XRD Studies Research Articles

Influence of Nitrogen-Doped Carbon Dots on H• Radical-Mediated Au-H Formation in the Hydrogenation of 4-Nitrophenol Using NCDs-Au Nanohybrids.

The hydrogenation of 4-nitrophenol using carbon dot-stabilized gold (Au) nanoparticles is well-studied, with Au-H species known to catalyze the reaction. However, the impact of specific nitrogen moieties in nitrogen-doped carbon dots on Au-H formation and catalytic activity remains unexplored. These nitrogen species, acting as surface ligands, may influence the catalytic properties through the generation of Au-H species via H• radicals. In this regard, modulation of the catalytic properties of Au nanoparticles has been explored by conjugating their surface with nitrogen-doped carbon dots (NCDs). Three distinct nanohybrid formulations comprising NCDs and Au nanoparticles (i.e., NCDs-Au) have been prepared, where the NCDs were derived from different carbon sources (e.g., citric acid and l-malic acid) and varying mole ratios of the nitrogen source (i.e., urea). The impact of NCDs on Au nanoparticle-mediated catalysis has been investigated using the model reaction of hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. The fractions of different nitrogen species (such as pyrrolic, pyridinic, and amidic) in the different NCDs-Au nanohybrids were quantified through XPS analysis, and their roles in catalytic performance have been studied. Further, the size, shape, crystallinity, defects, and exposed facets of the NCDs-Au nanohybrids have also been assessed (through XRD, HRTEM, and Raman studies), and their structure-activity relationships have been corroborated. The hydrogenation of 4-NP is proposed to happen through the formation of gold-hydride (Au-H) species facilitated by H• radicals, as confirmed by EPR analysis. The NCDs-Au nanohybrid, synthesized from NCDs derived from a 1:3 molar ratio of l-malic acid and urea (MU13-Au), exhibits superior catalytic efficiency with a rate constant of 1.013 min-1, attributed to its abundant defects and a notably high relative content of catalytically favorable pyridinic nitrogen species compared to other tested nanohybrids.

Enhanced Removal of Pb(II), Paracetamol and Rhodamine B from Aqueous Solutions Using Engineered Low‐Cost Tea Waste‐Based Magnetic Nanocomposite

AbstractThe development of engineered biomass‐based adsorbents capable of efficiently removing pollutants from aqueous solutions has received tremendous attention due to their cost‐effectiveness and renewal potential. Herein, we report a one‐pot synthesis of a low‐cost magnetic composite (Fe3O4‐tea) derived from waste tea and iron oxide magnetic nanoparticles and its application as nanosorbent for the removal of Pb2+, rhodamine B and paracetamol as model pollutants from aqueous solutions. The FTIR, XRD, TGA, BET, TEM and zeta potential studies confirmed the successful synthesis of Fe3O4‐tea with an organic content of 54.55 wt.% and a surface area of 25.32 m2 g−1. The high saturation magnetization (Ms) of the composite estimated to 45.47 emu g−1 allows for its effortless separation and recovery from wastewater solutions using a simple bar magnet. Various theoretical models were considered to study and discuss adsorption isotherms and kinetics. The equilibrium kinetics were found to follow a second‐order model, regardless of the system investigated. Maximum monolayer adsorption capacities of 113.63, 92.59 and 60.24 mg g−1 were obtained for Rhodamine B, Pb2+ and paracetamol, respectively. These values are greater than the adsorption capabilities of several conventional and magnetic sorbents reported in the literature, including activated carbon. The adsorption process mechanism was also discussed based on pH studies. The results suggest that the Fe3O4‐tea adsorbent shows a great potential for effectively removing heavy metal ions and organic pollutants with a rapid uptake rate and easy magnetic separation.

