Search Results (29)

The search for effective and reliable methods of photosensitization of oxide-based semiconductor materials is of great significance for their use in photocatalytic reactions of hydrogen production and environmental remediation under natural sunlight. The present study is focused on partial substitution of titanium with manganese in the structure of layered perovskite-like titanate Na₂La₂Ti₃O₁₀, which was employed to yield a series of photocatalytically active materials, Na₂La₂Mn_xTi_3−xO₁₀ (x = 0.002–1.0), as well as their protonated forms H₂La₂Mn_xTi_3−xO₁₀ and nanosheets. It was established that the manganese cations Mn⁴⁺ are embedded in the middle sublayer of oxygen octahedra in the perovskite slabs La₂Mn_xTi_3−xO₁₀²⁻ and that the maximum achievable manganese content x in the products is ≈0.9. The partial cationic substitution in the perovskite sublattice led to a pronounced contraction of the optical band gap from 3.20 to 1.35 eV (depending on x) and, therefore, allowed the corresponding photocatalysts to utilize not only ultraviolet, but also visible and near-infrared light with wavelengths up to ≈920 nm. The materials obtained were tested as photocatalysts of hydrogen evolution from aqueous methanol, and the greatest activity in this reaction was demonstrated by the samples with low manganese contents (x = 0.002–0.01). However, the materials with greater substitution degrees may be of high interest for use in other photocatalytic processes and, especially, in thermophotocatalysis due to their improved ability to absorb the near-infrared part of solar radiation. Full article

Layered Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been exfoliated into nanosheets in aqueous tetrabutylammonium hydroxide and systematically investigated as hydrogen evolution photocatalysts. The nanosheets were tested both in as-prepared pristine form and after reassembly by two methods (simple filtration and precipitation by hydrochloric acid). The nanosheet-based samples demonstrated by up to 88 times greater photocatalytic performance in comparison with the bulk precursors and, after modification with a Pt cocatalyst, provided apparent quantum efficiency of hydrogen generation up to 14.2% in 1 mol.% aqueous methanol and 3.15% in pure water. It was established that the form in which the nanosheets are used strongly affects the hydrogen production efficiency: the latter typically decreases when moving from the pristine nanosheets to filtered ones and then to those restacked by hydrochloric acid, which is determined by the difference in their physical–chemical characteristics being influenced by the reassembly approach. Full article

Water molecules from the environment or human breath are one of the main factors affecting the accuracy, efficiency, and long-term stability of electronic gas sensors. In this contribution, yttrium (Y)-doped La₂Ti₂O₇ (LTO) nanosheets were synthesized by a hydrothermal reaction, demonstrating improved proton conductivity compared to their non-doped counterparts. The response of Y-doped LTO with the optimal doping concentration to 100 ppm NO₂ at 43% relative humidity (RH) was −21%, which is four times higher than that of bare La₂Ti₂O₇. As the humidity level increased to 75%, the response of Y-doped LTO further increased to −64%. Unlike the gas doping effect observed in previous studies of semiconducting metal oxides, the sensing mechanism of Y-doped LTO nanosheets is based on the enhanced dissociation of H₂O in the presence of target NO₂ molecules, leading to the generation of more protons for ion conduction. This also resulted in a greater resistance drop and thus a larger sensing response at elevated humidity levels. Our work demonstrates that proton-conductive oxide materials are promising gas-sensing materials under humid conditions. Full article

The CsPbBr₃ perovskite exhibits strong environmental stability under light, humidity, temperature, and oxygen conditions. However, in all-inorganic perovskite solar cells (PSCs), interface defects between the carbon electrode and CsPbBr₃ limit the carrier separation and transfer rates. We used black phosphorus (BP) nanosheets as the hole transport layer (HTL) to construct an all-inorganic carbon-based CsPbBr₃ perovskite (FTO/c-TiO₂/m-TiO₂/CsPbBr₃/BP/C) solar cell. BP can enhance hole extraction capabilities and reduce carrier recombination by adjusting the interface contact between the perovskite and the carbon layer. Due to the coordination of the energy structure related to interface charge extraction and transfer, BP, as a new type of hole transport layer for all-inorganic CsPbBr₃ solar cells, achieves a power conversion efficiency (PCE) that is 1.43% higher than that of all-inorganic carbon-based CsPbBr₃ perovskite solar cells without a hole transport layer, reaching 2.7% (Voc = 1.29 V, Jsc = 4.60 mA/cm², FF = 48.58%). In contrast, the PCE of the all-inorganic carbon-based CsPbBr₃ perovskite solar cells without a hole transport layer was only 1.27% (Voc = 1.22 V, Jsc = 2.65 mA/cm², FF = 39.51%). The unencapsulated BP-based PSCs device maintained 69% of its initial efficiency after being placed in the air for 500 h. In contrast, the efficiency of the PSC without HTL significantly decreased to only 52% of its initial efficiency. This indicates that BP can effectively enhance the PCE and stability of PSCs, demonstrating its great potential as a hole transport material in all-inorganic perovskite solar cells. BP as the HTL for CsPbBr₃ PSCs can passivate the perovskite interface, enhance the hole extraction capability, and improve the optoelectronic performance of the device. The subsequent doping and compounding of the BP hole transport layer can further enhance its photovoltaic conversion efficiency in PSCs. Full article

