X-ray Photoelectron Spectroscopy Spectra Research Articles

Molecular mechanisms of iron nanominerals formation in fungal extracellular polymeric substances (EPS) layers during fungus-mineral interactions

Extracellular polymeric substances (EPS), which envelop on fungal hyphae surface, interact strongly with minerals and play a crucial role in the formation of nanoscale minerals during biomineralization in nature environments. However, it remains poorly understood about the molecular mechanisms of nanominerals (i.e., iron nanominerals) formation in fungal EPS halos during fungus-mineral interactions. This process is vital because fungi typically grow attached to various mineral surfaces in nature. According to the changes of thickness of the fungal cell and EPS layers during the Trichoderma guizhouense NJAU 4742 and hematite cultivation experiments, we found that fungal biomineralization could trigger the formation of EPS layers. Fe-dominated nanominerals, aromatic C (283-286.1 eV), alkyl C (287.6-288.3 eV), and carboxylic C (288.4-289.1 eV) were the dominant chemical groups on the EPS layers, as determined by nanoscale secondary ion mass spectrometry (NanoSIMS), high-resolution transmission electron microscope (HRTEM), and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Further, evidence from Fe K-edge X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) spectra indicated that oxygen vacancy (OV) was formed on the Fe-dominated nanomineral surface during fungus-mineral interactions, which played an important role in catalyzing H2O2 decomposition and HO∗ production. Taken together, the intrinsic peroxidase-like activity by reactive oxygen species (ROS) could modulate the Fe-dominated nanominerals formation in EPS layers to newly form a physical barrier between the cell and the external environments around hyphae, providing novel insights into the effects of ROS-mediated fungal-mineral interactions on fungal nutrient recycling, attenuation of contaminants, and biological control in nature environments.

Spectroscopic Differentiation of Structural Transitions from Carbon Nanobelts to Carbon Nanotubes.

In this study, simulated X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were utilized to differentiate the early stage structures as carbon nanobelts (CNBs) evolved into carbon nanotubes (CNTs). The effects of edge type, length, and diameter on the spectroscopic characteristics of armchair and zigzag CNTs were examined. Variations in XPS spectra were found to correspond to changes in the bandgap, while Raman spectra provided distinct bands associated with specific structural features. Notably, in armchair CNTs, the C 1s XPS peak positions exhibited clear differences depending on the structure. Additionally, the Kekulé vibration band and other characteristic bands in Raman spectra varied with length and diameter, enabling differentiation of armchair CNT structures. Although the structural analysis of zigzag CNTs was challenging using XPS, Raman spectroscopy proved to be effective in distinguishing structural differences. This study lays the groundwork for future spectroscopic analyses, contributing to the broader understanding of nanocarbon materials such as CNBs and CNTs and their potential applications in advanced electronic materials.

Unraveling Oxygen Vacancies Effect on Chemical Composition, Electronic Structure and Optical Properties of Eu Doped SnO2.

The influence of Eu doping (0.5, 1 and 2 mol.%) and annealing in an oxygen-deficient atmosphere on the structure and optical properties of SnO2 nanoparticles were investigated in relation to electronic structure. The X-ray diffraction (XRD) patterns revealed single-phase tetragonal rutile structure for both synthesized and annealed Eu-doped SnO2 samples, except for the annealed sample with 2 mol.% Eu. The results of X-ray photoelectron spectroscopy (XPS) emphasized that europium incorporated into the SnO2 host lattice with an oxidation state of 3+, which was accompanied by the formation of oxygen vacancies under cation substitution of tetravalent Sn. Moreover, XPS spectra showed the O/Sn ratio, which has been reduced under annealing for creating additional oxygen vacancies. The pulse cathodoluminescence (PCL) demonstrated the concentration dependence of Eu site symmetry. Combination of XRD, XPS and PCL revealed that Eu doping and following annealing induce strongly disordering of the SnO2 crystal lattice. Our findings provide new insight into the interaction of rare-earth metals (Eu) with host SnO2 matrix and new evidence for the importance of oxygen vacancies for optical and electronic structure formation.

Unveiling Structural Variations in Armchair-Edge Coronoids by Spectroscopies.

