X-ray Photoelectron Spectroscopy Studies Research Articles

Reaction mechanisms and diagnostic mineralogy of intertidal steel corrosion: An X-ray photoelectron spectroscopy study

The products of intertidal and super tidal (splash zone) corrosion on steel piles have been characterised at 3 UK sites with contrasting environmental conditions in order to determine corrosion reaction mechanism and if a common mechanism for accelerated low water corrosion occurs across sites. Intertidal corrosion samples at Shoreham and Newhaven ports show an internal composition of iron mono- and bi-sulphide, with intermediate sulphur oxidation state compounds, and an outer surface dominated by iron oxides and oxyhydroxides with a component of iron sulphates. The FTIR spectra are characteristic of sulphate green rust. In contrast, samples from Southend have all sulphur species below detection levels and are dominated by iron oxides and oxyhydroxides. Carbon binding energy spectra are consistent with the development of biofilms at all sites except for a splash zone sample at Southend. The results demonstrate a common mechanism for ALWC at Newhaven and Shoreham, involving the action of sulphate-reducing bacteria generating iron sulphides on the steel surface. These are subsequently oxidised to produce sulphate green rust, which may in turn oxidise to produce lepidocrocite. At Southend differences in environment are inferred to restrict the activity of sulphate reducing bacteria, resulting in direct oxidation of steel to generate iron oxyhydroxide gels, which subsequently recrystallise, dehydrate and oxidise to goethite, magnetite and ultimately hematite in both splash zone and intertidal samples. The multi-technique approach used here characterises the full range of corrosion products.

Improved contact of “Spiro-OMeTAD/perovskite” interface by hydrophilic 1, 6-hexanediammonium diiodide molecule and the accelerated charge extraction processes

Hydrophilic 1, 6-hexanediammonium diiodide (HDADI) is used to modify the perovskite surface, so as to improve the contact between the “Spiro-OMeTAD/perovskite” interface. It is observed that, after moderate HDADI modification, the wettability of Spiro-OMeTAD/chlorobenzene solution on perovskite is improved. After modified at moderate concentration of HDADI, surface roughness of perovskite film decreases from 19.4 to 15.8 nm, while that of Spiro-OMeTAD (coated on perovskite) decreases from 7.54 to 6.53 nm, indicating better interfacial contact. The improved interfacial contact is due to the hydrophilic nature of the HDADI molecule, and the formed two-dimensional (2D) Dion–Jacobson phase perovskite, as revealed by x-ray diffraction and x-ray photoelectron spectroscopy studies. Photoluminescence and Mott–Schottky studies show that defects are reduced. Accordingly, the charge-extraction rate is accelerated, while recombination is reduced according to transient photovoltaic/photocurrent decay curves tests and impedance spectroscopy. Photo-to-electric power conversion test demonstrates that the modification helps upgrade the power conversion efficiency of perovskite solar cells from 20.25 (±0.85)% to 22.28 (±0.53)% (with a champion efficiency of 23.08%). In addition, device stability has also been prolonged. This study provides an efficient strategy to strengthen the contact between the “Spiro-OMeTAD/perovskite” interface.

Bismuth sulfide micro flowers decorated nickel foam as a promising electrochemical sensor for quantitative analysis of melamine in bottled milk samples

