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Development of robust and cost-effective smart materials requires rational chemical nanoengineering to provide viable technological solutions for a wide range of applications. Recently, a powerful approach based on the electrografting of diazonium salts has attracted a great deal of attention due to its numerous technological advantages. Several studies on graphene-based materials reveal that the covalent attachment of aryl groups via the above approach could lead to additional beneficial properties of this versatile material. Here, we developed the covalently linked metalorganic wires on two transparent, cheap, and conductive materials: fluorine-doped tin oxide (FTO) and FTO/single-layer graphene (FTO/SLG). The wires are terminated with nitrilotriacetic acid metal complexes, which are universal molecular anchors to immobilize His6-tagged proteins, such as biophotocatalysts and other types of redox-active proteins of great interest in biotechnology, optoelectronics, and artificial photosynthesis. We show for the first time that the covalent grafting of a diazonium salt precursor on two different electron-rich surfaces leads to the formation of the molecular wires that promote p-doping of SLG concomitantly with a significantly enhanced unidirectional cathodic photocurrent up to 1 ?A cm-2. Density functional theory modeling reveals that the exceptionally high photocurrent values are due to two distinct mechanisms of electron transfer originating from different orbitals/bands of the diazonium-derived wires depending on the nature of the chelating metal redox center. Importantly, the novel metalorganic interfaces reported here exhibit minimized back electron transfer, which is essential for the maximization of solar conversion efficiency. © 2022 American Chemical Society. All rights reserved.

A new indium precursor, namely, indium(II) chloride, was tested as a precursor in the synthesis of ternary Ag−In−S and quaternary Ag−In−Zn−S nanocrystals. This new precursor, being in fact a dimer of Cl2In−InCl2 chemical structure, is significantly more reactive than InCl3, typically used in the preparation of these types of nanocrystals. This was evidenced by carrying out comparative syntheses under the same reaction conditions using these two indium precursors in combination with the same silver (AgNO3) and zinc (zinc stearate) precursors. In particular, the use of indium(II) chloride in combination with low concentrations of the zinc precursor yielded spherical-shaped (D = 3.7−6.2 nm) Ag−In−Zn−S nanocrystals, whereas for higher concentrations of this precursor, rodlike nanoparticles (L = 9−10 nm) were obtained. In all cases, the resulting nanocrystals were enriched in indium (In/Ag = 1.5−10.3). Enhanced indium precursor conversion and formation of anisotropic, longitudinal nanoparticles were closely related to the presence of thiocarboxylic acid type of ligands in the reaction mixture. These ligands were generated in situ and subsequently bound to surfacial In(III) cations in the growing nanocrystals. The use of the new precursor of enhanced reactivity facilitated precise tuning of the photoluminescence color of the resulting nanocrystals in the spectral range from ca. 730 to 530 nm with photoluminescence quantum yield (PLQY) varying from 20 to 40%. The fabricated Ag−In−S and Ag−In−Zn−S nanocrystals exhibited the longest, reported to date, photoluminescence lifetimes of ∼9.4 and ∼1.4 μs, respectively. It was also demonstrated for the first time that ternary (Ag−In− S) and quaternary (Ag−In−Zn−S) nanocrystals could be applied as efficient photocatalysts, active under visible light (green) illumination, in the reaction of aldehydes reduction to alcohols.

SnS-Ti/TiO2photoanode for anticancer drug degradation.

This paper presents application of Finite Element Method in designing of a vibroisolated object. A model of power generator of 113 MW was chosen for the analysis. Such the generator is used in one of power plants in Silesia district. Several frequency domain dynamic analyses aimed at assessment of influence of vibroisolation on acceleration level of the generator foundation were performed. Three different models of the generator were considered. For the purposes of verification of the obtained results measured vibration accelerations were used.

