Search Results (59)

We developed dye-sensitized solar cells based on anatase–titanium dioxide (A-TiO₂) nanotubes (TiNTs) and nanocubes (TiNcs) with {001} crystal facets generated using simple and facile electrochemical anodization. We also demonstrated a simple way of developing one-dimensional, two-dimensional, and three-dimensional self-assembled TiO₂ nanostructures via electrochemical anodization, using them as an electron-transporting layer in DSSCs. TiNTs maintain tubular arrays for a limited time before becoming nanocrystals with {001} facets. Using FESEM and TEM, we observed that the TiO₂ nanobundles were transformed into nanocubes with {001} facets and lower fluorine concentrations. Optimizing the reaction approach resulted in better-ordered, crystalline anatase TiNTs/Ncs being formed on the Ti metal foil. The anatase phase of as-grown TiO₂ was confirmed by XRD, with (101) being the predominant intensity and preferred orientation. The nanostructured TiO₂ had lattice values of a = 3.77–3.82 and c = 9.42–9.58. The structure and morphology of these as-grown materials were studied to understand the growth process. The photoconversion efficiency and impedance spectra were explored to analyze the performance of the designed DSSCs, employing N719 dye as a sensitizer and the I⁻/I³⁻ redox pair as electrolytes, sandwiched with a Pt counter-electrode. As a result, we found that self-assembled TiNTs/Ncs presented a more effective photoanode in DSSCs than standard TiO₂ (P25). TiNcs (0.5 and 0.25 NH₄F) and P25 achieved the highest power conversion efficiencies of 3.47, 3.41, and 3.25%, respectively. TiNcs photoanodes have lower charge recombination capability and longer electron lifetimes, leading to higher voltage, photocurrent, and photovoltaic performance. These findings show that electrochemical anodization is an effective method for preparing TiNTs/Ncs and developing low-cost, highly efficient DSSCs by fine-tuning photoanode structures and components. Full article

The monolithic integration of III-V semiconductors with silicon (Si) is a critical step toward advancing optoelectronic and photonic devices. In this work, we present GaAs nanoheteroepitaxy (NHE) on Si nanotips using gas-source molecular beam epitaxy (GS-MBE). We discuss the selective growth of fully relaxed GaAs nanoislands on complementary metal oxide semiconductor (CMOS)-compatible Si(001) nanotip wafers. Nanotip wafers were fabricated using a state-of-the-art 0.13 μm SiGe Bipolar CMOS pilot line on 200 mm wafers. Our investigation focuses on understanding the influence of the growth conditions on the morphology, crystalline structure, and defect formation of the GaAs islands. The morphological, structural, and optical properties of the GaAs islands were characterized using scanning electron microscopy, high-resolution X-ray diffraction, and photoluminescence spectroscopy. For samples with less deposition, the GaAs islands exhibit a monomodal size distribution, with an average effective diameter ranging between 100 and 280 nm. These islands display four distinct facet orientations corresponding to the {001} planes. As the deposition increases, larger islands with multiple crystallographic facets emerge, accompanied by a transition from a monomodal to a bimodal growth mode. Single twinning is observed in all samples. However, with increasing deposition, not only a bimodal size distribution occurs, but also the volume fraction of the twinned material increases significantly. These findings shed light on the growth dynamics of nanoheteroepitaxial GaAs and contribute to ongoing efforts toward CMOS-compatible Si-based nanophotonic technologies. Full article

A novel ultrasound-assisted method for synthesizing small, uniform stannous oxide (SnO) at room temperature was proposed in this work. The experimental results showed that the median particle size D₅₀ of SnO prepared by ultrasound was 5.2 μm, with a particle size distribution ranging from 2.9 to 8.7 μm and exhibiting a homogeneous micromorphology. This solves the problems of a median particle size D₅₀ higher than 20 μm, a wide range of particle size distributions, and uneven micromorphology in conventional preparation. The XRD and SEM results revealed that the introduction of ultrasound promoted the conversion of the intermediate product Sn₆O₄(OH)₄ to SnO, increased the exposure of the (001) and (002) crystal facets, promoted tetragonal growth, and suppressed particle aggregation, leading to finer and more uniformly distributed stannous oxide particles. BET and XPS analyses further demonstrated that ultrasound increased the specific surface area and the O-Sn²⁺ content, indicating enhanced surface reactivity. Full article