Here, we demonstrate hydrothermally grown bismuth sulfide (Bi2S3) micro flowers decorated nickel foam (NF) for electrochemical detection of melamine in bottled milk samples. The orthorhombic phase of hydrothermally grown Bi2S3 is confirmed by the detailed characterization of x-ray diffraction and its high surface area micro flowers-like morphology is investigated via field emission scanning electron microscope. Furthermore, the surface chemical oxidation state and binding energy of Bi2S3/NF micro flowers is analyzed by x-ray photoelectron spectroscopy studies. The sensor exhibits a wide linear range of detection from 10 ng l−1 to 1 mg l−1 and a superior sensitivity of 3.4 mA cm−2 to melamine using differential pulse voltammetry technique, with a lower limit of detection (7.1 ng l−1). The as-fabricated sensor is highly selective against interfering species of p-phenylenediamine (PPDA), cyanuric acid (CA), aniline, ascorbic acid, glucose (Glu), and calcium ion (Ca2+). Real-time analysis done in milk by the standard addition method shows an excellent recovery percentage of ̴ 98%. The sensor’s electrochemical mechanism studies reveal that the high surface area bismuth sulfide micro flowers surface interacts strongly with melamine molecules through hydrogen bonding and van der Waals forces, resulting in a significant change in the sensor’s electrical properties while 3D skeletal Nickel foam as a substrate provides stability, enhances its catalytic activity by providing a more number /of active sites and facilitates rapid electron transfer. The work presented here confirms Bi2S3/NF as a high-performance electrode that can be used for the detection of other biomolecules used in clinical diagnosis and biomedical research.

Methodical tuning of NH3 gas sensing in WO3 thin films by electron beam irradiation

The present work focuses on the structure, morphology, optical and sensing analysis of Electron Beam Irradiation (EBI) treated WO3 films synthesized by the spray pyrolysis technique. X-ray diffraction (XRD) revealed a slight shift in the 2θ position, indicating stress generated due to EBI process. Scanning Electron Microscopy (SEM) morphographs presented well-defined grains at higher irradiation dosages. X-ray Photoelectron Spectroscopy (XPS) studies showed increased oxygen vacancy defects for the 5 kGy treated sample compared to unirradiated WO3. Sensing analysis of unirradiated and EBI-treated films was conducted towards ammonia (NH3) at an optimum operating temperature of 200 °C. Sensor response of 5 kGy treated film increased by − 4.5 fold compared to unirradiated film at 5 ppm NH3 concentration. The current study demonstrates the importance of EBI in tailoring the NH3 sensing properties of WO3 films.

Low field-cooled induced large exchange bias effect and DFT calculations in ferromagnetic Sm2CoMnO6

In the present report, we study the large exchange bias effect in Sm2CoMnO6 (SCMO) polycrystalline samples synthesized with the presence of two crystallographic phases: ordered-phase (monoclinic; P21/n) and disordered-phase (orthorhombic; Pnma). X-ray photoelectron spectroscopy study revealed the presence of mixed valence states for Co (2+ & 3+) and Mn (4+ & 3+). M(T) data exhibits an inhomogeneous magnetic state with the presence of ferromagnetic ordering at TC ∼128 K due to the super-exchange interactions of Co2+-O2--Mn4+ and antiferromagnetic-like spin correlations for T < 50 K, attributed to Co3+-O2--Co3+, and Mn3+-O2--Mn3+ interactions. M(H) loop shift with a conventional exchange bias (EB) effect of 10 kOe for a field-cooled (HFC) of 10 kOe at 2 K was observed. Such a large value of the EB effect for low HFC in SCMO is comparable to that of large EB compounds, such as La1·5Sr0·5CoMnO6 and NiFe2O4/CoO nanocomposites. The zero-field cooled asymmetry in M(H) loop termed as spontaneous exchange bias effect (SEB) observed for T < 20 K. The systematic study of EB effects like HEB and MEB with T(K) and HFC was explained qualitatively by the presence of unidirectional anisotropy formed at the interface of inhomogeneous magnetic phases. Further, density functional theory (DFT) calculations validate the ferromagnetic ground state of SCMO with Co and Mn networks. Moreover, the semiconductor characteristics of SCMO are established with a band gap of 1.3 eV.