Inspired by the easy intercalation of quinoxaline heterocyclic aromatic amines (HAAs) in double-stranded DNA (dsDNA), we synthesized a nucleobase-functionalized molecularly imprinted polymer (MIP) as the recognition unit of an impedimetric chemosensor for the selective determination of a 2-amino-3,7,8-trimethyl-3H-imidazo[4,5-f]quinoxaline (7,8-DiMeIQx) HAA. HAAs are generated in meat and fish processed at high temperatures. They are considered to be potent hazardous carcinogens. The MIP film was prepared by potentiodynamic electropolymerization of a pre-polymerization complex of two adenine- and one thymine-substituted bis(2,2′-bithien-5-yl)methane functional monomer molecules with one 7,8-DiMeIQx template molecule, in the presence of the 2,4,5,2′,4′,5′-hexa(thiophene-2-yl)-3,3′-bithiophene cross-linking monomer, in solution. The as-formed MIP chemosensor allowed for the selective impedimetric determination of 7,8-DiMeIQx in the 47 to 400 μM linear dynamic concentration range with a limit of detection of 15.5 μM. The chemosensor was successfully applied for 7,8-DiMeIQx determination in the pork meat extract as a proof of concept.

Herein, we report the potential-driven electrochemical transformation carried out in basic media of two Ni

A new and active material in the form of ZnIn2S4 microspheres decorated by CuInS2 quantum dots have been obtained by hydrothermal method for the first time. The optimum amount of CuInS2 quantum dots (1.13 wt.%) introduced into rection medium during ZnIn2S4 microspheres synthesis increased the photocatalytic H2 generation rate by 2.5 times than that of bare ZnIn2S4 photocatalysis under visible light irradiation. This sample exhibited strong photoactivity in the extended visible range up to 540 nm with 30.6% apparent quantum efficiency (λ = 420 nm).

The structural and chemical modification of TiO2 nanotubes (NTs) by the deposition of a well-controlled Au deposit was investigated using a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), Raman measurements, UV-Vis spectroscopy and photoelectrochemical investigations. The fabrication of the materials focused on two important factors: the deposition of Au nanoparticles (NPs) in UHV (ultra high vacuum) conditions (1–2 × 10−8 mbar) on TiO2 nanotubes (NTs) having a diameter of ∼110 nm, and modifying the electronic interaction between the TiO2 NTs and Au nanoparticles (NPs) with an average diameter of about 5 nm through the synergistic effects of SMSI (Strong Metal Support Interaction) and LSPR (Local Surface Plasmon Resonance). Due to the formation of unique places in the form of “hot spots”, the proposed nanostructures proved to be photoactive in the UV-Vis range, where a characteristic gold plasmonic peak was observed at a wavelength of 580 nm. The photocurrent density of Au deposited TiO2 NTs annealed at 650 °C was found to be much greater (14.7 μA cm−2) than the corresponding value (∼0.2 μA cm−2) for nanotubes in the as-received state. The IPCE (incident photon current efficiency) spectral evidence also indicates an enhancement of the photoconversion of TiO2 NTs due to Au NP deposition without any significant change in the band gap energy of the titanium dioxide (Eg ∼3.0 eV). This suggests that a plasmon-induced resonant energy transfer (PRET) was the dominant effect responsible for the photoactivity of the obtained materials.

Developing functional materials from biomass is a significant research subject due to its unique structure, abundant availability, biodegradability and low cost. A series of chitosan–lignin (CL) composites were prepared through a hydrothermal method by varying the weight ratio of chitosan and lignin. Subsequently, these CL composites were combined with titania (T) to form a nanocomposite (T/CL) using sol–gel and hydrothermal based methods. T/CL nanocomposites exhibited improved photocatalytic performance in comparison with sol–gel and hydrothermally prepared pristine titania (SGH-TiO2), towards the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (Bnald) under UV (375 nm) and visible light (515 nm). More specifically, the 75T/CL(25 : 75) nanocomposite (a representative photocatalyst from the 75T/CL nanocomposite series) showed very high selectivity (94%) towards Bnald at 55% BnOH conversion under UV light. Whereas, SGH-TiO2 titania exhibited much lower (68%) selectivity for Bnald at similar BnOH conversion. Moreover, the 75T/CL(25 : 75) nanocomposite also showed excellent Bnald selectivity (100%) at moderate BnOH conversion (19%) under visible light. Whereas, SGH-TiO2 did not show any activity for BnOH oxidation under visible light. XPS studies suggest that the visible light activity of the 75T/CL(25 : 75) nanocomposite is possibly related to the doping of nitrogen into titania from chitosan. However, according to UV-visible-DRS results, no direct evidence pertaining to the decrease in band-gap energy of titania was found upon coupling with the CL composite and the visible light activity was attributed to N-doping of titania. Overall, it was found that T/CL nanocomposites enhanced the photocatalytic performance of titania via improved light harvesting and higher selectivity through mediation of active radical species.