Metal-polymer-clay nanocomposites based electrochemical sensor for detecting hydrazine in water sources

AgNPs embedded polymer-clay (AgNPs@PEI-HNT) nanocomposites were successfully employed to sensitively detect hydrazine in water samples using differential pulse voltammetry (DPV) and amperometry methods. In-situ polymerization was utilized for assembling the polymer-clay composites, which were subsequently coated with AgNPs. PEI improves conductivity and absorbs AgNPs on the surface of HNTs, as evidenced with the help of UV-Visible, IR spectroscopy, XRD, XPS and morphological studies (FE-SEM and TEM). Nanocomposites were coated with GCE, which improved their electrocatalytic performance during hydrazine oxidation. The Tafel plot, Galus and Cottrell equations were used to compute the electron transfer coefficient (0.64), catalytic reaction rate constant (4.81 × 104 M−1s−1) and diffusion coefficient (2.56 × 10−5 cm2/s) of hydrazine at AgNPs@PEI-HNT/GCE. Amperometry technique was used to determine the LOD along with sensitivity of hydrazine, which were 0.22 nm and 116.76 µA µM−1 cm−2. Modified electrode offers enhanced properties for example strong anti-interference capability, good reproducibility, long-term stability, sensitivity, and so on. The designed sensor successfully detects hydrazine in water samples with high recovery rates (R.S.D. < 5 %).

Mixed ligand complexes of Pt(II) Tertiary phosphines and 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea; Crystal structure and DFT of [Pt(C14H9N3S2)(dppe)].CH2Cl2

This paper describes a series of Pt(II) thiourea complexes (1–4). The complexes were synthesized by a reaction between [PtCl2(diphos)] and the ligand 1-(benzo[d]thiazol-2-yl)-3-phenylthioure in the presence of triethylamine, with all reactants present in equimolar amounts. The produced complexes exhibited square planar geometry, which was validated by FT-IR and 1HNMR . Single crystal XRD study revealed that the coordination geometry was distorted square planar in [Pt(Btzt)(dpppe)]. Hirshfeld surface analysis was used to delve deeper into the intermolecular interactions which showed that the combined contribution of H⋯H and H⋯C contacts in the stabilization of the supramolecular assembly was 81.3%. A void analysis was carried out which showed that there was no large cavity in the supramolecular assembly. Theoretical studies were also conducted on [Pt(Btzt)(dpppe)]. The DFT analysis was carried out using the B3LYP Hybrid method in combination with Def2-SVP. The theoretical findings indicated just 3% differences between the theoretical and experimental Figures. Furthermore, the computed HOMO-LUMO gap was 3.4 eV, which was close to the anatase photocatalyst's band gap. DFT predicted that all complexes are non-magnetic with μB=0. There are high electron donation and back-donation between heteroatoms and transition metals in the complexes.

Ti/CuO Nanothermite-Study of the Combustion Process.

A study of the combustion processes of Ti/CuO and Ti/CuO/NC nanothermites prepared via electrospraying was conducted in this work. For this purpose, the compositions were thermally conditioned at 350, 550 and 750 °C, as selected based on our initial differential scanning calorimetry-thermogravimetry (DSC/TG) investigations. The tested compositions were analysed for chemical composition and morphology using SEM-EDS, Raman spectroscopy and XRD measurements. Additionally, the thermal behaviour and decomposition kinetics of compositions were explored by means of DSC/TG. The Kissinger and Ozawa methods were applied to the DSC curves to calculate the reaction activation energy. SEM-EDS analyses indicated that sintering accelerated with increasing equivalence ratio and there was a strong effect on the sintering process due to cellulose nitrate (NC) addition. The main combustion reaction was found to start at 420-450 °C, as confirmed by XRD and Raman study of samples annealed at 350 °C and 550 °C. Moreover, increasing the fuel content in the composition led to lower Ea, higher reaction heats and a more violent combustion process. Conversely, the addition of NC had an ambiguous effect on Ea. Finally, a multi-step combustion mechanism was proposed and is to some extent in line with the more general reactive sintering (RS) mechanism. However, unusual mass transfer was observed, i.e., to the fuel core, rather than the opposite, which is typically observed for Al-based nanothermites.