This study explores the electronic and vibrational properties of armchair coronoids (ACs), a unique class of polycyclic aromatic hydrocarbons with varying molecular and cavity sizes. Through density functional theory simulations, we investigated the X-ray photoelectron spectroscopy (XPS) and Raman spectra of C222, C114, C42, and their derivatives with different cavity sizes. The results reveal that band gaps and electronic properties of ACs can be precisely tuned by adjusting the molecular and cavity dimensions. XPS spectra demonstrated shifts in binding energy correlating with bandgap variations, while Raman spectra exhibited distinct C-C stretching and breathing modes. Notably, the introduction of cavities led to shifts in the breathing mode band, providing insights into the structural identification of ACs through Raman spectroscopy. The findings suggest that combining XPS and Raman spectroscopy can effectively characterize ACs, offering a comprehensive understanding of their structure-property relationships. This research lays the groundwork for future experimental and theoretical studies on the potential applications of ACs in electronic materials.

Unlocking the Electrocatalytic Behavior of Cu2MnS2 Nanoflake-Anchored rGO for the Oxygen Evolution Reaction in an Alkaline Medium.

A catalyst of the oxygen evolution reaction (OER) that is viable, affordable, and active for effective water-splitting applications is critical. A variety of electrocatalysts have been discovered to replace noble metal-based catalysts. Of these, transition metal-based sulfides are essential for incorporating carbonaceous materials to improve electrical conductivity, resulting in better electrocatalytic performance. Our study illustrates the synthesis of Cu2MnS2 (CMS) nanoflakes and their different rGO composites (10 to 40 wt %) via a hydrothermal technique for an effective water oxidation reaction. The X-ray diffraction pattern reveals that the prepared Cu2MnS2 nanoflakes exhibit a cubic crystal structure. The high-resolution scanning electron microscopy and the high resolution transmission electron microscopy images corroborate the formation of the nanoflake-like morphology of Cu2MnS2 with the strong interaction of rGO. The selected area electron diffraction analysis pattern reveals a polycrystalline nature. The Fourier transform infrared spectrum shows the existence of a metal sulfur vibrational band at 590 cm-1, and Raman analysis infers the presence of rGO. The X-ray photoelectron spectroscopy spectra reveal the oxidation states of the elements present in the samples. Using Brunauer-Emmett-Teller analysis, the surface area of CMS-20 is found to be 117.04 m2/g. The measured OER overpotentials using linear sweep volammetry and the values are 380, 370, 340, 376, and 400 mV at 10 mA/cm2 for CMS, CMS-10, CMS-20, CMS-30, and CMS-40, respectively, and the corresponding Tafel slope values are 179, 158, 149, 206, and 240 mV/decade, respectively. The electrochemical active surface area is estimated using cyclic voltammetry for all of the catalysts, where CMS-20 showed a larger surface area. Also, the same catalyst exhibits good stability for ∼24 h at a constant potential, which is confirmed via chronoamperometry. Thus, combining transition metal-based sulfides with carbonaceous materials indicates improved catalytic behavior for the preparation of high-performance OER electrocatalysts. Overall, the prepared CMS-20 performed as an efficient OER electrocatalyst and can be utilized for practical applications in energy conversion.

XPS Binding Energy Shifts in 2D Ti3C2Tz MXene go largely Beyond Intuitive Explanations: Rationalization from DFT Simulations and Experiments.

MXenes are prototypes of surface tunable 2D materials with vast potential for properties tuning. Accurately characterizing their surface functionalization and its role in electronic structure is crucial, X-ray photoelectron spectroscopy (XPS) being among the go-to methods to do so. Despite extensive use, XPS analysis remains however intricate. Focusing on the benchmark MXene Ti3C2Tz, Density Functional Theory (DFT) calculations of core-level binding energy shifts (BE.s.) are combined with experiments in order to provide a quantitative interpretation of XPS spectra. This approach demonstrates that BE.s. are driven by the complex interplay between chemical, structural, and subtle electronic structure effects preventing analysis from intuitive arguments or comparison with reference materials. In particular, it is shown that O terminations induce the largest BE.s. at Ti 2p levels despite lower electronegativity than F. Additionally, F 1s levels show weak sensitivity to the F local environment, explaining the single contribution in the spectrum, whereas O 1s states are significantly affected by the local surface chemistry. Finally, clear indicators of surface group vacancies are given at Ti 2p and O 1s levels. These results demonstrate the combination of calculations with experiments as a method of the highest value for MXenes XPS spectra analysis, providing guidelines for otherwise complex interpretations.