Enhanced ammonia sensing performance of barium hexaferrite enabled through Zn doping: Mechanistic study considering modulation of Fe2+/Fe3+ ratio and oxygen vacancy

Barium hexaferrite (BaFe12O19) is an unexplored metal-oxide semiconductor with regard to ammonia (NH3) gas sensing. Herein, we have achieved substantial enhancement in response towards NH3 by virtue of Zn doping in BaFe12O19, synthesized via facile solid-state route. The improved response (Rgas/Rair) of Zn-doped BaFe12O19 towards 1 ppm NH3 was 7.36 at 250 °C which was ∼300% higher than pure BaFe12O19. Moreover, fast response/recovery time (2.66 s/35.25 s), good selectivity and long-term stability (100 days) towards NH3 has been achieved when Zn was incorporated. The lower limit of detection of Zn doped BaFe12O19 was estimated ∼150 ppb, that exceedingly favors lower concentration range of NH3 detection. Excellent sensing behavior of Zn-doped BaFe12O19 samples was attributed to modulation of Fe2+/Fe3+ ratio, oxygen vacancies and improved oxygen adsorbing ability as confirmed from X-ray photoelectron spectroscopy (XPS) study. Also, the improvement in sensing activity was validated through quenching of photoluminescence (PL) spectra in favor of electron-hole separation. The usefulness of developed Zn-doped BaFe12O19-based sensor for environmental air-quality surveillance and individualized health monitoring can be concluded through the sensor's notable resolution in detection of wide range (150 ppb - 100 ppm) of ammonia concentration.

Si4Al2O2N6 regulating chemical states of Co catalyst for improved hydrogen production from ethanol steam reforming

Tuning the metal-support interaction is a general strategy of regulating the chemical state of catalytic active site for high-efficiency hydrogen production from ethanol steam reforming (ESR) reaction. In this work, a Co catalyst supported on the Si4Al2O2N6 solid solution of Si3N4 and Al2O3 (Co/Si4Al2O2N6) has been developed to effectively catalyze ESR reaction. Our results demonstrate that the Co/Si4Al2O2N6 catalyst exhibits remarkably improved performances as compared with the Co/Si3N4 and Co/Al2O3 catalysts. In the Co/Si4Al2O2N6-catalyzed ESR reaction, ethanol conversion of 97 % has been achieved with hydrogen yield reaching 73 %. Long-time catalytic experiment manifests the Co/Si4Al2O2N6 catalyst possesses excellent durability. X-ray photoelectron spectroscopy (XPS) studies reveal that the enhanced metal-support interaction (MSI) and charge transfer from Si4Al2O2N6 support to Co species in the Co/Si4Al2O2N6 catalyst confer lower valence state on the Co catalyst supported on Si4Al2O2N6, thus promoting the C–C bond cleavage capability, leading to high C1 product yield and boosting the hydrogen-production efficiency. The catalytic mechanism studies explored by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveal that the Co/Si4Al2O2N6 exhibits a remarkable preference for C1 products over the Co/Si3N4 and Co/Al2O3 catalysts at low reaction temperature, thus resulting in high hydrogen-production efficiency with excellent catalytic durability.

Design of FeWO4@N-TiO2 nanocomposite and its enhanced photocatalytic activity in decomposing methylene blue and phenol under visible light

Effluents from textile industries contain high levels of methylene blue (MB) and phenol from other industries, which are serious health hazard and a threat to biodiversity as well as the environment. Nitrogen (N) doped TiO2 modified by iron tungstate (FeWO4) composite photocatalyst (FeWO4 @N-TiO2) working under visible light (λ ≥ 420 nm) could be a suitable candidate to degrade this pollutant. X-ray diffractometry (XRD) and X-ray Photoelectron Spectroscopy (XPS) study suggested that the N was introduced as substitutional doping into TiO2 lattice which leads to narrowing band gap of TiO2 nanoparticles. The prepared FeWO4 @N-TiO2 was utilized to measure efficiency in decomposing the methylene blue (MB) and phenol in aqueous phase under visible light (λ ≥ 420 nm) irradiation. The FeWO4 @N-TiO2 showed better catalytic efficiency to degrade MB and phenol in several compositions of FeWO4. The composite demonstrated 77% and 85% removal of MB and phenol from aqueous medium after 2 h of visible light illumination, respectively. Interestingly, radical-hole hunting identifying tests indicated the presence of hydroxyl radical (°OH) in the photocatalytic decomposition reaction medium. The higher efficiency of FeWO4 @N-TiO2 was originated from absorption of visible energy as well as the relative energy band positions of the components FeWO4 and N-TiO2. Thus, photoexcited electron (e‾) and hole (h+) could take part by inter-particle transfer through the formation of °OH radical which was experimentally confirmed and a photocatalytic reaction mechanism has been proposed to mineralize organics.