Characterization of ZnWO4, MgWO4, and CaWO4 Ceramics Synthesized in the Field of a Powerful Radiation Flux

This paper presents the results of a study on the morphology, structure, and luminescent properties of ceramics synthesized in the radiation field of MeWO4 compositions (where Me is Mg, Ca, and Zn). The synthesis of ceramics was carried out by the direct action of the electron flux on an initial mixture of powders of the given stoichiometric composition. WO3, ZnO, MgO, and CaO powders with particle sizes in the range of 1–50 microns were used for the synthesis of the samples. It was found that the yield of the radiation synthesis reaction (the ratio of the mass of the sample and the charge used), when treated with an electron flux with an energy of 1.4 MeV and a flux power density of 15–18 kW/cm2, was in the range of 75–99%. The synthesis of all compositions was carried out under the same radiation treatment modes, although the melting temperatures of the starting materials varied significantly and ranged from 1473 °C (WO3) to 2825 °C (MgO). The study of the ceramic structure showed that under the radiation effect of powerful radiation fluxes on the charge, a crystalline phase of the appropriate composition formed, regardless of the synthesis modes. The results of XRD studies show that during the radiation treatment of the charge, ceramics are formed mainly with the crystalline phases ZnWO4, MgWO4, and CaWO4. These resulting MeWO4 ceramics can be used for the same purposes as crystals. Photoluminescence (PL) and cathodoluminescence (CL) were studied under excitation using stationary ultraviolet radiation and nanosecond pulses of electron flux. In general, the PL and CL of synthesized ceramic samples ZnWO4, MgWO4, and CaWO4 showed that their luminescent properties are similar to those of luminescence in corresponding crystalline materials. This indicates the formation of a crystalline phase in synthesized ceramic samples.

Mg‐ZnO/CNT Nanocomposite as Electrode Materials with Enhanced Electrochemical Performance for Supercapacitor Applications

AbstractThe present research work reported the study of nanocomposites of undoped and Mg‐doped ZnO with CNT as electrode materials for supercapacitor application. The undoped ZnO/CNT and Mg‐doped ZnO/CNT nanocomposites (i.e., 10 % Mg‐doped and 20 % Mg‐doped) were synthesized using a cost‐effective blending‐assisted hydrothermal method. The morphological (FESEM &amp; TEM) studies revealed that the diameter of CNT was ~7 nm and the ZnO nanoparticles were spherical in shape with an average particle size of ~5 nm. In addition, it was also found that 10 % Mg‐ZnO and 20 % Mg‐ZnO had a sheet‐like structure. XRD and FTIR studies further confirmed the successful doping of Mg in ZnO and CNT nanocomposites. BET analysis showed that the value of specific capacitance increased with the increase in surface area. Further, the electrochemical performance of these nanocomposites revealed that the higher doping percentage, 20 % Mg‐ZnO/CNT nanocomposite achieved the highest specific capacitance value i.e., 458.5 F/g at 0.1 A/g current density in 3M H2SO4 electrolytic solution, having a retention of 99.8 % after 12,00 long cycles. In addition, the charge storage mechanism revealed that the as‐synthesized nanocomposites showed both the diffusion‐controlled and capacitive‐controlled behaviors. Thus, a higher value of specific capacitance with excellent cyclic stability indicated the higher efficiency of Mg‐doped ZnO/CNT nanocomposite for future supercapacitor applications.

Varied coordination geometries of an Alane/Tris(phosphine) ligand from its Reactions with Pt(0) and Au(I)

Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand 1 (AlP3) furnished an (AlP3)Pt complex 2, which was determined to possess a Pt → Al interaction. Compound 2 reacted with CO to form the corresponding isolable adduct 3. Exposure of 2 to H2 or HD in solution resulted in the observation of equilibrium binding which favors 2 at room temperature, and more strongly favored the adducts 2-H2 and 2-HD at −80 °C. The presence of the Pt–H2/HD moieties is supported by low temperature NMR determination of 1JPPt = 323 Hz (2-H2) and 1JHD=34 Hz (2-HD), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of 1 with (tht)AuCl (tht = tetrahydrothiophene) generated compound 4 with loss of tht. An XRD study of 4 revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from 4 did not lead to a tripodal structure isoelectronic to 2, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound 5.