A mechanism study of type i corrosion on the surface of ancient tin rich bronzes

This study compares the surface patina of ancient tin rich bronze with pure hydrothermally synthesized SnO2 nanoparticles using various analytical techniques, including metallographic microscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The primary crystalline component of the patina consists of approximately 5 nm SnO2 nanoparticles, which closely resemble pure SnO2, indicating their comparability. Cu was also detected in the patina; however, it did not form crystalline structures. The X-ray diffraction results showed a shift in the patina’s peak, suggesting the infiltration of Cu into the SnO2 lattice, which compromises its crystallinity. In comparison to synthetic SnO2, the X-ray photoelectron spectroscopy spectra of the patina revealed novel peaks corresponding to both Cu and O, indicating the presence of Cu−O−Sn bonding—a characteristic feature of type-I patina. This suggests that the primary structure of type-I patina consists of crystalline SnO2 nanoparticles, with a limited amount of Cu integrated into its lattice configuration. The concentration of Cu within the SnO2 crystal units is restricted, leading primarily to the formation of amorphous Cu2O in conjunction with Sn. The presence of Sn enhances the structural stability of Cu2O, facilitating its incorporation while inhibiting the crystallization of Cu2O. However, when the Sn concentration is insufficient, an inadequate Cu–O−Sn amorphous phase may form, allowing for the potential crystallization of Cu2O.

STUDY THE ELECTRICAL PROPERTIES OF GRAPHENE OXIDE – NANOCELLULOSE COMPOSITE

This study investigates the electrical properties of a graphene oxide (GO) and nanocellulose (NC) composite using impedance spectroscopy, complemented by thorough characterization through Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and scanning electron microscopy (SEM). FTIR analysis revealed characteristic peaks corresponding to functional groups present in both GO and NC, providing insights into their chemical composition. XPS spectra exhibited distinctive peaks indicative of carbon and oxygen bonding states, elucidating the surface chemistry of the materials. Raman spectroscopy provided information on the structural order and defects within the samples, particularly highlighting the graphitic structure of GO. SEM images revealed the morphological features of the composite membrane, showcasing the distribution of NC particles and structural modifications induced by their incorporation. Impedance spectroscopy was utilized to investigate the electrical conductivity of the GO-NC composite. Results indicated a temperaturedependent behavior, with an increase in conductance observed as the temperature rose within the operational range of fuel cells. Remarkably, the addition of NC did not significantly alter the conductive behavior of the composite, suggesting compatibility and stability. In summary, this comprehensive characterization using multiple analytical techniques offers valuable insights into the electrical properties of the GO-NC composite. The findings suggest its potential for various applications requiring enhanced electrical conductivity, particularly in fuel cell technology.

An in-depth study of the synthesis of ReSe2 for anisotropic Raman characteristics

Abstract Two-dimensional transition metal dichalcogenides (TMDs) have received more interest for their potential role in future electronic and optoelectronic applications. Unlike other TMDs, Rhenium diselenide (ReSe2) stands out for its distinctive anisotropic growth characteristics. These unique features arise from its low lattice symmetry and interlayer decoupling, this has sparked significant interest among researchers. Previous research has indicated the presence of various growth patterns, including dendritic formations and structures resembling flowers. In this study, we effectively produced ReSe2 using the ‘Tilting Boat’ method to achieve growth on a 21 μm scale. Through precise manipulation of the growth conditions, we successfully attained flakes of 21 μm scale in comparison to prior findings. Moreover, we successfully produced a variety of shapes, including triangles, diamonds, and hexagons, on 1 × 1 cm2 Si/SiO2 substrates. Furthermore, we achieved the successful production of a continuous ReSe2 film on a 1 × 3 cm2 Al2O3 substrate. We verified the distinct anisotropic properties of ReSe2 via Raman Spectroscopy. Furthermore, we acquired three-dimensional visual representations of ReSe2 flakes and continuous films via SEM measurements. By employing EDS data and analysing x-ray photoelectron spectroscopy spectra, we have established a compositional ratio of 1:2 for Re and Se, which aligns with the MX2 structure. This confirmation indicates the successful synthesis of high-quality ReSe2 flakes.