Applied cutting-edge electronic structure and phonon simulations provide a reliable knowledge about the stability of perovskite structures and their electronic properties, which are crucial for des...

CuO/ceria and CuO/Y-doped ceria catalysts were synthesized. The Y-modified supports (1.0, 2.5 and 5.0 wt% Y2O3) were prepared by coprecipitation. CuO (3 wt% Cu) was loaded by deposition-precipitation. Having in mind the known effect of Y3+ modification for the generation of oxygen vacancies in ceria, its positive role on the water-gas shift (WGS) performance was expected. However, the catalytic test showed a trend of decreased WGS activity by increasing the Y-dopant amount, nevertheless that the differences were not very substantial. On the basis of XRD, XPS, EPR, Raman spectroscopy and H2-TPR results the explanation related to the key role of the oxygen mobility influenced by Y-doping could be proposed. The reason of the inferior WGS performance with increasing Y-content would be the higher amount of surface oxygen vacancies around Y3+ ions which disturbed the Cu–Ovac–Ce active sites for WGS reaction. Though, during the long run catalytic tests in WGS reaction a positive effect of Y-doping for improved stability of CuO/ceria catalysts was evidenced.

The demands for high-purity hydrogen required in fuel-cell applications impose new goals and challenges for design of well performing water-gas shift (WGS) catalysts. Gold-based catalysts have exhibited high activity in the WGS reaction at low temperature. Preparation of appropriate and economically viable supports with complex composition by various synthesis procedures is an attractive approach to WGS performance improvement. The effect of two different preparation methods (wet impregnation or mechanical mixing) and ceria content (10, 20 or 30 wt%) on textural, structural, surface and reductive properties and WGS activity of gold catalysts was studied. Additionally, the role of Y2O3 as a promoter of ceria was examined. Long-term stability test was carried out at 260 °C over the most active catalyst. The composition of the best performing sample (composed of about 70 wt% alumina), prepared by mechanical mixing, was considered promising in case of practical applications because of its cost efficiency. The combination of gold nanoparticles and alumina supported Y-doped ceria proved an advantageous approach for developing new catalytic formulations with high effectiveness in clean hydrogen production.

Stable polymeric materials with embedded nano-objects, retaining their specific properties, are indispensable for the development of nanotechnology. Here, a method to obtain Pt, Pd, Au, and Ag nanoparticles (ca. 10 nm, independent of the metal) by the reduction of their ions in pectin, in the absence of additional reducing agents, is described. Specific interactions between the pectin functional groups and nanoparticles were detected, and they depend on the metal. Bundles and protruding nanoparticles are present on the surface of nanoparticles/pectin films. These films, deposited on the electrode surface, exhibit electrochemical response, characteristic for a given metal. Their electrocatalytic activity toward the oxidation of a few exemplary organic molecules was demonstrated. In particular, a synergetic effect of simultaneously prepared Au and Pt nanoparticles in pectin films on glucose electro-oxidation was found.

The morphology of a series of Bi–B co-doped titanium oxide photocatalysts and its optical properties were characterized. The results suggested that boron and bismuth as co-dopants were incorporated into the framework of titanium matrix. For the B and Bi-doped TiO2 samples, surface area decreased while the Bi content increased. Based on the photoluminescence spectra, a decrease in recombination rate of photogenerated carriers was observed with the increasing amount from 0.5 to 3 mol% of Bi in Bi–B–TiO2 composites. The most active photocatalyst in 5-fluorouracil (5-FU) photodegradation was 3 mol% of Bi in Bi–B–TiO2. The effects of operating parameters: pH, drug concentration and natural organic matter presence (NOM) in the effluent from wastewater treatment plant, were investigated. The highest efficiency of 5-FU photodegradation was observed at neutral pH for the drug concentration equal to 1 mg/L and photocatalyst of 0.05 g/L. While in distilled water solutions, the catalyst showed good removal efficiency of the drug, the process was totally inhibited by NOM in the complex matrix which was the treated sewage, what could be connected with the internal filter and scavenging effect. Based on the identification of organic and inorganic by-products of the photooxidation, the pathway of 5-FU degradation was proposed. The mineralization was poor (5–7%) in the case of both 3Bi–B–TiO2 and pure TiO2 for the drug of 50 mg/L, but photocatalytic oxidation of drug led to non-toxic products toward Lemma minor.