Spinel nickel ferrite (NiFe2O4) materials synthesized via spray-pyrolysis for electrochemical supercapacitor application

To explore potential applications of NiFe2O4-based supercapacitors in various energy storage systems, including portable electronic devices, electric vehicles, and grid energy storage, highlighting the advantages and challenges of using NiFe2O4 in these applications. To identify and propose future research directions for further improving the performance of NiFe2O4 supercapacitors. In the study focuses on optimizing concentration of synthesis to achieve desirable structural and electrochemical properties, characterizing the synthesized materials, and assessing their specific capacitance, energy density, power density, cycle stability, and rate capability. The different molar precursor solutions were utilized for the formation of NiFe2O4 thin films by using the cost-effective spray pyrolysis technique. The impact of different molarities on the structural, morphological, elemental, optical, and charge storage performance of NiFe2O4 thin films has been studied. In the XRD studies identified the cubic crystalline structure with Fd-3 m space group symmetry of NiFe2O4. The FE-SEM shows the grain-like surface morphology of NiFe2O4 thin films. The EDAX study reveals that NiFe2O4 thin films were stoichiometric. Bandgap energy values of the thin films were observed in the range of 1.97 to 2.2 eV with allowed direct band gap transitions. The maximum specific capacitance for NiFe2O4 thin film was found to be 707 Fg−1 at 2 mVs−1 with the wider potential window of − 0.8 to + 1 .6 V in 1 M KOH aqueous electrolyte. GCD study confirms the pseudocapacitive behavior of NiFe2O4 thin films. The maximum specific energy and specific power were found to be 83.88 WhKg−1 and 5.294 KWkg−1 at a current density of 0.002 Ag−1. Such as spinel ferrite NiFe2O4 thin film electrodes as an excellent candidate material for electrochemical supercapacitor applications.

Electrodeposited manganese carbonate as an electrocatalyst for hydrogen evolution reaction in acidic medium

The electrolysis of water is the key method for hydrogen production but the high overpotential necessitates electrocatalysts. Traditionally, Pt is used, but it is scarce and costly. Herein, MnCO3 is unveiled as an electrocatalyst for the production of hydrogen. MnCO3 is electrodeposited onto pencil graphite by chronoamperometric method and confirmed by XRD and vibrational spectroscopic studies. MnCO3 electrodeposited for 15 min at 2 V demonstrates a good HER activity (overpotential of 123 mV to reach 10 mA cm−2) in 0.5 M H2SO4 with a Tafel slope of 79 mV dec−1. In addition, MnCO3 exhibited good stability during continuous operation (over 3000 cycles and 14 h). Though MnCO3 requires higher overpotential than the benchmark catalyst (Pt/C) to reach 10 mA cm−2, it outperforms Pt/C at higher current density (≥75 mA cm−2) demonstrating that MnCO3 could be used as an electrocatalyst to produce H2 at a high rate from acidic medium.

Beam Effects in Synchrotron Radiation Based Operando Characterization of Battery Materials: XRD and XAS Study of LiNi0.33Mn0.33Co0.33O2 and LiFePO4 Electrodes