Sol-gel synthesized flexible Na2Ti6O13–aluminium oxide fibres for photocatalytic degradation of Acid red 1

Sodium titanate (Na2Ti6O13; NTO) was loaded onto aluminium oxide fibres (AFs) using the sol–gel method to synthesize NTO/AF fibres. The surface roughness of NTO/AF-n fibres increased with increasing number of dip-coating cycles (n = 1–3). The Fourier transform infrared spectra and X-ray photoelectron spectroscopy spectra of NTO/AF-n demonstrated the loading of NTO onto AF. The bandgap energies of NTO/AF-1, NTO/AF-2, NTO/AF-3 and NTO were determined to be 3.08, 3.12, 3.38 and 3.45 eV, respectively. The production of hydroxyl radicals by fibres under irradiation decreased in the order of NTO, NTO/AF-1, NTO/AF-2 and NTO/AF-3. NTO/AF-n fibres were designed for convenient separation from water, with NTO/AF-1 exhibiting the highest activity among the NTO/AF-n samples. The photocatalytic degradation efficiencies of NTO/AF-1, NTO/AF-2 and NTO/AF-3 after 30 min of reaction were determined to be 61.4 %, 51.7 % and 44.3 %, respectively. Complete removal of Acid Red 1 from the solution was achieved through a photocatalytic reaction using NTO/AF-n. The activity of NTO/AF-n samples remained stable over five reaction cycles, indicating their application potential for large-scale water treatment.

Synthetic and natural antibacterial carbon adsorbents for clinical nuclear waste management

Patients undergoing high-dose radioiodine ablation (RAI) therapy in Nuclear Medicine Department need to be isolated in a special designed ward for a few days. Large amount of clinical radioactive wastewater from patient body is produced during high-activity RAI therapy. The radioactive wastewater needs to store in a delay tank until the radioactivity decayed below acceptable limit before being discharged and indirectly limit the patient admission and treatment. This study is to propose an alternative antibacterial adsorbent for I-131 extraction from clinical radioactive wastewater at the nuclear medicine department using graphene oxide silver (GOAg) and bamboo activated carbon (BAC). The synthesised adsorbents and their sediments (filtered sample) were analysed using field emission scanning electron microscopy (FESEM) for morphological analysis and analysed using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and X-ray diffraction (XRD). XPS spectra for C 1s adsorbents show intensity peaks at 284.45 eV (C=C) and 285.3 eV (C–C) for GOAg and its sediments, and 284.35 eV (C–C), 287.00 eV (C=O), and 290.07 eV (π–π∗ transitions) for BAC and its sediments. FTIR spectra reveal various functional groups of adsorbents: C=C (1637.50772 cm−1), C=O (1340.48041 cm−1), and C–O–C (1031.88060 cm−1) for GOAg and its sediments, and C=C (1635.57897 cm−1), C–C (1257.54421 cm−1), and C–O (1188.10925 cm−1) for BAC and its sediments. XRD patterns exhibit peaks at 2θ = 27.82°, 29.39°, 32.24°, and 46.22°, which can be attributed to the (002) diffraction plane, (220) crystallographic plane, (111) plane of Ag2O, and (200) crystallographic plane, respectively, for GOAg and its sediments. Meanwhile, the peaks at 2θ = 26.56° and 42.41°, which correspond to (002) and (100) planes, respectively, for BAC and its sediments. The d-spacing and the crystallinity index of each adsorbent were also determined. The estimation of the remaining β− particles during the adsorption of I-131 was carried out using PHITS. The finding of this study is beneficial for alternative radionuclide extractions technique from clinical radioactive wastewater in nuclear medicine.

