2p X-ray Photoelectron Spectroscopy Research Articles

Atomic-level insights into the activation of nitrogen via hydrogen-bond interaction toward nitrogen photofixation

Summary As the activation of N2 molecules is generally regarded as the bottleneck in N2 reduction, it is of significant importance to develop promising strategies to efficiently activate N2 molecules. Herein, we discovered an innovative approach to activate N2 molecules via hydrogen-bond interaction in N2 photofixation. Porous Cu with surface modification of S atoms (3%-S/Cu) exhibited remarkable catalytic activity and stability in N2 photofixation. Further mechanistic studies revealed that surface S atoms directly participated in the catalytic process by accepting and donating H atoms. In addition, the forming S–H bond significantly promoted the activation of N2 molecules via hydrogen-bond interaction, contributing to the enhanced catalytic activity.

Combined multiplet theory and experiment for the Fe 2p and 3p XPS of FeO and Fe2O3.

The Al K alpha, 1486.6 eV, based x-ray photoelectron spectroscopy (XPS) of Fe 2p and Fe 3p for Fe(III) in Fe2O3 and Fe(II) in FeO is compared with theoretical predictions based on ab initio wavefunctions that accurately treat the final, core-hole, multiplets. The principal objectives of this comparison are to understand the multiplet structure and to evaluate the use of both the 2p and 3p spectra in determining oxidation states. In order to properly interpret the features of these spectra and to use the XPS to provide atomistic insights as well as atomic composition, it is necessary to understand the origin of the multiplet energies and intensities. The theoretical treatment takes into account the ligand field and spin-orbit splittings, the covalent mixing of ligand and Fe 3d orbitals, and the angular momentum coupling of the open shell electrons. These effects lead to the distribution of XPS intensity into a large number of final, ionic, states that are only partly resolved with energies spread over a wide range of binding energies. For this reason, it is necessary to record the Fe 2p and 3p XPS spectra over a wide energy range, which includes all the multiplets in the theoretical treatment as well as additional shake satellites. We also evaluate the effects of differing assumptions concerning the extrinsic background subtraction, to make sure our experimental spectrum may be fairly compared to the theory. We conclude that the Fe 3p XPS provides an additional means for distinguishing Fe(III) and Fe(II) oxidation states beyond just using the Fe 2p spectrum. In particular, with the use of the Fe 3p XPS, the depth of the material probed is about 1.5 times greater than for the Fe 2p XPS. In addition, a new type of atomic many-body effect that involves excitations into orbitals that have Fe f,ℓ = 3, symmetry has been shown to be important for the Fe 3p XPS.

Metal–Organic Framework-Derived CuS Nanocages for Selective CO 2 Electroreduction to Formate

Electroreduction of CO2 to target products with high activity and selectivity has techno-economic importance for renewable energy storage and CO2 utilization. Herein, we report a hierarchical CuS h...

Synergistic Effect of Platinum Single Atoms and Nanoclusters Boosting Electrocatalytic Hydrogen Evolution

Maximizing atomic utilization of precious metal-based catalysts is of great significance in heterogeneous catalysis, also becoming a useful strategy to develop efficient electrocatalysts for hydrog...

Fabrication and characterization of potassium-doped ZnO thin films

To develop a simple and effective method for fabricating a type of transparent p-type zinc oxide (ZnO) thin films, potassium-doped ZnO (K-ZnO) thin films were designed and prepared via molten-salt treatment (MST) in KNO3 for n-type ZnO thin film. The influence of filming temperature during sputtering and the followed MST on the crystalline structure, transmittance, bonding environment, surface morphology, and electrical property of the ZnO thin films has been investigated. The formed compound on quartz glass could be identified as wurtzite ZnO. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results show that the crystalline quality improves with raising the filming temperature. In addition, K 2p XPS spectra hint that the outside surface of ZnO thin films contains a certain amount of K, after MST for ZnO thin films. Compared with that of the followed MST, atomic force microscope (AFM) results also show that the filming temperature significantly affects surface morphology. More importantly, the ZnO thin films obtain p-type characteristics after MST for ZnO n-type thin films, with excellent transmittance and increased mobility.