Operando synchrotron radiation-based characterization techniques applied to energy storage materials are becoming a widespread characterization tool as they allow for non-destructive probing of materials with various depth sensitivities through spectroscopy, scattering, and imaging techniques. Moreover, they allow for faster acquisition rates, variable penetration depths, higher spectral or spatial resolution, or access to techniques that are only possible with a continuous tuneable source over a wide photon energy range. Compatibility between the electrochemical cell designs and the experimental setups may force some specific design features and care must be taken to ensure that these do not perturb the electrochemical response of the materials under investigation. The use of operando techniques has intrinsic advantages, as they enable the detection of metastable intermediates, if any, and ensure characterization under real conditions avoiding the risk of ex situ sample evolution during its preparation. However, they do not come with the extent of risks. The interaction between synchrotron radiation and samples, particularly within the intricate milieu of an operational electrochemical cell, can induce unexpected effects in the sample at the measurement spot, thereby jeopardizing the experiment's reliability and biasing data interpretation. While beam-induced effects are well-recognized for their critical impact on characterizing biological samples, macromolecules, or soft matter, they have, until recently, received scant attention within the battery research community, being vaguely referenced and incompletely understood. With the aim of contributing to this ongoing debate, a systematic investigation into these phenomena was carried out conducting a root cause analysis of beam-induced effects during the operando characterization of two commercially employed positive electrode materials: LiNi0.33Mn0.33Co0.33O2 and LiFePO4. The study spans across diverse experimental conditions involving various cell types, absorption and scattering techniques and seeks to correlate beam effects with factors such as radiation energy, photon flux, exposure time, and other parameters associated with radiation dosage. As a conclusion, a set of guidelines and recommendations are provided to evaluate and mitigate beam-induced effects that can affect the outcome of battery operando experiments.

Novel Damsissa carbon quantum dots (DCQDs) to improve the protection efficiency of permanganate phosphate conversion coats (PPC) on steel

Carbon quantum dots (CQDs) are spherical zero dimensional nanoparticles, generally below 10 nm in size, which received increasing attention in diverse application fields owing to their important characteristics and advantages as good water solubility, potential of environmental protection and preparation from abundant and sustainable raw materials. In this work, Damsissa carbon quantum dots (DCQDs) were generated via hydrothermal reaction microwaves irradiation. The DCQDs material was characterized by FTIR, TEM, EDX, XRD, and XPS to confirm the morphological and functionality aspects as well as particle size distribution, elemental composition, crystallite structure, and elemental identification in terms of chemical state. The FTIR analysis referred to associated assignments of C-H, C=O, C=C, C-N, besides other groups. The TEM study confirmed a ranged homogenous particle distribution at 3-6 nm. The EDX and XPS results verified carbon, nitrogen and oxygen as the main elements in DCQDs. The protection efficiency performance of permanganate phosphate conversion coat (PPC) was investigated and monitored by using different concentrations of DCQDs in the coating bath utilizing the potentiodynamic polarization technique, besides electrochemical impedance spectroscopy. The results referred to 97.4% maximum protection efficiency for the coat in presence of 400 mg/L DCQDs. The impedance results showed that as the concentration of DCQDs increase, the capacity of the double layer (Cdl) decreases due to the adsorption ofDamsissa carbon dots on the steel surface. However, the potentiodynamic polarization results indicated that the presence of DCQDs in HCl solution could lead to the polarization of the cathodic and anodic curves to denote that these retard the cathodic and anodic reactions at the steel surface inhibiting the corrosion process. The coats synthesized in absence and in presence of diverse amounts of DCQDs were examined by the TEM, EDX, XPS, and XRD studies to elucidate the role of DCQDs in the improvement of the corrosion protection of the coat. The results indicated that the DCQDs molecules ofDamsissa were adsorbed at the steel surface to efficiently retard the dissolution of iron and decrease the Fe2+ ions concentration in the coating solution causing higher nucleation rate over the crystal growth and thus leading to the formation of a uniform protective film.