Wastewater containing triphenylmethane dyes such as malachite green (MG), discharged by textile and food industries, poses significant carcinogenic risks and ecological hazards. Conventional physical adsorption methods fail to degrade these pollutants effectively. To address this challenge, we focused on two-dimensional SnSe₂ semiconductor materials. While their narrow bandgap and unique structure confer exceptional optoelectronic properties, prior research has predominantly emphasized heterojunction systems. We synthesized SnSe₂ with well-defined hexagonal plate-like structures via a one-step hydrothermal method by precisely controlling precursor ratios (Sn:Se = 1:2) and reaction temperatures (120–240 °C). Systematic investigations revealed that hydrothermal temperature modulates the van der Waals forces between crystal planes, enabling selective exposure of (001) and (011) facets, as confirmed by XRD, SEM, and XPS analyses, thereby influencing the exposure of specific crystal facets. Experiments demonstrated that pure SnSe₂ synthesized at 150 °C achieved complete degradation of MG (40 mg/L) within 60 min under visible light irradiation, exhibiting a reaction rate constant (k) of 0.099 min⁻¹. By regulating the exposure ratio of the active (001)/(011) facets, we demonstrate that crystal facet engineering directly optimizes carrier separation efficiency, thereby substantially enhancing the catalytic performance of standalone SnSe₂. This work proposes a novel strategy for designing noble-metal-free, high-efficiency standalone photocatalysts, providing crystal facet-dependent mechanistic insights for the targeted degradation of industrial dyes. Full article

The structure and catalytic activity of Pd monolayers versus single Pd atoms were studied for the reverse water–gas shift reaction (rWGSR) at the anatase (101) and (001) facets for which Pd flat fragments have been observed experimentally. Thermodynamic and partial kinetic analyses of five steps of the rWGSR scheme were considered on the two facets. The projected density of states for the d-orbitals of single Pd atoms of the (101) facet of a-TiO₂ are compared to the ones for Pd atoms in both monolayers at (101) and (001) facets to interpret the different activity of Pd. The low activity of single Pd atoms is probably related to the (001) facet, while a Pd monolayer participates at the (101) facet due to its heterogeneity induced by the support. Full article

The adsorption of toxic metals onto iron oxides is a prevalent geochemical process in natural environments. Organic acids are known to modify the adsorption features of toxic ions through either competitive or cooperative effects. Nowadays, the toxic metal adsorption influenced by organic acids on iron oxides with varying facet exposures is not fully understood. This study explored how L-Aspartic acid (LA) influences Cr(VI) adsorption on two different exposure facets of lepidocrocite through batch adsorption experiments, in situ ATR-FTIR spectroscopy, and 2D-COS analysis. The results reveal that LA competes for available binding sites on lepidocrocite, consequently inhibiting the adsorption of Cr(VI). Rod-shaped lepidocrocite (R-LEP) owns more (001) facets and shows stronger Cr(VI) adsorption and LA competition than plate-like lepidocrocite (P-LEP), which mainly has (010) facets. The data for Cr(VI) uptake on both P-LEP and R-LEP within the effect of LA are well-fitted by the pseudo-second-order kinetics and the Freundlich isotherm model, suggesting chemical interaction as the dominant process for Cr(VI) coordination on lepidocrocite. Cr(VI) ions favor interaction with R-LEP over P-LEP, forming inner-sphere complexes on (001) facets. Concurrently, LA’s carboxyl groups can compete for the active sites on the lepidocrocite surfaces, engaging in anion exchange with hydroxyl groups, and forming outer-sphere and inner-sphere structures. This competitive effect is particularly pronounced in the R-LEP system. The current findings are expected to broaden insights into how the exposed facets of lepidocrocite influence the fate of Cr(VI) in the organic acid coexistence environment. Full article

The integration of noble metal nanoparticles (NPs) effectively modifies the electronic properties of semiconductor photocatalysts, leading to improved charge separation and enhanced photocatalytic performance. TiO₂ nanorods decorated with Au NPs were successfully synthesized using a cost-effective, rapid microwave-assisted method in H₂O₂ and HF media for methylene blue (MB) degradation under visible light illumination. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 physisorption, and UV–vis spectroscopy were employed to characterize the structures, morphologies, compositions, and photoelectronic properties of the as-synthesized materials. The fusing of Au NPs effectively alters the electronic structure of TiO₂, enhancing the charge separation efficiency and improved electrical conductivity. The HF treatment promotes the exposure of the highly reactive (001) and (101) crystalline facets. The improved photocatalytic activity of Au/TiO₂, achieving 97% efficiency, is attributed to the surface plasmon resonance (SPR) effect of the Au NPs and the presence of oxygen vacancies. The photodegradation of MB using the TiO₂/Au photocatalysts follows pseudo-first-order kinetics, highlighting the enhanced catalytic efficiency of the synthesized nanostructures. The exceptional properties of the binary Au/TiO₂ photocatalysts, including the SPR effect, exposed crystallographic faces, and efficient charge carrier separation through a decrease in the recombination of electrons and holes, contribute to the photocatalytic degradation of MB. Full article