Photocatalytic water splitting has great potential in solar-hydrogen production as a low-cost and environmentally friendly method. Different unique techniques used to obtain photocatalysts with various modifications to improve H2 generation have been introduced. In the present work, SrTiO3 was successfully synthesized via the solvothermal method in the presence of ionic liquid (IL) - 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) followed by surface decoration with Pt particles using the photodeposition method. The effect of the noble metal content and presence of IL on the morphology, optical and surface properties of SrTiO3, thereby the effectiveness of hydrogen generation, has been thoroughly examined and presented. Unexpectedly, the presence of [BMIM][Br] at the SrTiO3 surface affected the interaction between the semiconductor surface and platinum particles formed throughout photodeposition. Platinum particles at the surface of SrTiO3_IL were found to be in the form of 2D clusters with a size of 1 nm. In comparison, Pt deposited on SrTiO3 photocatalyst without application of IL created larger, three-dimensional structures with a diameter exceeding 5 nm. This is the reason why the total amount of platinum deposited on the SrTiO3_IL sample is smaller than that on SrTiO3 and justifies a higher efficiency of hydrogen generation of Pt modified SrTiO3 photocatalyst in comparison to SrTiO3 prepared in the presence of IL. The mechanism of H2 generation in the water-splitting reaction in the presence of SrTiO3_Pt photocatalyst was discussed.

The structural and chemical modification of TiO

One of the challenges in research into photoelectrocatalytic (PEC) degradation of pollutants is finding the appropriate photoanode material, which has a significant impact on the process efficiency. Among all others, photoelectrodes based on an ordered TiO

Modifying the geometric and surface parameters of oriented TiO2 nanotubes (NTs) is beneficial to the utilization of solar energy for chemical reactions, and this performance may be further improved. Thus, the effects of adding an ionic liquid (IL), 1-butylpiridinium chloride [BPy][Cl], and the effects of the water content and preparation conditions on the surface morphological, physicochemical, photocatalytic, and photoelectrochemical properties of TiO2 NTs were thoroughly examined and presented. The anodic oxidation of Ti foil in an organic electrolyte containing a small amount of [BPy][Cl] allowed for obtaining IL_NTs with a well-ordered structure, even at low voltages (10 V). Additionally, the application of [BPy][Cl] enabled one of the geometric parameters of the IL_NTs, namely, the diameter, to be tuned, whereas the length remained the same (i.e., control over the diameter was first noted). Improvements in the photocatalytic and photoelectrochemical activities of the IL_NTs in comparison with those o...

Understanding how Sb atoms are located in the ZnO crystal lattice and how they affect the layer parameters is essential to obtain p-type conductivity in ZnO:Sb. In this paper, the results of our extensive research (XPS, Raman, X-Ray, SIMS) of Sb doped ZnO films grown by Molecular Beam Epitaxy are presented. It is shown with use of high resolution X-ray Photoemission Spectroscopy (XPS) that three charge states of the Sb impurity: Sb3+, Sb5+, and Sb3− can exist in ZnO:Sb layers. The dominant charge state of Sb ions is 3 + while the contribution of 5 + is very low. The relative fraction of Sb atoms located at the Zn sites is about ∼90%, while ∼10% are incorporated in oxygen sites. It was found that increasing the Sb content in the layers increases the intensity of Raman modes at 511 cm−1, 533 cm−1, and 575 cm−1, which confirms their correlation with Sb doping. Additionally, a blue shift of the E2High Raman mode of ZnO was observed, related to the increase of strain in the oxygen sublattice. The relation between strain and stress for different Sb chemical states (Sb3+, Sb5+, Sb3−) in ZnO is calculated and compared with experimental results.