Hybridization of CuFe2O4 by carbon microspheres with improved charge storage characteristics for high energy density solid-state hybrid supercapacitor

The hybrid nanocomposite of Copper Ferrite/Carbon sphere (CuFe2O4/C-sphere NC) has been synthesized and their combined electrochemical activity for supercapacitors is achieved. XRD study reveals the average crystallite size of CuFe2O4/C-sphere NC as 112 nm. CuFe2O4/C-sphere NC provides a huge specific surface area of 532 m2/g. Cyclic voltammetry (CV) analysis exhibits the competitive specific capacity of CuFe2O4/C-sphere NC as 320 C/g at the sweep rate of 10 mV/s. The galvanostatic charge-discharge (GCD) study shows a good specific capacity of 264 C/g at 1 A/g and excellent cyclic stability of 82.4% for 5000 cycles. The CuFe2O4/C-sphere//AC solid-state hybrid supercapacitor provides a high specific capacity of 131 C/g along with remarkable energy density and power density of 40.9 Wh/kg and 11248 W/kg respectively.

Investigation of diodic behavior in p-NiO/n-SnO2 bilayer heterojunctions fabricated via DC magnetron reactive sputtering

Tin oxide (SnOx) thin films at varying oxygen flow rates and Nickel oxide (NiO) thin films were deposited by reactive dc magnetron sputtering on glass substrates. Structural, chemical, morphological, optical and electrical properties of the deposited films were studied. XRD studies confirmed that the deposited films were polycrystalline in nature. SnOx thin films have shown two phases such as SnO and SnO2. AFM and SEM were used to analyse the morphology of the films and EDS confirmed the presence of Sn and Ni in the respective films. The examination of the x-ray photoelectron spectrum showed that the sputtered SnOx films contain both Sn2+ and Sn4+ oxidation states and NiO films contain Ni+2 and Ni+3 oxidation states. Photoluminescence study shows strong violet and weak red emission peaks for SnOx films and NiO showed strong emission peaks in the orange-red region. The optical results demonstrate that the films were transparent. The bandgap of SnOx and NiO samples were ∼3.3 eV and − 3.42 eV, respectively. Further we constructed a p-NiO/n-SnO2 heterojunction diode and its electrical characteristics were thoroughly assessed. Using dark current–voltage measurements, electrical characteristics such saturation current, ideality factor and barrier height were determined. The increase in oxygen flow rate led to reduction in the rectification of the devices. Our findings support the creation of high-performance metal oxide heterojunction for optoelectronic devices.

Curcumin- β-Cyclodextrin Molecular Inclusion Complex: A Water-Soluble Complex in Fast-dissolving Tablets for the Treatment ofNeurodegenerative Disorders.

Orally disintegrating tablets (ODTs) have become an excellent choice for delivering drugs as their palatability is greatly improved. In this work, β-cyclodextrin has been used to improve the solubility of curcumin by encapsulating it into the hydrophobic cavity for the treatment of neurodegenerative disorders. The current study aimed to present the design, formulation, and optimisation of fastdissolving oral tablets of curcumin- β-cyclodextrin molecular inclusion complex using a 32-factorial design. The drug-excipient compatibility was studied by FTIR spectroscopy. The inclusion complex of curcumin-β-cyclodextrin was prepared using solvent casting and confirmed using XRD studies. Powder blends were evaluated for flow properties. Tablets prepared by direct compression were evaluated for post-compression parameters. Further, the effect of formulation variables, such as sodium starch glycolate (X1) and Neusilin® ULF2 (X2), on various responses, including disintegration time and dissolution at 2 hours, was studied using statistical models. Post-compression parameters, i.e., hardness (4.4-5 kg/cm2), thickness (3.82-3.93 mm), weight variation (±7.5%), friability (< 1%), wetting time (51-85 seconds) and drug content (96.28- 99.32%) were all found to be within the permissible limits and the disintegration time of tablets with super-disintegrants ranged between 45-58 seconds. The in-vitro dissolution profile of tablets showed that higher SSG and Neuslin® ULF2 levels promoted drug release. For statistical analysis, the 2FI model was chosen. Optimised variables for formulation have been determined and validated with the experimental findings based on the significant desirability factor. The current study reveals the validated curcumin-β-cyclodextrin inclusion complex fastdissolving tablets with SSG and Neusilin® ULF2 to be an ideal choice for effectively treating neurodegenerative disorders.

