized products are characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and Fourier transform infrared spectroscopy （FT-IR）. The results show that a homogeneous transparent gel can be obtained with EDTA as the organic complexing reagent under the pH value of 3.0. Further thermal decomposition of the as-synthesized transparent gel by increasing the temperature up to 600℃ for 3 h results in the formation of La2Mo2O9 nanoparticles with a crystal size of about 30 nm. Moreover, the nanoparticles tend to form micrometer-sized aggregates with a three-dimensional network structure, which shows promising applications in solid oxide fuel cells （SOFC）, catalysts and so on.

Investigation of Loss Weight and Densification of SiC-Al_2O_3-Y_2O_3 Ceramic Composite on Sintering

α-SiC, Al_2O_3 and Y_2O_3 powders were all used as raw materials. The SiC-Al_2O_3-Y_2O_3 ceramic composites were made by pressureless liquid phase sintering technology. The effects of sintering temperature, loss weight and coordination number on sintering densification were studied. The reason for producing loss weight on sintering was analysed. The results show that the primary reason for producing loss weight on sintering in SiC-Al_2O_3-Y_2O_3 ceramic composite was that chemical reactions between SiC and Al_2O_3 are happened during sintering, and given out volatile gases. If sintering temperature is excessively lower, grain size would be finer, and coordination number would be higher, well then material would be on no sintering densification. If sintering temperature is excessively higher, grains would grow up, though small coordination number would benefit to make pore eliminate and shrink, but coarse microstructure would also block gliding and resetting of grains, together affected by expansion stress from volatile gas, the material densification would instead go down. Only under the sintering process of 1850 ℃ for 30 min, material densification is better, and the mechanical property of ceramic composites is also improved.

Preparation of CuInSe_2 thin films by paste coating

Precursor pastes were obtained by milling Cu-In alloys and Se powders. CulnSe2 thin films were successfully prepared by precursor layers, which were coated using these pastes, and were annealed in a H2 atmosphere. The pastes were tested by laser particle diameter analyzer, simultaneous thermogravimetric and differential thermal analysis instruments （TG-DTA）, and X-ray diffractometry （XRD）. Selenized films were characterized by XRD, scanning electron microscopy （SEM）, and energy dispersive spectroscopy （EDS）. The results indicate that chalcopyrite CuInSe2 is formed at 180℃ and the crystallinity of this phase is improved as the temperature rises. All the CuInSe2 thin films, which were annealed at various temperatures, exhibit the preferred orientation along the （112） plane. The compression of precursor layers before selenization step is one of the most essential factors for the preparation of perfect CuInSe2 thin films.