Interactions in Al2O3 - graphene oxide composite: XPS study

The structure of an aluminum oxide/graphene oxide (GO) composite was studied using X-ray photoelectron spectroscopy (XPS). High-energy resolved XPS measurements of Al 2p-core level spectra revealed the formation of Al–O–C bonds, which indicated the occurrence of interfacial reactions between Al2O3 and GO in the process of composite synthesis. An increase in intensity in the near-edge region of XPS valence band (VB) spectrum was observed with increasing GO concentration, indicating possible contribution of the electronic states of carbon. Filling the electronic states on the edge of VB allows to associate GO doping with the loss of dielectric properties of the original Al2O3 compound. Addition of graphene oxide to Al2O3 ceramics changed conductive properties of the composite due to formation of new chemical bonds.

Characterization of peroxide on coal surface: A combined △SCF and XPS study

X‐ray photoelectron spectroscopy (XPS) is widely used to determine the composition of elements and oxygen‐containing functional groups. Accurate determination of core‐electron binding energies (CEBEs) is essential for identifying the types and contents of oxygen‐functional groups present on the surface of coal. The △SCF method has been carried out on CEBEs for an extensive series of oxygen‐containing organic systems encompassing the most common functionalities. The polymers for which experimental values are available for comparison demonstrate the adequacy of the treatment for describing CEBEs for the O1s core level. Therefore, a sound basis is provided for the discussion of CEBEs (O1s) for functionalities for which experimental values are not accurate or available, such as carbonyl, carboxyl, and peroxide. The results are applied to the XPS study of oxidized coal. The change law of peroxide and oxygen‐containing functional groups was discussed. The calculation method and results in this paper can provide a guide for readers to use XPS to study the oxidation of coal surfaces.

Influence of gadolinium doping on structural, optical, and electronic properties of polymeric graphitic carbon nitride.

Polymeric graphitic carbon nitride (gCN) materials have received great attention in the fields of photo and electrocatalysis due to their distinct properties in metal-free systems with high physicochemical stability. Nevertheless, the activity of undoped gCN is limited due to its relatively low specific surface area, low conductivity, and poor dispersibility. Doping Gd atoms in a gCN matrix is an efficient strategy to fine-tune its catalytic activity and its electronic structure. Herein, the influence of various wt% of gadolinium (Gd) doped in melon-type carbon nitride was systematically investigated. Gadolinium-doped graphitic carbon nitride (GdgCN) was synthesized by adding gadolinium nitrate to dicyandiamide during polymerization. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the crystallinity and the morphological properties are influenced by the % of Gd doping. Furthermore, X-ray photoelectron spectroscopy (XPS) studies revealed that the gadolinium ions bonded with nitrogen atoms. Complementary density functional theory (DFT) calculations illustrate possible bonding configurations of Gd ions both in bulk material and on ultrathin melon layers and provide evidence for the corresponding bandgap modifications induced by gadolinium doping.

Ag4Br6] cluster-based 3D bromoargentate hybrid: crystal structure, optical/photoelectrical performance and theoretical study.