The formation of barium sulfate scale is a persistent and formidable challenge across various industrial processes. In order to effectively mitigate this problem, this study proposed the development of an innovative azacrown ether-based macrocycle descaling agent. Using density functional theory, an in-depth analysis of the surface energy of different barium sulfate crystal facets was carried out, together with a detailed investigation into the adsorption properties of the functional groups on the (001) surface. A further comprehensive investigation was carried out to determine how changes in the nitrogen and oxygen atoms in the crown ether framework influence its adsorption affinity to barium ions. In addition, a detailed analysis was carried out to elucidate the molecular interactions between crown ethers with pyridine carboxylic acid side chains and barium sulfate. The newly developed decalcifying macrocycle descaling agent exhibited superior adsorption performance, achieving an adsorption energy for barium ions approximately −4.1512 ev higher than that of conventional DTPA decalcifiers. This remarkable improvement is mainly attributed to the pivotal role of electrostatic forces in the coordination process between the macrocycle descaling agent and barium ions, with an electrostatic potential value reaching −143.37 kcal/mol. This discovery not only introduces a novel approach to the removal of barium sulfate scale but also highlights the significant potential of macrocycle chemistry in industrial applications. Full article

In view of the flue gas characteristics of cement kilns in China, the development of low-temperature denitrification catalysts with excellent anti-poisoning performance has important theoretical and practical significance. In this work, a series of MnCeO_x@TiO₂ and tourmaline-containing MnCeO_x@TiO₂-T catalysts was prepared using a chemical pre-deposition method. It was found that the MnCeO_x@TiO₂-T2 catalyst (containing 2% tourmaline) exhibited the best low-temperature NH₃-selective catalytic reduction (NH₃-SCR) performance, yielding 100% NO_x conversion at 110 °C and above. When 100–300 ppm SO₂ and 10 vol.% H₂O were introduced to the reaction, the NO_x conversion of the MnCeO_x@TiO₂-T2 catalyst was still higher than 90% at 170 °C, indicating good anti-poisoning performance. The addition of appropriate amounts of tourmaline can not only preferably expose the active {001} facets of TiO₂ but also introduce the acidic SiO₂ and Al₂O₃ components and increase the content of Mn⁴⁺ and O_α on the surface of the catalyst, all of which contribute to the enhancement of reaction activity of NH₃-SCR and anti-poisoning performance. However, excess amounts of tourmaline led to the formation of dense surface of catalysts that suppressed the exposure of catalytic active sites, giving rise to the decrease in catalytic activity and anti-poisoning capability. Through an in situ DRIFTS study, it was found that the addition of appropriate amounts of tourmaline increased the number of Brønsted acid sites on the catalyst surface, which suppressed the adsorption of SO₂ and thus inhibited the deposition of NH₄HSO₄ and (NH₄)₂HSO₄ on the surface of the catalyst, thereby improving the NH₃-SCR performance and anti-poisoning ability of the catalyst. Full article

The formation of heterojunctions for efficient charge separation has been practiced for the preparation of efficient semiconductor-based photocatalysts for applications such as hydrogen production and environmental remediation. In this study, we synthesized a composite structure with a heterojunction between SnS₂ and TiO₂ through a microwave-assisted hydrothermal process, in which SnS₂ nanoparticles grew on nanocrystalline TiO₂ nanosheets preferentially at the exposed {101} facets. Appropriate exposure of the {001} and {101} facets of the TiO₂ nanosheet in the composite with a preferential growth of SnS₂ nanoparticles at the {101} facets was the origin of the charge separation following a direct Z-scheme mechanism to result in enhanced photocatalytic performances in photodegradation of organic dyes such as methylene blue (MB) and rhodamine B (RhB) compared to that of SnS₂ and TiO₂ alone. A plot of photodegradation rates vs. SnS₂ ratios in the composites gave an overall volcano-shaped curve with a maximum at the SnS₂ ratio of about 33% at which small SnS₂ nanoparticles were populated at the {101} facets of the TiO₂ nanosheets with a high surface area (118.2 m²g⁻¹). Our results suggest the microwave-assisted hydrothermal process can be a good synthetic approach for composite-based photocatalysts with a preferential heterojunction structure. Full article

We investigated the electronic structure of Mg-, Si-, and Zn-doped four-faceted [001]- and [110]-oriented SnO₂ nanowires using first-principles calculations based on the linear combination of atomic orbitals (LCAO) method. This approach, employing atomic-centered Gaussian-type functions as a basis set, was combined with hybrid density functional theory (DFT). Our results show qualitative agreement in predicting the formation of stable point defects due to atom substitutions on the surface of the SnO₂ nanowire. Doping induces substantial atomic relaxation in the nanowires, changes in the covalency of the dopant–oxygen bond, and additional charge redistribution between the dopant and nanowire. Furthermore, our calculations reveal a narrowing of the band gap resulting from the emergence of midgap states induced by the incorporated defects. This study provides insights into the altered electronic properties caused by Mg, Si, and Zn doping, contributing to the further design of SnO₂ nanowires for advanced electronic, optoelectronic, photovoltaic, and photocatalytic applications. Full article