Regulating Electronic Status of Platinum Nanoparticles by Metal–Organic Frameworks for Selective Catalysis

Selective hydrogenation of alkynes to alkenes remains challenging in the field of catalysis due to the ease of over-hydrogenated of alkynes to alkanes. Favorably, the incorporation of metal nanopar...

Multiplet structure for perovskite-type Ba0.9Ca0.1Ti0.9Zr0.1O3 by core–hole spectroscopies

Core–hole spectroscopies such as x-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HR-EELS) in combination with multiplet calculation are important tools to elucidate the electronic structure of transition metal compounds. This work presents a comparison between the electronic structure obtained by XPS and HR-EELS for polycrystalline perovskite-type Ba0.9Ca0.1Ti0.9Zr0.1O3. Raman analysis suggests that Ca2+ cations could partly occupy the Ti4+ cations in the B-site of a perovskite structure with the tetragonal phase. A multiplet structure was determined by XPS for Ti 2p and by HR-EELS for Ca L2,3 and Ti L2,3 edges. Octahedral (Oh) symmetry in the crystal field (CF) effects reproduces the local distortion of TiO6 octahedra. The charge transfer (CT) effects were also considered to reproduce L3-edge EELS shoulders and the satellite in the Ti 2p XPS region. CF and CT parameters, 10 Dq, (charge transfer energy) Δ, and (Coulomb repulsion energy) Udd, are reported for future reference. The broadening of the Ti L2-edge suggests the presence of the Coster–Kronig electron decay process. Multiplet calculation in Oh symmetry for the Ca L2,3-edge could support the Raman interpretation.

Controllable growth of Ga2O3 hexagonal prism with pyramid end and monitoring size-dependent electron transfer process in perylene/Ga2O3 conjugate system via FLIM

Hexagonal prisms with hexagonal pyramid end of Ga2O3 microstructures were successfully prepared on gallium arsenide substrate by double cell electrochemical etching method under various growth conditions. The field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and fluorescence lifetime imaging microscopy (FLIM) were used to characterize the hexagonal prisms. The EDS analysis confirmed that the prepared prisms were composed dominantly of gallium (Ga) and oxygen (O) with atomic ratio of ~ 2:3. The binding energy of the Ga 2p and Ga 3d XPS peaks revealed that the formation of Ga–O bonding with the highest oxidation state of Ga (Ga3+) and the formed hexagonal microstructures were Ga2O3. The PL spectra at room temperature under excitation at 290 nm exhibit a strong blue emission peak located at about 470 nm. The origin of this PL peak can be attributed to exciton recombination at different intrinsic defect sites such as O vacancies and Ga vacancies. Moreover, FLIM technique has been employed to probe time-resolved photoluminescence properties of individual Ga2O3 prisms with hexagonal tip. FLIM images provide two-dimensional spatial maps of the carrier recombination lifetime which considered the most critical parameter to improve the performance of optoelectronic devices. It has been concluded that the carrier recombination lifetime was strongly sensitive to the size of the hexagonal prism-shaped structures due to surface-related defects. Additionally, a quantitative analysis of a conjugate system prepared by functionalizing hexagonal Ga2O3 prisms with perylene organic dye molecules was reported in this work. The size-dependent electronic coupling between the conduction band level of gallium oxide and excited states of perylene molecules was investigated. We observed that highly efficient electron transfer process occurs for aggregated molecules due to excimer trap states. The grown prism structures seem to be interesting for applications in optoelectronic devices as well as to be used as an effective host medium for organic dye molecules in solar cell applications.

Engineering Electronic Structure of Single-Atom Pd Site on Ti 0.87 O 2 Nanosheet via Charge Transfer Enables C–Br Cleavage for Room-Temperature Suzuki Coupling

The palladium (Pd)-catalyzed Suzuki reaction is widely applied in the pharmaceutical industry, where constructing highly active and low-cost Pd sites are impendent. Here, we report the fabrication ...