Plasma treatment on flame soot: view from nanostructure and reactivity of soot

In recent years, the use of plasma for pollutant emission control has an expected potential. In this study, soot particles from flames were sampled from an ethylene inverse diffusion flame, which were placed in a self-designed dielectric barrier discharge plasma device for reaction treatment. The nanostructure and oxidation reactivity of soot particles after plasma treatment were evaluated by transmission electron microscopy, Raman spectroscopy, X-ray diffraction analysis and X-ray photoelectron spectroscopy. With 16 kV, 2.5 kHz as an example, with the treatment of plasma, the fringe length decreases (1.3% and 9.6%), and the fringe tortuosity increases (1.1% and 8.7%) in both high-maturity and low-maturity soot particles, which means that the oxidation activity of soot is enhanced after plasma discharge. Raman spectra, X-ray diffraction analysis spectra and X-ray photoelectron spectroscopy spectra have confirmed this phenomenon, especially the oxidation activity of soot particles under the action of plasma at high maturity is more obvious. It is worth noting that the enhancement of soot oxidation activity after plasma discharge has certain limitations, that is, the oxidation activity will not continue to increase after it is enhanced to a certain intensity, which may be related to the selection of Ar as the atmosphere gas.

Epitaxial growth and characterization of copper gallate (CuGa2O4) thin films by pulsed laser deposition

High-quality crystalline copper gallate (CuGa2O4) thin films were grown on c-plane sapphire substrates using the pulsed laser deposition (PLD) technique by optimizing the growth parameters (i.e., temperature, oxygen chamber pressure, and laser energy density). The obtained XRD patterns validated that the preferred orientation of the crystalline CuGa2O4 thin film is along the [111] direction, and the crystallinity of the films improved with increasing substrate temperature while maintaining a constant O2 pressure, as assessed by measuring the full width at half maximum (FWHM) of the prominent (222) plane. Reducing the oxygen pressure leads to the emergence of β-Ga2O3 peaks rather than the CuGa2O4 peaks due to the incomplete oxidation of copper (Cu). Subsequent XRD phi (φ) scans revealed a sixfold rotational symmetry of CuGa2O4 and a 30° epitaxial relationship between the film and the sapphire substrate. X-ray photoelectron spectroscopy (XPS) spectra confirmed the presence of Cu1+, Cu2+, and Ga3+ oxidation states in the films. Increasing laser energy density resulted in the complete oxidation of Cu and an increase in the film thickness from 51.8 nm to 183.4 nm. The direct bandgap of CuGa2O4 films was determined to be approximately 4.50 eV by analyzing the UV–Vis absorbance spectra using the Tauc equation. The refractive index was found to be approximately 2.05 ± 0.01 based on the spectroscopic ellipsometry data. While the impact of increasing laser energy density was negligible on the parameters such as crystal structure, rotational symmetry, oxidation states of gallium (Ga), oxygen (O), bandgap, and refractive index of CuGa2O4 thin film, notable alterations in the oxidation state of Cu and film thickness were observed. The surface roughness (Rrms) measured from AFM images showed a strong correlation with the values derived from ellipsometry analysis.

Activated carbon from agricultural industry waste for use as an adsorbent of sulfamethazine: Fascinating and environmentally friendly process

Lignocellulosic wastes have garnered interest in activated carbon (AC) production owing to their abundance and cost-effectiveness. This research utilized coffee husk as a precursor for AC. The methodology involves impregnating the waste with varying proportions of phosphoric acid (H3PO4), 1:1 and 1:3 (masswaste:massH3PO4), and activation in a microwave oven, with different power and activation times. The N2 adsorption/desorption results demonstrated high surface areas (SBET) for the ACs. The optimized AC (C1:3-1000-10) was obtained using a time of 10 min, high impregnation ratio, and power, resulting in an SBET of 1200 m2 g−1. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra confirmed the presence of functional groups, such as hydroxyl and ester, on the AC surface. Adsorption tests with sulfamethazine (SMZ) showed a 225 mg g−1 remotion capacity, highlighting the waste potential for sustainable and economical AC production. This underscores the importance of optimizing activation parameters to enhance performance and application versatility in AC production from lignocellulosic sources.