The effect of SiO2 crystallization in enhancing the luminescence of Dy3+-Sm3+ co-doped glass ceramics for cool white light application.

The present work investigates the structural and luminescence behaviour of Dy3+-Sm3+ co-doped glass ceramics obtained through heat treatment of precursor glasses. The growth of SiO2 polycrystalline particles and evolution of these crystallites in the glass domain are witnessed via XRD and FESEM study. The presence of network vibrational bands, hydroxyl groups and the increased quantity of bridging oxygens (BOs) in glass ceramics are analysed through FTIR spectroscopy study. The absorption study (UV-Visible-NIR) showed the possible electronic transitions of Dy3+ and Sm3+ ions. The red shift in the absorption band edges and the lower bandgap values are obtained as a result of improved heat treatment in glass ceramics. Emission studies show the enhanced luminescence intensity of glass ceramics under 350 and 402 nm excitations. Decay measurement of glass ceramics showed the improved lifetimes of Dy3+ and Sm3+ ions to have appeared in microseconds (×10-6s). The colour characteristics of glass ceramics analysed using CIE colour chromaticity diagram and correlated colour temperature (CCT) values suggest the neutral to cool white light emissions. Therefore, prepared glass ceramics with SiO2 polycrystalline phase are considered to be suitable materials in cool white LEDs applications.

Synthesis of nickel-containing metal-polymer nanocomposites and their use as a humidity sensor

In recent years, the synthesis of new gas-sensitive materials for resistive humidity sensors has attracted significant interest. In the present paper, nickel-containing metal-polymer nanocomposites were obtained by thermolysis of nickel itaconate (I) and its complexes with 2,2′-dipyridyl (II), 1,10-phenanthroline (III) and 4′-phenyl-2,2′:6′,2''-terpyridine (IV). The formed nanocomposites were characterized by FTIR, elemental analysis, EDX, SEM, TEM and XRD studies. The most common particle sizes are 28, 12.8, 10.7 and 12.3 nm for the thermolysis products of compounds I–IV respectively. The manufactured sensor samples have good sensitivity to air relative humidity (RH) of 3.24 %/%RH, 4.72 %/%RH, 2.18 %/%RH and 4.37 %/%RH for thermolysis products of compounds I–IV with the polymer binder polyacrylamide, respectively. The average initial resistance of the sensors is 4.54, 15.33, 20.8 and 35.75 MΩ, respectively. Due to the high porosity and moisture absorption of the film, the maximum sensitivity was about 0.003 MΩ/%RH, which indicates a fairly effective behavior of the film with respect to humidity. The response times were 27, 25, 33, 30 s, and the recovery time 47, 44, 51, 49 s, respectively, and repeating the experiment resulted in 87–92 % reproducible results. The fabricated sensors have great potential for use as a humidity sensing element in sensors that can be used for humidity monitoring.

Chromium Complexes with Benzanellated N-Heterocyclic Phosphenium Ligands-Synthesis, Reactivity and Application in Catalytic CO2 Reduction.

A chromium complex carrying two benzanellated N-heterocyclic phosphenium (bzNHP) ligands was prepared by a salt metathesis approach. Spectroscopic studies suggest that the anellation enhances the π-acceptor ability of the NHP-units, which is confirmed by the facile electrochemical reduction of the complex to a spectroscopically characterized radical anion. Co-photolysis with H2 allowed extensive conversion into a σ-H2-complex, which shows a diverse reactivity towards donors and isomerizes under H-H bond fission and shift of a hydride to a P-ligand. The product carrying phosphenium, phosphine and hydride ligands was also synthesized independently and reacts reversibly with CO and MeCN to yield bis-phosphine complexes under concomitant Cr-to-P-shift of a hydride. In contrast, CO2 was not only bound but reduced to give an isolable formato complex, which reacted with ammonia borane under partial recovery of the metal hydride and production of formate. Further elaboration of the reactions of the chromium complexes with CO2 and NH3BH3 allowed to demonstrate the feasibility of a Cr-catalyzed transfer hydrogenation of CO2 to methanol. The various complexes described were characterized spectroscopically and in several cases by XRD studies. Further insights in reactivity patterns were provided through (spectro)electrochemical studies and DFT calculations.