Tailored Alkali Resistance of DeNOx Catalysts by Improving Redox Properties and Activating Adsorbed Reactive Species

SummaryIt is still challenging to develop strongly alkali-resistant catalysts for selective catalytic reduction of NOx with NH3. It is generally believed that the maintenance of acidity is the most important factor because of neutral effects of alkali. This work discovers that the redox properties rather than acidity play decisive roles in improving alkali resistance of some specific catalyst systems. K-poisoned Fe-decorated SO42−-modified CeZr oxide (Fe/SO42−/CeZr) catalysts show decreased acidity but reserve the high redox properties. The higher reactivity of NHx species induced by K poisoning compensates for the decreased amount of adsorbed NHx, leading to a desired reaction efficiency between adsorbed NHx and nitrate species. This study provides a unique perspective in designing an alkali-resistant deNOx catalyst via improving redox properties and activating the reactivities of NHx species rather than routinely increasing acidic sites for NHx adsorption, which is of significance for academic interests and practical applications.

Core level photoemission line shape selection: Atomic adsorbates on iron

Robust fitting of core level photoemission spectra is often central to reliable interpretation of X‐ray photoelectron spectroscopy (XPS) data. One key element is employment of the correct line shape function for each spectral component. In this study, we consider this topic, focusing on XPS data from atomic adsorbates, namely, O and S, on Fe(110). The potential of employing density functional theory (DFT) for generating adsorbate projected electronic density of states (PDOS) to support line shape selection is explored. O 1s core level XPS spectra, acquired from various ordered overlayers of chemisorbed O, all display an equivalent asymmetric line shape. Previous work suggests that this asymmetry is a result of finite O PDOS in the vicinity of the Fermi level, allowing O 1s photoexcitation to induce a weighted continuum of final states through electron‐hole pair excitation. This origin is corroborated by O DFT‐PDOS generated for an optimised five‐layer Fe(110)(2 × 2)‐O slab. Adsorbate DFT‐PDOS were also computed for Fe(110) ‐S. As, similar to adsorbed O, there is a significant continuous distribution of states about the Fermi level, it is proposed that the S 2p XPS core levels should also have asymmetric profiles. S 2p XPS data acquired from Fe(110) ‐S, and their subsequent fitting, verify this prediction, suggesting that DFT‐PDOS could aid line shape selection.

ZnCl2 Enabled Synthesis of Highly Crystalline and Emissive Carbon Dots with Exceptional Capability to Generate O2⋅–

Summary Highly crystalline and emissive carbon dots (CDs) are firstly synthesized via an ionothermal method in organic solvents. In contrast to well-established approaches, ZnCl2 is utilized as the pyrolysis-promoting agent to prepare emissive CDs with tunable wavelengths, directly by carbonization from different O and N precursors under a mild reaction condition at 210°C. More than 50% synthetic yield and 39% photoluminescent quantum yield (blue CD) are obtained. XAFS measurements, in conjunction with TEM, HAADF-STEM, UPS, and ESR analyses, allow us to obtain energy diagram configuration and confirm the luminescent nature of these hard-core structured CDs. Importantly, the resulting CDs exhibit excellent capability to photogenerate superoxide radical anion (O2⋅–), which can be exemplified by both photodynamic therapy and photooxidative cyclization synthesis of tetrahydroquinolines. Representative pharmaceutical mifepristone can be derivatized in 90% yield within 10 min of irradiation of the CDs in an elegant flow reactor.

Spectroscopic investigation on tetrahedral Co2+ in thin-film CoFe2O4

CoFe2O4 has been attracting attention for its ferrimagnetism applicable to spin transfer, resonance imaging, drug delivery etc. CoFe2O4 thin films were synthesized on Si(100) substrates by using a sol–gel deposition process. The CoFe2O4 specimen produced by post-annealing in air at 800 °C showed flat surface and polycrystalline grains with no secondary phase. The specimen exhibited magnetic hysteresis curve with magnetization up to 415 emu/cm3 and coercivity of 1.7 kOe. Such a large magnetization implies migration of a number of Co2+ ions from octahedral to tetrahedral sites of the spinel lattice. The distribution of Co2+ ions among tetrahedral and octahedral sites of CoFe2O4 was estimated by curve-fitting analysis on the Raman scattering spectrum of the specimen. The result suggests 30% of the Co2+ ions residing in the tetrahedral sites. The coexistence of Co2+ ions in both tetrahedral and octahedral sites of CoFe2O4 was also detectable by using Co 2p X-ray photoelectron spectroscopy.

