Search Results (63)

This work explored an electrochemical approach for synthesizing lanthanum-modified nickel oxide (NiO_x:La) as a hole transport layer (HTL) in inverted perovskite solar cells (IPSCs). By varying the La³⁺ concentration, the chemical, charge transport, structural, and morphological properties of the NiO_x:La film and the HTL/PVK interface were evaluated to enhance photovoltaic performance. X-ray photoelectron spectroscopy (XPS) confirmed La³⁺ incorporation, a higher Ni³⁺/Ni³⁺ ratio, and a valence band shift, improving p-type conductivity. Electrochemical impedance spectroscopy and Mott–Schottky analyses indicated that NiO_x:La 0.5% exhibited the lowest resistance and the highest carrier density, correlating with higher recombination resistance. The NiO_x:La 0.5% based cell achieved a PCE of 20.08%. XRD and SEM confirmed no significant changes in PVK structure, while photoluminescence extinction demonstrated improved charge extraction. After 50 days, this cell retained 80% of its initial PCE, whereas a pristine NiO_x device retained 75%. Hyperspectral imaging revealed lower optical absorption loss and better homogeneity. These results highlight NiO_x:La as a promising HTL for efficient and stable IPSCs. Full article

Recent measurements of the band properties of AlN and GaN by fluorescence yield absorption and soft X-ray emission spectroscopies revealed that their valence band (VB) is composed of two separate subbands. The upper VB subband of GaN is composed of gallium sp and nitrogen p orbitals; the lower subband consists of metal d and nitrogen s orbitals. These findings were confirmed by extensive ab initio simulations. These results are not consistent with the standard tetrahedrally coordinated semiconductors, which are bonded by sp³-hybridized orbitals of metal and nonmetal atoms. The new analysis techniques and ab initio simulations create a new picture, allowing the calculation of overlap integrals to determine the bond order in these crystals. According to these results, bonding occurs between resonant p-states of nitrogen and sp³-hybridized metal orbitals in tetrahedral nitrides, allowing tetrahedral symmetry to be maintained. A similar resonant bonding mechanism is observed in hexagonal BN, where the p orbitals of nitrogen create three resonant states necessary for maintaining the planar symmetry of the lattice. In addition, nonresonant $\pi$-type bonds in BN are created by the overlap of $p_z$ orbitals of boron and nitrogen. BN bonding differs from that in graphene, where carbon states are fully sp²-hybridized. Additionally, $\pi$-type bonds in graphene have no ionic contributions, which leads to the formation of Dirac states with linear dispersion close to the K point, closing the band gap. Full article

This study provides a comprehensive structural, chemical, and optical characterization of CZTS thin films deposited on flexible Kapton substrates via the Successive Ionic Layer Adsorption and Reaction (SILAR) method. The investigation explored the effects of varying deposition cycles (40, 60, 70, and 80) and annealing treatments on the films. An X-ray diffraction (XRD) analysis demonstrated enhanced crystallinity and phase purity, particularly in films deposited with 70 cycles. These films exhibited a notable reduction in secondary phases in the as-deposited state, with further improvements observed after annealing at 400 °C and 450 °C in a sulfur atmosphere. A pole figure analysis indicates a decrease in texture disorder with annealing, suggesting improved crystalline orientation at higher temperatures. Field emission scanning electron microscopy (FE-SEM) showed enhancements in surface morphology, with increased grain size and uniformity post-annealing. Chemical uniformity was confirmed through Secondary Ion Mass Spectrometry (SIMS), Energy-Dispersive Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). XPS revealed the presence of CZTS phases alongside oxidized phases. Annealing effectively reduced secondary phases, such as ZnO, SnO₂, CuO, and SO₂, enhancing the CZTS phase. An optical analysis demonstrated that annealing at 200 °C in an air atmosphere reduced the band gap from 1.53 eV to 1.38 eV. In contrast, annealing at 400 °C and 450 °C in a sulfur atmosphere increased the band gap to 1.59 eV and 1.63 eV, respectively. The films exhibited p-type conductivity, as inferred from a valence band structure analysis. Density Functional Theory (DFT) calculations provided insights into the observed band gap variations, further substantiating the findings. Full article