Fabrication of ZnO[sbnd]Cu3SnS4 NCs for enhanced visible light-induced photocatalytic degradation of carvedilol

The widespread use of pharmaceutical drugs like carvedilol (CAR) has raised concerns regarding antibiotic resistance, environmental pollution, and potential human health risks. This study addresses these issues by employing advanced pristine nanomaterials, including ZnO and Cu3SnS4 to intricately engineer ZnOCu3SnS4 nanocomposite (NCs). These NCs are designed for enhanced photocatalytic degradation of CAR. Detailed characterization through SEM, and elemental mapping reveals the nanocluster morphology, amorphous nature, proper deposition distribution, and heterojunction formation. XRD studies confirm the purity of the synthesized materials, while XPS validate their chemical states and bonding nature. BET and BHJ analyses demonstrate the enhanced surface area and mesoporous nature of the NCs respectively. UV–visible DRS illustrates successful visible-light sensitization of the ZnOCu3SnS4 NCs with a bandgap of 2.96 eV. Photoluminescence studies indicate reduced charge carrier recombination in the NCs. .OH being the dominant radical involved in photodegradation. The photocatalytic degradation of CAR by ZnOCu3SnS4 NCs achieves a remarkable degradation efficiency of 98 % under optimal condition. These NCs also show outstanding stability across several cycles and remain to function in the presence of ions. Finally, GC–MS analysis suggests the potential CAR degradation routes that result in less hazardous end products. In conclusion, the present research highlights the potential of ZnOCu3SnS4 NCs for efficient wastewater treatment and highlights their capacity to tackle issues related to pharmaceutical drug contamination.

Investigation of structural, morphological, optical and electronic properties of Cu-doped PbS thin films: a comparative experimental and theoretical study

Thin film technology has emerged as a cornerstone in optoelectronics, enabling the fabrication of compact, lightweight devices with enhanced performance and efficiency through precise control of the nanoscale thicknesses of functional materials. The current study explores the impact of copper (Cu) doping (3.125%, 6.25%, and 12.5%) on lead (Pb) sites in PbS to examine the structural, morphological, electronic, optical, and thermoelectric characteristics, employing both experimental and theoretical approaches. Polycrystalline thin films of PbS are deposited by spin coating technique on glass substrates. The XRD study discloses the cubic crystal structure of pristine and Cu-doped PbS with nominal variation in d-spacing. Surface morphological investigations reveal that Cu-doping transforms the coffee beans like grains to nanoplates that significantly affect the surface homogeneity and porosity. The tuning of band structure in the visible range, 1.64–2.21 eV is witnessed in the band structure analysis. Moreover, the experimental results are complemented by a theoretical study using WIEN2k software. Theoretical study exhibits the direct bandgap nature and with the incorporation of Cu, it increases from 0.89 to 2.11 eV. The density of states spectra for Cu-doped PbS exhibits strong hybridization between p-states of Pb and S, and d-states of Cu. Optical findings demonstrate significant variations in the absorption spectrum, which result in modifications in the optical energy band gap and peculiar optical parameters of doped samples. At room temperature, the increase in electrical conductivity (σ/τ) from 0.2 × 1020 (Ω.m.s)−1 for PbS to 0.3 × 1020, 3.1 × 1020 and 7.8 × 1020 (Ω.m.s)−1, thermal conductivity from 0.25 × 1014 W m.K.s−1 to 0.30 × 1014, 2.4 × 1014 and 5.2 × 1014 W m.K.s−1 and decrease in Seebeck coefficient from 72 to 35, 13 and 8 μV/K with the inclusion of Cu up to 3.125, 6.25 and 12.5% offer the potential for advancing thermoelectric technology. This could lead to improved efficiency and practical utilization in energy harvesting and waste heat recovery.