Encapsulating Cs₄PbBr₆ quantum dots in silicon nano-sheets not only stabilizes the halide perovskite, but also takes advantage of the nano-sheet for a compatible integration with the traditional silicon semiconductor. Here, we report the preparation of un-passivated Cs₄PbBr₆ ellipsoidal nanocrystals and pseudo-spherical quantum dots in silicon nano-sheets and their enhanced photoluminescence (PL). For a sample with low concentrations of quantum dots in silicon nano-sheets, the emission from Cs₄PbBr₆ pseudo-spherical quantum dots is quenched and is dominated with Pb²⁺ ion/silicene emission, which is very stable during the whole measurement period. For a high concentration of Cs₄PbBr₆ ellipsoidal nanocrystals in silicon nano-sheets, we have observed Förster resonance energy transfer with up to 87% efficiency through the oscillation of two PL peaks when UV excitation switches between on and off, using recorded video and PL lifetime measurements. In an area of a non-uniform sample containing both ellipsoidal nanocrystals and pseudo-spherical quantum dots, where Pb²⁺ ion/silicene emissions, broadband emissions from quantum dots, and bandgap edge emissions (515 nm) appear, the 515 nm peak intensity increases five times over 30 min of UV excitation, probably due to a photon recycling effect. This irradiated sample has been stable for one year of ambient storage. Cs₄PbBr₆ quantum dots encapsulated in silicon nano-sheets can lead to applications of halide perovskite light emitting diodes (PeLEDs) and integration with traditional semiconductor materials. Full article

Halide perovskite Cs₃Bi₂Br₉ (CBB) has excellent potential in photocatalysis due to its promising light-harvesting properties. However, its photocatalytic performance might be limited due to the unfavorable charge carrier migration and water-induced properties, which limit the stability and photocatalytic performance. Therefore, we address this constraint in this work by synthesizing a stable halide perovskite heterojunction by introducing hydrogen titanate nanosheets (H₂Ti₃O₇-NS, HTiO-NS). Optimizing the weight % (wt%) of CBB enables synthesizing the optimal CBB/HTiO-NS, CBHTNS heterostructure. The detailed morphology and structure characterization proved that the cubic shape of CBB is anchored on the HTiO-NS surface. The 30 wt% CBB/HTiO-NS-30 (CBHTNS-30) heterojunction showed the highest BnOH photooxidation performance with 98% conversion and 75% benzoic acid (BzA) selectivity at 2 h under blue light irradiation. Detailed optical and photoelectrochemical characterization showed that the incorporating CBB and HTiO-NS widened the range of the visible-light response and improved the ability to separate the photo-induced charge carriers. The presence of HTiO-NS has increased the oxidative properties, possibly by charge separation in the heterojunction, which facilitated the generation of superoxide and hydroxyl radicals. A possible reaction pathway for the photocatalytic oxidation of BnOH to BzH and BzA was also suggested. Furthermore, through scavenger experiments, we found that the photogenerated h⁺, e⁻ and •O₂⁻ play an essential role in the BnOH photooxidation, while the •OH have a minor effect on the reaction. This work may provide a strategy for using HTiO-NS-based photocatalyst to enhance the charge carrier migration and photocatalytic performance of CBB. Full article

Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications. Full article

Xylene gas is highly toxic, can irritate the skin, and is also very harmful to the body. Therefore, it is necessary to prepare sensors that can accurately detect xylene. In this paper, NiTiO₃ nanoparticles were synthesized by the hydrothermal method and used to modify NiO, and a NiTiO₃-modified NiO (NiTiO₃-NiO) nanosheet material was successfully prepared. Its microstructure and internal composition were observed and analyzed by various characterization methods. When detecting 100 ppm xylene gas at the optimum temperature, comparing the response level of the NiTiO₃-NiO sensor with that of a pure nickel oxide sensor, the former was 20 times that of the latter, and the sensitivity was greatly improved. In a 100 ppm xylene gas environment, the response level of the sensor reached 21, the minimum detection limit was 1 ppm, and the recovery time was 135.75 s. NiTiO₃ is a perovskite-structured material, with many active sites and good catalytic properties that promote redox reactions. Full article