Gold catalysts on Y-doped ceria dispersed on high surface area ?-Al2O3 were synthesized and tested in preferential CO oxidation in hydrogen rich stream (PROX). The effect of ceria loading (10, 20 or 30 wt%) was studied. The gold catalyst with the lowest ceria amount exhibited the highest PROX activity. The addition of Y2O3 (1 wt%) led to improved performance. The most favorable effect was observed in the sample with 20 wt% ceria amount. This gold catalyst showed good PROX activity and stability in the presence of CO2 and water. Catalysts characterization by XRD, HRTEM/HAADF, XPS and H2-TPR was used to elucidate the relationship between the chemical composition, state of gold, support features and catalytic properties.object Object]

Novel visible light responsive materials for water splitting are essential for the efficient conversion of solar energy into hydrogen bond energy. Among other semiconductors, gadolinium orthovanadate has appropriate conduction and valence band edges positioned to split water molecules and a narrow band gap that allows the use of visible light for hydrogen generation. Thus, we present here that hydrogen evolution under visible light (λ > 420 nm) could be accomplished using hierarchical 3D GdVO4 particles, obtained by a simple, one pot hydrothermal synthesis. We found that applying various reaction components, such as EDTA-Na2 and EDTA, and adjusting the pH of the solution allow one to tune the shape of GdVO4 (such as short nanowires, long nanowires, short nanorods, long nanorods, nanoparticles and spheres – all having a tetragonal crystal structure) as well as optical and photocatalytic properties. The highest ability to photocatalytically split methanol solution into hydrogen under UV-Vis irradiation was detected for the long nanowire sample (42 μmol h−1), having almost 11 times higher efficiency in comparison with the weakest sample – short nanowires. In addition, GdVO4 spheres generated H2 more than 2 times (5.75 μmol h−1) in comparison with the short nanorod sample (2.5 μmol h−1) under visible light excitation. Photostable in three-hour work cycles, long nanowires and spheres were even able to generate hydrogen from pure water, reaching values of 17 and 3 μmol under UV-Vis and Vis light, respectively.

A series of novel ZnO quantum dots modified with rare earth metals was successfully prepared by a simple sol-gel approach. The effects of types (Eu, Er, Tb, Yb, Ho, La) and amounts (from 0.09 to 0.45 mmol) of lanthanides on the optical properties, structural characterization and photocatalytic activity of ZnO/RE QDs were systematically investigated. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) with energy dispersive X-ray analysis (EDX) and UV–Vis diffuse reflectance spectroscopy were used to characterize surface properties, while photoluminescence (PL) emission spectroscopy and UV–Vis-driven degradation of phenol in aqueous phase were applied to understand optical and photocatalytic properties. The experiments demonstrated that generally modification of ZnO QDs by lanthanides resulted in increase of photoactivity while photoluminesce decrease at the same moment. The highest photocatalytic activity among all obtained nanomaterials and the lowest photoluminescence quantum yield among ZnO/Er photocatalysts were observed for ZnO QDs modified with 0.09 mmol of erbium. Increased photocatalytic activity has been shown in successive samples: ZnO/0.09_Er > ZnO/0.18_Eu > ZnO/0.09_La > ZnO/0.27_Er > ZnO/0.18_Tb > pristine ZnO QDs. The experimental results were supported by calculations based on density functional theory (DFT) which revealed atomic and electronic structure of Er/La modified ZnO QDs.

Silver phosphate (Ag3PO4) could be considered as visible light induced photocatalyst for pollutants degradation, due to its narrow band gap (∼2.4 eV). However, Ag3PO4 photoactivity depends on surface properties and synthesis route. In this study, differently shaped Ag3PO4 photocatalysts have been synthesized through the precipitation, ion exchange, soft-chemical or hydrothermal method. To correlate surface properties with photoactivity all samples were characterized towards morphology, crystal structure, specific surface area, optical properties, chemical composition and activity in phenol degradation upon visible light irradiation (λ > 420 and 455 nm). It is worthwhile noting that the most active Ag3PO4 samples possessed almost the same activity in phenol degradation upon irradiation from visible range (λ > 455 nm) that P25 TiO2 upon UV light. Phenol degradation rate equaled to 3.31 and 3.23 μmol/dm3/min in the presence of branched and rhombic dodecahedral Ag3PO4 particles, while it reached 3.36 μmol/dm3/min in the presence of P25 and UV light. Analysis of the degradation intermediates indicated that the benzoquinone was the primary byproducts of phenol degradation. Scavengers-assisted photocatalytic test confirmed that mainly O2− has been involved in phenol degradation under visible radiation. Surface composition analysis by XPS suggested that higher total silver content favors photoactivity, while higher ratio of Ag0 to Ag+ suppress photoactivity. Long term photocatalytic tests also implies that increase in Ag0 amount at the Ag3PO4 surface, due to photoreduction of Ag ions, rusulted in activity drop.