The self-assembly of cluster-based halide framework materials has been a matter of great interest but with great challenges. Herein, by exploiting hexamethylenetetramine (Hmta) with Td symmetry as a structural modifier, we successfully constructed and systematically characterized an unusual three-dimensional (3D) hybrid bromoargentate, namely K[NH4][Ag4Br6(Hmta)] (1), bearing a diamond-type [Ag4Br6(Hmta)]n2n- anionic skeleton built up from adamantane-like units of inorganic [Ag4Br6] clusters and organic Hmta ligands. UV-Vis diffuse reflectance analysis showed that the optical bandgap of the title compound was 2.68 eV, indicating a visible-light-responsive semiconductive behavior. More importantly, upon alternate light illumination, the so-designed compound exhibited remarkable photoelectric switching properties, with photocurrent densities (0.38 and 1.10 μA cm-2 for visible and full-spectrum light, respectively) that compete well with and even exceed those of some high-performance metal halide counterparts. Further theoretical calculations, including band structure, density of states, and wave functions, revealed that compound 1 has a unique valence band and conduction band distribution, rendering it with small effective masses (especially the electrons), which may be responsible for its good photoelectricity. Furthermore, in this work, Hirshfeld surface analysis, thermogravimetric analysis, and X-ray photoelectron spectroscopy (XPS) studies were performed.

Influence of Au0 metallic particles on NIR laser emission of Yb3+ ions in Li2O−HfO2−SiO2 glass ceramic

This study consists of the synthesis, characterization, and analysis of photoluminescence (PL) spectra for Li2O−HfO2−SiO2−Yb2O3 glass ceramics sensitized with small amounts of Au2O3. Using the results of XRD and X-ray photoelectron spectroscopy (XPS) studies indicated a progressive reduction of Au3+ ions into Au0 metallic particles (MPs) with increase of Au2O3 content. Investigations into the infrared spectra highlighted a growing concentration of induced defects in the samples due to the increased proportion of Au0 MPs. Optical absorption (OA) spectra exhibited a distinct band attributed to the 2F7/2 → 2F5/2 transition of Yb3+ within wavelength range of 800–980 nm. Furthermore, a wide absorption band linked to the surface plasmon resonance (SPR) of Au0 MPs was identified in the visible region. PL spectra, recorded at λexc = 450 nm, revealed a band between 980 to 1025 nm, associated with the 2F5/2 → 2F7/2 transition of Yb3+ ions. Another emission band was observed due to the sp → d transition of Au0 MPs within the visible region. Observed enhanced PL emission from Yb3+ ions in the NIR range was ascribed to the energy transfer from Au0 MPs to Yb3+ ions. Ultimately, it was deduced that Au0 MPs played a pivotal role in enhancing the PL output of Yb3+ ions in the Li2O−HfO2−SiO2 glass ceramic. Thus, glass ceramics incorporating an optimal concentration of Au2O3 hold significant potential as materials for NIR lasers.

Structural, optical and photoluminescence properties of BaLa2ZnO5: Eu3+ phosphor: A prospective red-emitting phosphor for LED applications

Herein, we report the synthesis of red-emitting Eu3+-activated BaLa2ZnO5 phosphors using a high-temperature solid-state reaction technique. The phase confirmation and crystal structure were established through X-ray powder diffraction patterns. Density-functional theory calculations revealed an indirect bandgap in the material. The bandgaps of both undoped and doped BaLa2ZnO5 phosphors were analyzed using diffuse reflectance spectra. The influence of Eu3+ doping on the bandgap was confirmed by applying the Kubelka-Munk function to the diffuse reflectance spectra. The effects of doping on the surface morphology and elemental composition were investigated through field emission scanning electron microscopy and energy-dispersive spectroscopy, respectively. Additionally, X-ray photoelectron spectroscopic studies were conducted to analyze the electronic structure, chemical states and impact of doping on the crystal structure. Using near ultraviolet excitation at 329 nm, the synthesized phosphor exhibited strong red emission attributed to various 5D0 → 7FJ transitions. Concentration quenching phenomena were observed due to dipole-dipole interactions. Judd-Ofelt analysis was performed to elucidate the coordination nature of the doping element in the host lattice. Excellent thermal stability was observed with an activation energy of 0.64 eV for discharging via lattice vibrations. The better color purity (98–99.3 %) and stable Commission Internationale de l’Elcairage coordinates in the red region of the gamut suggest that the prepared phosphor material holds potential as an efficient candidate for ultra violet and blue light-emitting diode chips, as well as an efficient component in the fabrication of white light-emitting diodes.