Structural Characterizations of Aluminosilicates in Two Types of Fly Ash Samples from Shanxi Province, North China

In order to determine the structural characterization of aluminosilicates in two types of fly ashes, two samples from Shanxi Province, China were selected for study. One was from a pulverized coal boiler (FA-1), and the other from a circulating fluidized bed boiler (FA-2). FA-1 had a much higher content of silicon dioxide (SiO2) (70.30%) than FA-2(42.19%), but aluminum oxide (Al2O3) was higher in FA-2 (25.41%) than in FA-1 (17.04%). The characterizations were investigated using various methods including X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), magic angle spinning nuclear magnetic resonance (MAS–NMR) spectrometry, and X-ray photoelectron spectroscopy (XPS). The XRD analysis showed that FA-1 contained aluminosilicate glass, quartz and mullite, while FA-2 contained significant amounts of amorphous aluminosilicate, quartz and gypsum. The FTIR results showed an increased substitution of Al3+ for Si4+ as the band of asymmetric stretching vibrations Si–O(Si) (1100 cm−1) moved to 1090 cm−1 for FA-2, much lower than for FA-1(1097 cm−1). Moreover, the sharpness of the bands in the 1250–1000 cm−1 region for FA-2 indicates that the silicate structure of FA-2 was more ordered than for FA-1. It can be understood from the 29Si MAS–NMR results that Q4(mAl) (Q4 are connected via 4 bridging O atoms to mAl) is the main structural type in FA-1 and FA-2, and that FA-2 contains more Al, which substitutes for Si in the Q4 structure. 27Al MAS–NMR demonstrated that a combination of tetrahedral, pentahedral, and octahedral Al existed in FA-1 and FA-2. The Si 2p XPS spectra suggested that there were three forms of Si, including bridging Si (Si–O2), non–bridging Si (Si–O), and SiO2 gel. The content of Si–O2 for FA-1 was 37.48% higher than Si–O (28.57%), while the content of Si–O2 was 30.21% lower than Si–O (40.15%) for FA-2. The Al 2p XPS spectra showed that octahedral Al was the dominant form for FA-1 with a content of 40.25%, while the main phase was tetrahedral Al for FA-2 with a proportion of 37.36%, which corresponds well with the 27Al MAS–NMR results.

Taming Active Material-Solid Electrolyte Interfaces with Organic Cathode for All-Solid-State Batteries

Summary Attaining stable active material-solid electrolyte interfaces is a great challenge in sulfide-based all-solid-state sodium batteries (ASSSBs). A resistive layer forms at the interface upon charging above the anodic stability potential of sulfide electrolytes. In addition, contact failure at the interface during cycling is long known, but a fundamental solution is not yet available. Herein, we use an organic cathode material, pyrene-4,5,9,10-tetraone (PTO), to enable high-performance ASSSBs. We report, for the first time, a reversible active material-electrolyte interfacial resistance evolution during cycling. We further show for the first time that a low-modulus cathode material such as PTO maintains intimate interfacial contact with solid electrolytes during cycling, thus improving cycle life. The PTO-based cells exhibit a high specific energy (587 Wh kg−1) and a record cycling stability (500 cycles) among ASSSBs. This work reveals an effective cathode material design strategy toward compatibility with solid electrolytes and thus high-performance ASSSBs.

Floc structure and membrane fouling affected by sodium alginate interaction with Al species as model organic pollutants

Membrane filtration combined with pre-coagulation has advantages in advanced wastewater treatment. As a model of a microbial polysaccharide, research on the effect of sodium alginate (SA) on alum hydrolysis has been rare; therefore, it is necessary to gain insight into the interface interaction between SA molecules and Al species, and the role SA plays during floc formation. In this study, the interaction mechanism between SA and Al species has been investigated, by evaluating the effect of SA on floc characteristics and membrane fouling during coagulation–ultrafiltration with different Al species coagulants (AlCl3 and preformed Al13). Al 2p X-ray photoelectron spectroscopy (XPS) confirmed that the complexation of ligands and Al species strongly affects the reaction pathways for Al hydrolysis and the final nature of the flocs, as Al13 can be decomposed into octahedral precipitates when SA is added. The presence of SA can affect floc properties, which have important impacts on the characteristics of the cake layer and membrane fouling. Due to the bridging ability of SA, the floc strength increased by about 50% using Ala, which was much better than preformed Al13, with a percentage increase of only about 6%. Moreover, the recovery factor of HA-flocs was decreased from 96% to 43% with SA addition of 0.5 mg/L. It was concluded that SA can affect the characteristics of the cake layer and membrane fouling through participating in the formation of primary flocs and altering the Al hydrolysis pathway.