Barium titanate photocatalysts were synthesized via a sol–gel method involving a unique, cost-effective calcination technique that includes rapid heating and short exposure. The samples were characterized by X-ray diffractometry, scanning electron microscopy, diffuse reflectance spectroscopy, photoluminescence spectroscopy, infrared spectroscopy, and nitrogen adsorption–desorption measurements. The photooxidation activity and stability of the samples were evaluated by the degradation of phenol, oxalic acid, and chlorophenol. Their photoreduction activity was also investigated by the photocatalytic conversion of CO₂ to CO. In both cases, UV irradiation was applied to activate the catalysts. As references, commercially available cubic and tetragonal barium titanates were used, with the addition of benchmark P25 TiO₂ in some cases. Increasing the calcination temperature resulted in increased primary crystallite sizes, decreased specific surface areas, and slightly redshifted band gaps. On the one hand, the overall photooxidation activity of the samples for pollutant degradation was rather low, possibly due to their unfavorable valence band maximum position. On the other hand, our samples displayed significantly superior photoreduction activity, surpassing that of all the references, including P25 TiO₂. The high photoactivity was mainly attributed to the specific surface areas that changed per the efficiency of the samples. Last, the cost comparison calculations showed that applying our calcination technique is 29.5% more cost-efficient than conventional calcination, and the same amount of energy is sufficient for preparing even a 1.4 times higher amount of barium titanite. Full article

Utilizing hydrothermal methods, Ce-doped iron oxide nanoparticles were synthesized from precursor solutions under different c(Ce⁴:c(Fe³⁺) precursor solutions. The effects of the c(Ce⁴⁺):c(Fe³⁺) ratio in the precursor solutions on the nanoparticle morphology and nanoparticle structure of the Ce-doped iron oxide were investigated using X-Ray diffraction, transmission electron microscopy, and scanning electron microscopy. Fourier transform infrared spectroscopy (FTIR) was used to examine the bond energy strength of the Ce-doped iron oxide nanoparticles. The electrochemical properties of the Ce-doped iron oxide nanoparticles were tested using an electrochemical workstation and a saltwater immersion resistance test. The corrosion resistance of Ce-doped iron oxide coatings at different c(Ce⁴⁺):c(Fe³⁺) ratios was systematically analyzed, uncovering corrosion resistance mechanisms and self-healing capabilities. The results show that as the c(Ce⁴⁺):c(Fe³⁺) ratio decreases, the lattice constants of the samples increase along with the average grain size. Both smaller and larger c(Ce⁴⁺):c(Fe³⁺) ratios are detrimental to lattice distortion in α-Fe₂O₃. The reduced number of valence electrons provided by cerium ions in Ce-doped iron oxide hinders the generation of holes and exerts a minor influence on the crystal band structure, leading to weaker electrochemical stability. The Ce-doped iron oxide coating prepared at a c(Ce⁴⁺):c(Fe³⁺) ratio of 1:60 readily generates a higher number of reactive hydroxyl radicals during corrosion, thus exhibiting enhanced self-healing capabilities and corrosion resistance. Full article

Recalcitrant compounds resulting from anthropogenic activity are a significant environmental challenge, necessitating the development of advanced oxidation processes (AOPs) for effective remediation. This study explores the synthesis of cuprous oxide nanoparticles on cellulose-based paper (Cu₂O@CBP) using Eucalyptus globulus leaf extracts, leveraging green synthesis techniques. The scanning electron microscopy (SEM) analysis found the average particle size 64.90 ± 16.76 nm, X-ray diffraction (XRD) and Raman spectroscopy confirm the Cu₂O structure in nanoparticles; Fourier-transform infrared spectroscopy (FTIR) suggests the reducing role of phenolic compounds; and ultraviolet–visible diffuse reflectance spectroscopy (UV-Vis DRS) allowed us to determine the band gap (2.73 eV), the energies of the valence band (2.19 eV), and the conduction band (−0.54 eV) of Cu₂O@CBP. The synthesized Cu₂O catalysts demonstrated efficient degradation of methylene blue (MB) used as a model as recalcitrant compounds under LED-driven visible light photocatalysis and heterogeneous Fenton-like reactions with hydrogen peroxide (H₂O₂) using the degradation percentage and the first-order apparent degradation rate constant (k_app). The degradation efficiency of MB was pH-dependent, with neutral pH favoring photocatalysis (k_app = 0.00718 min⁻¹) due to enhanced hydroxyl (·OH) and superoxide radical (O₂·⁻) production, while acidic pH conditions improved Fenton-like reaction efficiency (k_app = 0.00812 min⁻¹) via ·OH. The reusability of the photocatalysts was also evaluated, showing a decline in performance for Fenton-like reactions at acidic pH about 22.76% after five cycles, while for photocatalysis at neutral pH decline about 11.44% after five cycles. This research provides valuable insights into the catalytic mechanisms and supports the potential of eco-friendly Cu₂O nanoparticles for sustainable wastewater treatment applications. Full article