Unraveling the Photoluminescence Properties of a Boron Nitride Nanosheet Dispersed in Different Solvents and Its Application to Generate White Light.

Hexagonal boron nitride (h-BN) is an influential 2D nanomaterial; however, its practical optoelectronic applications rely primarily on controlling the structural defects. The photoluminescence depends explicitly on the developed vacancies and substitutional defects. The present work utilizes the concept of facile liquid-phase exfoliation of hexagonal (h) boron nitride (BN) powder in common organic solvents and cosolvent mixtures to obtain a layered boron nitride nanosheet (BNNS). Although the literature concerning the layered structure of BNNS obtained by different methods is substantial, what is lacking is a detailed photoluminescence study of the layered structure obtained by changing the solvent and cosolvent mixtures, and here lies the novelty of our work. The obtained layered structure was subjected to a detailed photoluminescence study by varying the temperature. We tried to correlate how the defects originating upon changing the solvent and cosolvent affected the photoluminescence of the layered BNNS. The obtained layered structure is suitably supported by optical and electron microscopy images. High-resolution transmission electron microscopy confirm the presence of a few layers, and X-ray photoelectron spectroscopy studies give an idea of the atomic composition of the obtained BNNS. The photoluminescence properties of the obtained BNNS in water were modulated by the addition of two different classes of block copolymers, e.g., Pluronic (F-68, P-407, and P-123) and Tetronic (T-904, T-908, and T-90R4) copolymers. As an application, we were successful in constructing a nanocomposite material made up of a BNNS-copolymer-organic fluorophore to check the possibilities of generating white light.

Metal doped silica nanohybrids with extensive bacterial coverage for antibacterial applications exhibit synergistic activity

Nanotechnology has triumphantly overcome several barriers that have formed in modern life. Bacterial infections are a critical public health issue. They emphasized the failure of conventional treatments, high mortality and morbidity rates, antibiotic resistance, and other factors leading to the development of novel and affordable antibacterial medications. In this study, three types of metals (Ag, Cu, and Co) were doped separately into a silanol network in silica nanoparticles. The synthesized monometallic nanohybrids were combined in equal proportions to formulate bi and trimetallic nanohybrids. They were characterized structurally and morphologically. Fourier transform infrared (FTIR) and Raman spectroscopy studies were used to investigate the formation of the bonds and the pertinent peak positions. X-ray diffractograms (XRD) validated the crystalline structures of the metal nanohybrids. X-ray photoelectron spectroscopic study (XPS) confirmed the successful addition of metals to the silanol network. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images were used to characterize the morphology of nanohybrids and demonstrate their dimensions are on the nanoscale. The fraction of each metal doped in the silanol network was determined using energy dispersive spectroscopy (EDS) and atomic absorption spectrometry (AAS). To assess activity and confirm antibacterial synergy, the antibacterial activity of all synthesized nanohybrids was examined. The minimum inhibitory concentration-MIC (Ranged from 12.25 to 1560.00 μg/mL), minimum bactericidal concentration-MBC (Ranged from 197.00 to 3125.00 μg/mL), IC50 values (Ranged from 30.56 to 1683.00 μg/mL-) and fractional inhibitory concentration index (FICI) were determined and compared. Well diffusion assay was conducted against both ATCC cultures and clinical samples of gram-positive bacteria; Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), MRSA (ATCC 33591) and gram-negative bacteria; Escherichia coli (ATCC 25922), Klebsiella pneumoniae (ATCC BAA 1706) and Pseudomonas aeruginosa (ATCC 27853). The highest synergistic radical scavenging performance of trimetallic nanohybrid (90.67 ± 0.095 %) was established by the DPPH (2,2 diphenyl-1-picrylhydrazil) experiment. Finally, when compared to monometallic nanohybrids, it was demonstrated that the synthesized multimetallic nanohybrids have a substantial potential as an emerging and cost-effective antibacterial agent.