Photoelectric catalysis is a green and efficient way to degrade pollutants, which has been paid more and more attention by researchers. Among them, Bi₂WO₃ has been proved to have excellent photocatalytic oxidation activity on its {001} facets. In this study, {001}-oriented facets with high exposure were successfully integrated into Bi₂WO₆ nanoplate arrays (Bi₂WO₆ NAs) to create a photoelectrode. This structure was grown in situ on an indium tin oxide (ITO) substrate. To promote photogenerated carrier separation efficiency and reduce agglomeration of Bi₂WO₆ photocatalysts, the electrochemical deposition of NiFe–layered double hydroxide (NiFe-LDH) and Ti₃C₂ (MXene) were introduced in this research to synergistically catalyze pollutant degradation. Morphology, spectral characterization, and electrochemical analysis jointly confirmed that the outstanding performance of hole capture behavior with LDH and electron conduction properties with MXene were the main reasons for the improvement in catalytic activity of the photoelectrode. Taking bisphenol A (BPA) as the model pollutant, the rate constant k of the NiFe-LDH/Ti₃C₂/Bi₂WO₆ NAs photoelectrode reaches 0.00196 min⁻¹ under photoelectrocatalytic (PEC) conditions, which is 4.5 times that of the pure Bi₂WO₆ NAs photoelectrode. This work provides a new way to improve the reaction kinetics of the PEC degradation of pollutants. Full article

Deposited by a reactive atmospheric pressure non-thermal TiCl₄/O₂/Ar plasma, anatase TiO₂ single crystal sheet-connected film exhibits two large exposed {001} facets and a high concentration of oxygen defects. Strong white photoluminescence centered at 542 nm has been observed with naked eyes, whose internal quantum efficiency is 0.62, and whose intensity is comparable to that of commercial fluorescent lamp interior coatings. Based on the simulation results of a hybrid global–analytical model developed on this atmospheric pressure non-equilibrium plasma system, the mechanism of a self-confined growth of single crystal sheets was proposed. A high concentration of oxygen defects is in situ incorporated into the anatase crystal lattice without damaging its crystallographic orientation. This method opens a new way to construct 3D porous metal-oxide single crystal sheet-connected films with two exposing high energy surfaces and a large concentration of oxygen defects. Full article

Al-Sc alloys containing high Sc content are employed as sputtering targets for the fabrication of high-performance piezoelectric films during magnetic sputtering. Due to the high proportion of the Al₃Sc phase, their workability is quite limited, and they are often used in the as-cast state. In this study, the crystallography of Al₃Sc dendrites in as-casted Al-10at.%Sc and Al-20at.%Sc samples is examined using electron backscatter diffraction (EBSD). With increasing Sc content, the fraction of Al₃Sc also increases. The Al₃Sc dendrites exhibit a cubic relationship with the Al matrix in both alloys. However, in Al-10%Sc alloys, the facets of the Al₃Sc dendrites are parallel to {001} planes, while twinning is observed in Al-20at.%. The twinning plane is parallel to the {111} plane, and the dendrite growth direction aligns with the <110> directions. The different morphologies of the dendrite structures in these two alloys are discussed in relation to thermodynamic and kinetic considerations based on the phase diagram and nucleation rate. Full article

The surface configurations of the low-index facets of a set of spinel oxides are investigated using DFT+U calculations to derive surface energies and predict equilibrium nanoparticle shapes via the Wulff construction. Two very different conditions are investigated, corresponding to application either in heterogeneous catalysis or in electrocatalysis. First, the bare stoichiometric surfaces of NiFe₂O₄, CoFe₂O₄, NiCo₂O₄, and ZnCo₂O₄ spinels are studied to model their use as high-temperature oxidation catalysts. Second, focusing attention on the electrochemical oxygen evolution reaction (OER) and on the CoFe₂O₄ inverse spinel as the most promising OER catalyst, we generate surface configurations by adsorbing OER intermediates and, in an innovative study, we recalculate surface energies taking into account adsorption and environmental conditions, i.e., applied electrode potential and O₂ pressure. We predict that under OER operating conditions, (111) facets are dominant in CoFe₂O₄ nanoparticle shapes, in fair agreement with microscopy measurements. Importantly, in the OER case, we predict a strong dependence of nanoparticle shape upon O₂ pressure. Increasing O₂ pressure increases the size of the higher-index (111) and (110) facets at the expense of the (001) more catalytically active facet, whereas the opposite occurs at low O₂ pressure. These predictions should be experimentally verifiable and help define the optimal OER operative conditions. Full article