Stabilization of arsenic-cadmium co-contaminated soil with the iron-manganese sludge derived amendment: Effects and mechanisms

An iron-manganese sludge-derived amendment was proposed to remediate arsenic (As) and cadmium (Cd) co-contaminated soil, with a strong adsorptive capacity across pH 4 to 10. The Langmuir model defined maximum adsorption at 78.17 mg/g for As(III), 110.48 mg/kg for As(V), and 65.77 mg/g for Cd(II). The X-ray photoelectron spectroscopy (XPS) spectra provided insights into the chemical interactions: As was predominantly complexed or ligand exchanged with iron(hydr)oxides. In contrast, cadmium exhibited a tendency to bond with acylamino and carboxyl groups, in addition to the ferric hydroxyl groups. Notably, 42.15% of the adsorbed As(III) was oxidized into As(V) by Mn(IV) oxides present in the amendment. The soil-verification experiment demonstrated that an amendment dosage of 40 g/kg was efficacious in reducing the leaching concentration of As and Cd to maintained below the safety thresholds of 0.1 mg/L and 0.01 mg/L, respectively, for pH levels 4 to 11, meeting the Chinese Surface Water Quality Standard V (GB3838-2002). After the stabilization, the exchangeable fractions of As and the acid-soluble fractions of Cd were significantly reduced, with these elements being transformed into more stable forms. The amendment maintained the soil's neutral pH and adjusted the soil physicochemical properties. This article presents a holistic approach by examining the organic-inorganic composite of iron-manganese oxides with polyacrylamide, modified as a stabilizing amendment for As and Cd co-contaminated soil. This innovative amendment adeptly navigates the previously conflicting stabilization mechanisms for anionic and cationic metals. Offering dual advantages, the amendment not only remediates soil but also addresses the disposal of waste, presenting a win-win solution for environmental management.

Low-energy argon ion beam irradiation for the surface modification and reduction of graphene oxide: Insights from XPS

Developing environmentally friendly methods for reducing graphene oxide (GO) is essential. This study investigates the surface modification and reduction of GO films using 200 eV argon ion (Ar+) beam irradiation. X-ray Photoelectron Spectroscopy (XPS) analysis reveals significant chemical changes on the GO surface. GO was irradiated with a 200 eV Ar+beam for varying times (0–80 s). XPS survey spectra showed the presence of carbon and oxygen, with an increasing carbon atomic percentage over time. High-resolution XPS spectra of C 1s revealed peaks corresponding to sp2, C–OH, O–C–O, CO, and O–CO bonds. In the O 1s spectra, CO, O–C–O, and C–OH groups were observed. Upon irradiation, the CO peak consistently decreased, the O–C–O peak fluctuated, and the C–OH peak increased, indicating effective reduction of CO groups, dynamic changes in O–C–O functionalities, and the formation of additional C–OH groups. The C/O ratio increased from ∼2.4 to 2.7, underscoring the reduction process and enhanced carbon content. This method proves to be an efficient approach for producing reduced graphene oxide (rGO) with improved properties for advanced applications.

Benchmark Study of Core-Ionization Energies with the Generalized Active Space-Driven Similarity Renormalization Group.

X-ray photoelectron spectroscopy (XPS) is a powerful experimental technique for probing the electronic structure of molecules and materials; however, interpreting XPS data requires accurate computational methods to model core-ionized states. This work proposes and benchmarks a new approach based on the generalized active space-driven similarity renormalization group (GAS-DSRG) for calculating core-ionization energies and treating correlation effects at the perturbative and nonperturbative levels. We tested the GAS-DSRG across three data sets. First, the vertical core-ionization energies of small molecules containing first-row elements are evaluated. GAS-DSRG achieves mean absolute errors below 0.3 eV, which is comparable to high-level coupled cluster methods. Next, the accuracy of GAS-DSRG is evaluated for larger organic molecules using the CORE65 data set, with the DSRG-MRPT3 level yielding a mean absolute error of only 0.34 eV for 65 core-ionization transitions. Insights are provided into the treatment of static and dynamic correlation, the importance of high-order perturbation theory, and notable differences from density functional theory in the predicted energy ordering of core-ionized states for specific molecules. Finally, vibrationally resolved XPS spectra of diatomic molecules (CO, N2, and O2) are simulated, showing excellent agreement with experimental data.

Regulated Photocatalytic CO2-to-CH3OH Pathway by Synergetic Dual Active Sites of Interlayer.