High-capacity all-solid-state Li-ion battery using MOF-derived carbon-encapsulated iron phosphide as anode material

Iron Phosphide (Fe2P) particles embedded within in-situ generated tubular carbon structures uniformly doped with nitrogen heteroatoms (Fe2P @ NC) have been investigated as an anode in all-solid-state lithium-ion batteries (ASSLIBs). The designed morphology offered a number of suitable features, such as high conductivity, robust framework, and abundant redox active sites for augmenting overall battery performance. As anode, Fe2P @ NC has provided a high lithiation/delithiation capacity of 1214.8 mA h/g /1367.01 mA h/g at a current density of 66.6 mA/g (100 μA) with a high coulombic efficiency (>100%). Further, Fe2P @ NC also demonstrated an excellent rate performance and moderate structural stability during cycling. The charge storing mechanism for Fe2P @ NC investigated via ex-situ X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) studies indicates irreversible conversion of Fe2P → Li3P & Fe in the initial cycle and reversible Li3P ↔ LiP reaction in subsequent cycles. Analysis of reaction kinetics for Fe2P @ NC nanocomposite is carried out using CV measurements at different scan rates. This study explores the possibility of MOF-derived iron-phosphide-based composite material as a high-performance anode for ASSLIBs.

Synthesis of novel nanocomposite of g-C3N4 coated ZnO–MoS2 for energy storage and photocatalytic applications

Fabrication of heterostructures for energy storage and environmental remedial applications is an interesting subject of research that has been undertaken in this present investigation. The incorporation of g-C3N4 into ZnO:MoS2 heterojunction nanocomposite was accomplished by wet-chemical route and characterized by various techniques to ascertain its structure, morphology, and study its potential electro-optical characteristics. The g-C3N4@ZnO:MoS2 sample was investigated by x-ray diffraction (XRD) which reveals the co-existence of the ZnO, MoS2 and C3N4 phases linked to characteristic crystallographic planes in the spectrum, validating the formation of ternary nanocomposite. The XRD patterns of the pristine samples were also considered as reference to understand the structural evolution and phase transformations. Field emission scanning electron microscopy (FESEM) study states the formation of heterogeneous nanostructures having nanoparticles embedded on 2-D nanosheets like structures. Studies using energy dispersive spectroscopy (EDS) and elemental mapping show that all the elements that are linked to the above hybrid nanocomposite are present. Transmission electron microscopy (TEM) provided clear insights on the microstructure as we can identify the distribution of ZnO and MoS2 nanostructures on layered g-C3N4 nanosheets. The chemical composition and oxidation states of elements were elucidated by X-ray photoelectron spectroscopy (XPS) study, which added another layer of confirmation on the structural evolution of the ternary nanocomposite. Fourier transformed infrared (FTIR) study revealed the layered structure of sp2 hybridized bonding features of C and N in g-C3N4, besides Zn–O and Mo–S stretching vibrations. The nanocomposite demonstrated improved photodegradation efficacy and decomposed alizarin red and methylene blue dyes significantly with better stability and reusability. MoS2 as a co-catalyst acts as an electron acceptor/accelerator in the Z-scheme composite photocatalysis leading to improved photocatalytic efficiency. The resulting heterostructured material delivered a higher specific capacitance of 10.85 F/g with good capacitance retention. Electrochemical study revealed the energy storage capability of the hybrid system.