Photocatalytic activity of HB₂Nb₃O₁₀ perovskite nanosheets (B = Ca, Sr) has been systematically investigated in the reactions of hydrogen production, depending on the method of the photocatalyst preparation: using the pristine nanosheets in the parent suspension without reassembly, filtered nanosheets as well as nanosheets restacked by hydrochloric acid. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample as well as stability and pH of the reaction suspension. Exfoliation of the niobates into nanosheets allowed obtaining efficient photocatalysts surpassing the initial bulk materials in the activity up to 55 times and providing apparent quantum efficiency up to 20.8% after surface decoration with a Pt cocatalyst. Among the reassembled samples, greater hydrogen evolution activity was exhibited by simply filtered nanosheets that, unlike the HCl-restacked ones, were found to possess much lower specific surface area in a dry state but contain a perceptible amount of tetrabutylammonium cations on the surface. The activity difference, potentially, is associated with the fact that the filtered nanosheets undergo ultrasonic disaggregation before photocatalytic tests much easier than their HCl-restacked counterparts and, thanks to this, have greater active surface in the reaction suspension. In addition, the enhanced activity of the filtered nanosheets may be due to the presence of tetrabutylammonium as an organic modifier on their surface, which is consistent with the high photocatalytic performance of organically modified layered perovskites considered in our previous reports. Full article

In the present research work, the state-of-art label-free electrochemical genosensing platform was developed based on the hybridization process in the presence of [Fe(CN)₆]^3−/4− as an efficient redox probe for sensitive recognition of the miRNA-21 in human gastric cell lines samples. To attain this aim, perovskite nanosheets were initially synthesized. Afterward, the obtained compound was combined with the graphene oxide resulting in an effective electrochemical modifier, which was dropped on the surface of the Au electrode. Then, AuNPs (Gold Nano Particles) have been electrochemically-immobilized on perovskite-graphene oxide/Au-modified electrode surface through the chronoamperometry (CA) technique. Finally, a self-assembling monolayer reaction of ss-capture RNA ensued by the thiol group at the end of the probe with AuNPs on the modified electrode surface. miRNA-21 has been cast on the Au electrode surface to apply the hybridization process. To find out the effectiveness of the synthesized modifier agent, the electrochemical behavior of the modified electrode has been analyzed through DPV (differential pulse voltammetry) and CV (cyclic voltammetry) techniques. The prepared biomarker-detection bioassay offers high sensitivity and specificity, good performance, and appropriate precision and accuracy for the highly-sensitive determination of miRNA-21. Different characterization methods have been used, such as XRD, Raman, EDS, and FE-SEM, for morphological characterization and investigation of particle size. Based on optimal conditions, the limit of detection and quantification have been acquired at 2.94 fM and 8.75 fM, respectively. Furthermore, it was possible to achieve a wide linear range which is between 10⁻¹⁴ and 10⁻⁷ for miRNA-21. Moreover, the selectivity of the proposed biosensing assay was investigated through its potential in the detection of one, two, and three-base mismatched sequences. Moreover, it was possible to investigate the repeatability and reproducibility of the related bio-assay. To evaluate the hybridization process, it is important that the planned biomarker detection bio-assay could be directly re-used and re-generated. Full article

Heterojunctions based on metal halide perovskites (MHPs) are promising systems for the photocatalytic hydrogen evolution reaction (HER). In this work, we coupled Cs₃Bi₂Br₉ nanocrystals (NCs), obtained by wet ball milling synthesis, with g-C₃N₄ nanosheets (NSs), produced by thermal oxidation of bulk g-C₃N_4, in air. These methods are reproducible, inexpensive and easy to scale up. Heterojunctions with different loadings of Cs₃Bi₂Br₉ NCs were fully characterised and tested for the HER. A relevant improvement of H₂ production with respect to pristine carbon nitride was achieved at low NCs levels reaching values up to about 4600 µmol g⁻¹ h⁻¹. This work aims to provide insights into the synthesis of inexpensive and high-performing heterojunctions using MHP for photocatalytic applications. Full article