Herein, composites of nanosheets with van der Waals contacts are employed to disclose how the interlayer-microenvironment affects the product selectivity of carbon dioxide (CO2) photoreduction. The concept of composites of nanosheets with dual active sites is introduced to manipulate the bonding configuration and promote the thermodynamic formation of methanol (CH3OH). As a prototype, the CoNi2S4-In2O3 composites of nanosheets are prepared, in which high-resolution transmission electron microscopy imaging, X-ray photoelectron spectroscopy spectra, and zeta potential tests confirm the presence of van der Waals contacts rather than chemical bonding between the In2O3 nanosheets and the CoNi2S4 nanosheets within the composite. The fabricated CoNi2S4-In2O3 composites of nanosheets exhibit the detection of the key intermediate *CH3O during CO2 photoreduction through in situ Fourier transform infrared spectra, while the In2O3 nanosheets and CoNi2S4 nanosheets alone do not show this capability, further verified by the density functional theory calculations. Accordingly, the CoNi2S4-In2O3 composites of nanosheets show the ability to produce CH3OH, whereas the CoNi2S4 and In2O3 nanosheets solely generate carbon monoxide products from CO2 photoreduction.

MoⅣ boosted carrier density of MoO3-X for surface-enhanced Raman spectroscopy

Molybdenum oxides (MoO3-X) with the same surface plasmon resonance (SPR) effect as Au/Ag, and occupies an irreplaceable value in SERS detections. MoO3-X SERS substrates with oxygen-rich defects tend to show better SERS performance, but the preparation and characterization of tunable O defects remain challenging. It cannot be ignored that the oxidation state of metal cations is also influenced by O defects. Here, a series of MoO3-X SERS sensors with regulable Mo valence state were fabricated using magnetron sputtering technology. By changing the Mo sputtering power and the O2/Ar2 ratio, the Mo/O element ratio of the substrate can be easily regulated to readjust the O defects. The X-ray Photoelectron Spectroscopy (XPS) and Raman spectra were performed to investigate the change and related relationship between Mo mixed valence state and SERS sensitivity. The abundant incompletely coordinated electrons produced by low valence MoⅣ act as free carriers, increasing the free carrier density of MoO3-X substrates, which is beneficial for the SERS effect. It has also been proven by Hall effect measurement. The SERS measurement shows that the enhancement factor (EF) reached 3.70 × 105, which is exceedingly close to Au/Ag. The MoO2.5 substrate also exhibited a repeatable and consistent response, high stability, and repeatability, which proves the splendid application potential in complex environments.

Ligand-free Ni-Cu bimetallic nanocatalyst: Laser synthesis, characterization and its high performance for borohydride assisted catalytic reduction of 4-nitrophenol

In the present work, nickel and copper bimetallic nanoparticles with three different concentration ratios of 70:30, 50:50, and 30:70 were synthesized by laser ablation of Ni and Cu in deionized water. The suitability of Ni-Cu bimetallics as nanocatalysts was investigated in the catalytic reduction of pollutant 4-nitrophenol. The nanocatalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible (UV–Vis) spectroscopy. The morphology using SEM and TEM indicated that Cu had an elongated or flake-like structure, whereas Ni had a quasi-spherical structure. XPS investigation has been performed to study the elemental composition and chemical states near-surface regions of the generated Ni-Cu bimetallic nanoparticles. XRD and XPS confirm high oxidation of Cu to CuO with approximately no residual Cu metal. However, the XRD patterns did not show complete Ni oxidation to NiO, confirming the presence of a Ni dopant part in the Ni-Cu samples. The behavior of the photoelectron peaks in the XPS spectra suggested that the Ni-Cu nanocomposites exhibited surface charge transfer. Pulsed laser ablation developed ligand-free Ni-Cu nanoparticles, which affected the structure and catalytic properties. The nanocatalyst for 50:50 of Ni and Cu had the highest rate constant, corresponding to the shortest time required to achieve 100 % conversion/reduction of the pollutant dye. The apparent synergistic effect between Ni and Cu is clearly dictated by the amount of Cu embedded in the nanocomposites, with this becoming a key factor in lowering the band gap energy values. Overall, the surface charge transfer rate can enhance the catalytic performance by tuning the Ni and Cu concentrations.