Promotion of Sulfur Vacancies and Mn Substitution in Few-Layered Molybdenum Disulfide Towards Superior Hydrogen Evolution in Acid

The superior features of hydrogen as an energy source with high energy density (120 MJ kg-1) and zero CO2 emission, makes it a strong candidate for replacing fossil fuels. Recently the European Commission has pledged to invest €470 billion in renewable hydrogen technologies by 2050, with a significant portion of this investment expected to be allocated for the deployment of renewable hydrogen electrolyzers by 2030. Water electrolysis via Proton Exchange Membrane (PEM) with Pt/Pd-based noble metals as a cathode, is currently the most effective method for hydrogen production, but alternatives are highly needed due to the scarcity and the higher cost of these metals. One of the promising classes of electrocatalysts for hydrogen evolution reaction (HER) is transition metal dichalcogenides (TMDs), and among them molybdenum disulfide (MoS2) has shown promising properties as an electrocatalyst for hydrogen production. MoS2 has different phases of 1T, 2H, and 3R with 2H-MoS2 being the most promising electrocatalyst for hydrogen production due to its semiconductive behavior and long-term stability. However, the poor conductivity, large band gap and no active basal plane towards HER limits the applications of 2H-MoS2 for water electrolysis in PEM cells. Strategies such as introduction of defects, S-vacancies, edge engineering and doping can result in enhanced HER activity of 2H-MoS2. Incorporating different transition metals (Ni, Co, Mn, Fe) into MoS2 lattice can increase the number of active sites and improve charge transfer during the electrocatalytic reaction. Based on Density Functional Theory (DFT) studies, insertion of Mn into MoS2 layer can decrease the bandgap to zero, resulting in large number of available electronic states around the Fermi level. In this work we introduce Mn doped MoS2 produced via a cost-effective microwave-assisted solid-state approach to explore the potential of few-layered MoS2, doped with different levels of manganese (5%, 10% and 15% at.) for HER in acidic media. The electrocatalytic activity towards HER reveals that 10% at. Mn incorporation into MoS2 lattice, reduces the overpotential (η10) from 210 mV for pristine MoS2 to 148 mV for 10%Mn-MoS2, respectively. In addition, Tafel slope analysis has confirmed a faster kinetics of 10%Mn-MoS2 (53 mV dec-1) compared to MoS2 (75 mV dec-1) revealing the Volmer–Heyrovsky mechanism as the rate determining step (rds). Further characterization by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and DFT studies show that Mn substitution promotes the creation of sulfur vacancies, which in turn enhances the catalytic activity towards HER. Additionally, the 10% Mn-doped MoS2 demonstrates remarkable activity in a single-cell PEM electrolyzer with long-term durability. This study highlights the potential of Mn doped MoS2 as an efficient, low-cost electrocatalyst for hydrogen production, with implications for the development of a sustainable hydrogen economy. Figure 1

Alcohol Vapor Sensor Based on Quasi-2D Nb2O5 Derived from Oxidized Nb2CTz MXenes.

MXenes are two-dimensional (2D) materials with a great potential for sensor applications due to their high aspect ratio and fully functionalized surface that can be tuned for specific gas adsorption. Here, we demonstrate that the Nb2CTz-based sensor exhibits high performance towards alcohol vapors at temperatures up to 300-350 °C, with the best sensitivity towards ethanol. We attribute the observed remarkable chemiresistive effect of this material to the formation of quasi-2D Nb2O5 sheets as the result of the oxidation of Nb-based MXenes. These findings are supported by synchrotron X-ray photoelectron spectroscopy studies together with X-ray diffraction and electron microscopy observations. For analyte selectivity, we employ a multisensor approach where the gas recognition is achieved by linear discriminant analysis of the vector response of the on-chip sensor array. The reported protocol demonstrates that MXene layers are efficient precursors for the derivation of 2D oxide architectures, which are suitable for developing gas sensors and sensor arrays.