Gadolinium aluminate is an effective host for doping with various ions, and it can emit various colors. However, it is not easy to prepare transparent ceramics of gadolinium aluminate using traditional methods, although transparent ceramics are very suitable for solid lighting. In this work, a two-dimensional guidance strategy has been successfully carried out for perovskite-structured aluminate ceramic film. Through the two-dimensional interfacial reaction, GdAlO₃:Eu³⁺ (GAP:Eu³⁺) transparent ceramic films were successfully fabricated using nanosheets exfoliated from layered gadolinium hydroxide, a rare earth source. The final films were tested by characterization techniques, including XRD, SEM, TEM, FT-IR, PLE/PL spectroscopy, temperature-dependent PL spectroscopy, and luminescence decay analysis. The perovskite film of transparent ceramics can be obtained by calcining LRH nanosheets on the substrate of amorphous alumina at 1550 °C in air with a reaction time of 2 h. During the interface reaction, temperature-dependent element diffusion takes the dominant role, and increased reactants take in the reaction with increasing calcination temperature. The grain for ceramic film is only 2–5 μm, which is much smaller than that for bulk ceramic. This is mainly due to the lower temperature and the interface diffusion. Ceramic film has a high transmittance larger than 90% at the visible range. Upon UV excitation at 254 nm, the film exhibits intense emission at the red wavelength range. The outcomes described in this work may have wide implications for transparent ceramics and layered rare-earth hydroxides. Full article

Two-dimensional (2D) organic−inorganic perovskites have great potential for the fabrication of next-generation photodetectors owing to their outstanding optoelectronic features, but their utilization has encountered a bottleneck in anisotropic carrier transportation induced by the unfavorable continuity of the thin films. We propose a facile approach for the fabrication of 0D ZnO quantum dot (QD)/2D (PEA)₂PbI₄ nanosheet hybrid photodetectors under the atmospheric conditions associated with the ZnO QD chloroform antisolvent. Profiting from the antisolvent, the uniform morphology of the perovskite thin films is obtained owing to the significantly accelerated nucleation site formation and grain growth rates, and ZnO QDs homogeneously decorate the surface of (PEA)₂PbI₄ nanosheets, which spontaneously passivate the defects on perovskites and enhance the carrier separation by the well-matched band structure. By varying the ZnO QD concentration, the Ion/Ioff ratio of the photodetectors radically elevates from 78.3 to 1040, and a 12-fold increase in the normalized detectivity is simultaneously observed. In addition, the agglomeration of perovskite grains is governed by the annealing temperature, and the photodetector fabricated at a relatively low temperature of 120 °C exhibits excellent stability after a 50-cycle test in the air condition without any encapsulation. Full article

Quantum dots (QDs) have an unparalleled ability to mimic true colors due to their size-tunable optical and electronic properties, which make them the most promising nanoparticles in various fields. Currently, the majority of QDs available in the market are cadmium, indium, and lead-based materials but the toxicity and unstable nature of these QDs restricts their industrial and practical applications. To avoid using heavy metal ions, especially cadmium, the current research is focused on the fabrication of perovskite and vanadate QDs. Herein, we report the facile synthesis of a novel and cost-effective CsVO₃ QDs for the first time. The sizes of the CsVO₃ QDs produced were tuned from 2 to 10 nm by varying the reaction temperature from 140 to 190 °C. On increasing QD size, a continuous red shift was observed in absorption and emission spectra, signifying the presence of quantum confinement. In addition, along with CsVO₃ QDs, the CsVO₃ nanosheets self-assembled microflower-like particles were found as residue after the centrifugation; the X-ray diffraction indicated an orthorhombic structure. Under 365 nm excitation, these CsVO₃ microflower-like particles exhibited broad emission with CIE coordinates in the white emission region. The acquired results suggest that CsVO₃ QDs may represent a new class of cadmium-free materials for optoelectronic and biomedical applications. Full article

Chemically exfoliated nanosheets have been extensively employed as functional nanofillers for the fabrication of polymer nanocomposites due to their remarkable electrical, magnetic and optical properties. However, achieving a good dispersion of charged nanosheets in polymer matrix, which will determine the performance of polymer nanocomposites, remains a challenge. Herein, we investigated the dispersion and aggregation behavior of negatively charged Ca₂Nb₃O₁₀ (CNO) perovskite nanosheets in negatively charged sodium alginate (SA) aqueous dispersion using dynamic light scattering (DLS). When CNO nanosheets meet with SA, aggregation and coagulation inevitably occurred owing to the absorption of SA on nanosheets. By controlling the electrostatic attraction between positively charged poly(ethylene imine) (PEI) and negatively charged SA, the charge density and hydrodynamic size of SA can be tuned to enable the good dispersion of CNO nanosheets in SA. This result may provide a new strategy to achieve the good dispersion of charged nanosheets in charged polymers for the rational design of multifunctional nanocomposites. Full article