Ag₃PO₄/g-C₃N₄ photocatalytic composites were synthesized via calcination and hydrothermal synthesis for the degradation of rhodamine B (RhB) in wastewater, and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS). The degradation of RhB by Ag₃PO₄/g-C₃N₄ composites was investigated to evaluate their photocatalytic performance and cyclic degradation stability. The experimental results showed that the composites demonstrated notable photocatalytic activity and stability during degradation. Their high degradation efficiency is attributed to the Z-scheme transfer mechanism, in which the electrons in the Ag₃PO₄ conduction band and the holes in the g-C₃N₄ valence band are annihilated by heterojunction recombination, which greatly limits the recombination of photogenerated electrons and holes in the catalyst and enhances the activity of the composite photocatalyst. In addition, measurements of photocurrent (PC) and electrochemical impedance spectroscopy (EIS) confirmed that the efficient charge separation of photo-generated charges stemmed from strong interactions at the close contact interface. Finally, the mechanism for catalytic enhancement in the composite photocatalysts was proposed based on hole and radical trapping experiments, electron paramagnetic resonance (EPR) analysis, and work function evaluation. Full article

All-inorganic metal halide perovskite is promising for highly efficient and thermally stable perovskite light-emitting diodes (PeLEDs). However, there is still great room for improvement in the film quality, including low coverage and high trap density, which play a vital role in achieving high-efficiency PeLEDs. In this work, lead acetate (Pb(Ac)₂) was introduced into the perovskite precursor solution as an additive. Experimental results show that perovskite films deposited from a one-step anti-solvent free solution process with increased surface coverage and reduced trap density were obtained, leading to enhanced photoluminescence (PL) intensity. More than that, the valence band maximum (VBM) of perovskite films was reduced, bringing about a better energy level matching the work function of the hole-injection layer (HIL) poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS), which is facilitated for the hole injection, leading to a decrease in the turn-on voltage (V_th) of PeLEDs from 3.4 V for the control device to 2.6 V. Finally, the external quantum efficiency (EQE) of the sky blue PeLEDs (at 484 nm) increased from 0.09% to 0.66%. The principles of Pb(Ac)₂ were thoroughly investigated by using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). This work provides a simple and effective strategy for improving the morphology of perovskite and therefore the performance of PeLEDs. Full article

The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0–30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2–3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp³ component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp³ bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG). Full article

The tetrafluoroborate salt of the cationic Cu(I) complex [Cu(CHpz₃)(PPh₃)]⁺, where CHpz₃ is the tridentate N-donor ligand tris(pyrazol-1-yl)methane and PPh₃ is triphenylphosphine, was synthesized through a displacement reaction on the acetonitrile complex [Cu(NCCH₃)₄][BF₄]. The compound crystallizes in the monoclinic P2₁/c space group. The single-crystal X-ray diffraction revealed that the copper(I) centre is tetracoordinated, with a disposition of the donor atoms surrounding the metal centre quite far from the ideal tetrahedral geometry, as confirmed by continuous shape measures and by the τ₄ parameter. The intermolecular interactions at the solid state were investigated through the Hirshfeld surface analysis, which highlighted the presence of several non-classical hydrogen bonds involving the tetrafluoroborate anion. The electronic structure of the crystal was modelled using plane-wave DFT methods. The computed band gap is around 2.8 eV and separates a metal-centred valence band from a ligand-centred conduction band. NMR spectroscopy indicated the fluxional behaviour of the complex in CDCl₃ solution. The geometry of the compound in the presence of chloroform as implicit solvent was simulated by means of DFT calculations, together with possible mechanisms related to the fluxionality. The reversible dissociation of one of the pyrazole rings from the Cu(I) coordination sphere resulted in an accessible process. Full article

Currently, electrically conductive polymers based on transition metal complexes [M(Salen)], as well as their composites, are among the systems showing promise as catalysts, electrochromic and electroluminescent materials, and electrodes for energy storage (for batteries and supercapacitors). The current review focuses on elucidating the atomic and electronic structure of metal–salen complexes, their polymers, and composites with nanostructured carbon (carbon nanotubes and graphene) using modern X-ray spectroscopy methods (X-ray photoelectron (XPS) and valence-band photoemission (VB PES) spectroscopy, as well as near-edge (NEXAFS) and extended (EXAFS) X-ray absorption fine structure spectroscopy). We trust that this review will be of valuable assistance to researchers working in the field of synthesizing and characterizing metal–salen complexes and composites based on them. Full article

The reduction of Ce cations in CeO₂ can be enhanced by their partial substitution with Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for the thermal water-splitting reaction when compared to CeO₂ alone. This mixed oxide has a smaller crystallite size when compared to CeO₂, in addition to a smaller lattice size. In this work, two Fe-substituted Ce oxides are studied (Ce_0.95Fe_0.05O_2-δ and Ce_0.75Fe_0.25O_2-δ; δ < 0.5) by core and valence level spectroscopy in their as-prepared and Ar-ion-sputtered states. Ar ion sputtering substantially increases Ce4f lines at about 1.5 eV below the Fermi level. In addition, it is found that the XPS Ce5p/O2s ratio is sensitive to the degree of reduction, most likely due to a higher charge transfer from the oxygen to Ce ions upon reduction. Quantitatively, it is also found that XPS Ce3d of the fraction of Ce³⁺ (u_o, u′ and v_o, v′) formed upon Ar ion sputtering and the ratio of Ce5p/O2s lines are higher for reduced Ce_0.95Fe_0.05O_2-δ than for reduced Ce_0.75Fe_0.25O_2-δ. XPS Fe2p showed, however, no preferential increase for Fe³⁺ reduction to Fe⁰ with increasing time for both oxides. Since water splitting was higher on Ce_0.95Fe_0.05O_2-δ when compared to Ce_0.75Fe_0.25O_2-δ, it is inferred that the reaction centers for the thermal water splitting to hydrogen are the reduced Ce cations and not the reduced Fe cations. These reduced Ce cations can be tracked by their XPS Ce5p/O2s ratio in addition to the common XPS Ce3d lines. Full article

A reported water-stable Zn-MOF ([Zn(L)₂(bpa)(H₂O)₂]·2H₂O, H₂L = 5-(2-cyanophenoxy) isophthalic acid has been prepared via a low-cost, general and efficient hydrothermal method. It is worth noting the structural features of Zn-MOF which exhibit the unsaturated metal site and the main non-covalent interactions including O⋯H, N⋯H and π-π stacking interactions, which lead to strong antibacterial and good tetracycline degradation ability. The average diameter of the Zn-MOF inhibition zone against Escherichia coli and Staphylococcus aureus was 12.22 mm and 10.10 mm, respectively. Further, the water-stable Zn-MOF can be employed as the effective photocatalyst for the photodegradation of tetracycline, achieving results of 67% within 50 min, and it has good cyclic stability. In addition, the photodegradation mechanism was studied using UV-vis diffuse reflection spectroscopy (UV-VIS DRS) and valence-band X-ray photoelectron spectroscopy (VB-XPS) combined with the ESR profile of Zn-MOF, which suggest that ·O₂⁻ is the main active species responsible for tetracycline photodegradation. Also, the photoelectric measurement results show that Zn-MOF has a good photocurrent generation performance under light. This provides us with a new perspective to investigate Zn-MOF materials as a suitable multifunctional platform for future environmental improvement applications. Full article

X-ray reflectometry (XRR) and X-ray photoelectron spectroscopy (XPS) measurements (core levels and valence bands) were made of Cu thin films that were prepared and coated by capping Ta layers with different thicknesses (5, 10, 15, 20, and 30 Å), and are presented. The XRR and XPS Ta 4f-spectra revealed a complete oxidation of the protective layer up to a thickness of 10 Å. From the thickness of the capping layer of 15 Å, a pure Ta-metal line appeared in the XPS Ta 4f-spectrum, the contribution of which increased up to 30 Å. The XPS Cu 2p-spectra of the underlying copper layer revealed the oxidation with the formation of CuO up to a thickness of the Ta-layer of 10 Å. Starting from a thickness of 15 Å, the complete protection of the Cu layer against oxidation was ensured during exposure to the ambient atmosphere. Full article

Compared with traditional hydrothermal synthesis, microwave-assisted synthesis has the advantages of being faster and more energy efficient. In this work, the MoS₂/BiVO₄ heterojunction photocatalyst was synthesized by the microwave-assisted hydrothermal method within 30 min. The morphology, structure and chemical composition were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM). The results of characterizations demonstrated that the synthesized MoS₂/BiVO₄ heterojunction was a spherical structure with dimensions in the nanorange. In addition, the photocatalytic activity of the samples was investigated by degrading tetracycline hydrochloride (TC) under visible light irradiation. Results indicated that the MoS₂/BiVO₄ heterojunction significantly improved the photocatalytic performance compared with BiVO₄ and MoS₂, in which the degradation rate of TC (5 mg L⁻¹) by compound where the mass ratio of MoS₂/BiVO₄ was 5 wt% (MB5) was 93.7% in 90 min, which was 2.36 times of BiVO₄. The active species capture experiments indicated that •OH, •O₂⁻ and h⁺ active species play a major role in the degradation of TC. The degradation mechanism and pathway of the photocatalysts were proposed through the analysis of the band structure and element valence state. Therefore, microwave technology provided a quick and efficient way to prepare MoS₂/BiVO₄ heterojunction photocatalytic efficiently. Full article