Comment on “removal of hexavalent chromium by biochar supported nZVI composite: Batch and fixed-bed column evaluations, mechanisms, and secondary contamination prevention”

This article aims to discuss (1) the incorrect identification of Cr(III) and Cr(VI) binding energies in the Cr 2p XPS (X-ray photoelectron spectroscopy) spectra of the laden adsorbent (the nZVI-BC sample after Cr(VI) adsorption), (2) misconception regarding the Weber–Morris intraparticle diffusion model, and (3) inconsistency between the experiential data and the Thomas adsorption rate constants. The authors hope that our comments are beneficial for other researchers to avoid the undesirable mistakes.

Enhanced photoelectrochemical performance of CdO-TiO2 nanotubes prepared by direct impregnation

A direct impregnation technique was adopted to prepare a series of CdO-TiO2 nanotubes. Self-organized TiO2 nanotubes were prepared using an optimized two-step anodization process. The morphology, crystallinity, elemental composition, and photoelectrochemical properties of the CdO-TiO2 nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–Vis diffuse reflection spectra (UV–Vis DRS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and photoelectric cell (PEC) measurements. At lower Cd(NO3)2 concentration, no obvious CdO crystalline particle formed on the TiO2 NTbs surface, while the EDS and XPS measurements shows the increasing doping amount of CdO as the Cd(NO3)2 concentration increasing. At a relatively high precursor concentration (800 mM), the formation of particle clusters and nanocrystals on the surface of the TiO2 nanotubes could be easily detected, and the sample presented XRD diffraction peaks indicative of CdTiO3. Meanwhile, the Ti 2p XPS spectra displayed an obvious shift (∼0.3 eV), which could be attributed to the change in the lattice structure. A negative shift in the flatband potential (Vfb) and a decrease in charge carrier density were observed after doping. The maximum incident photon to charge carrier efficiency (IPCE) value calculated for the CdO-TiO2 nanotubes was 10.16%, much higher than that of pure TiO2 nanotubes.

Improving the performance of Li-ion battery carbon anodes by in-situ immobilization of SiOx nanoparticles

A 30% improvement of the capacity of a lithium ion battery was demonstrated by introducing a C/SiOx nanocomposite electrode having a SiOx nanoparticle loading of 15 wt.%. The nanocomposite was tailored from tetraethyl orthosilicate (TEOS) and 3-aminophenol which simultaneously underwent hydrolysis-condensation and polymerization, respectively, to produce a C/SiO2 intermediate when subjected to microwave irradiation. SiO2 was present as nanoparticles on the carbon surface, which allowed for facile reduction. Under a mild reducing agent, concurrent carbonization of the 3-aminophenol polymer and the reduction of SiO2 nanoparticles were performed. The value of x in the synthesized C/SiOx was 1.24 according to the binding energy from the Si 2p x-ray photoelectron spectroscopy spectrum. The synthesized C/SiOx nanocomposite delivered a reversible capacity of 383 mA h/g as a lithium battery anode—a 30% improvement on the carbon-only electrode. Charge-discharge cycling shows 84% capacity retention after 100 cycles.

Annealing-induced evolution in interface stability and electrical performance of sputtering-driven rare-earth-based gate oxides

Annealing temperature-dependent ultrathin Dy2O3 gate dielectric films, grown on Si substrates by reactive sputtering, were characterized in terms of structural, optical and electrical properties using x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), UV–Vis transmission spectroscopy and electrical measurements of Dy2O3/Si gate stack. Additionally, the thickness of the interfacial SiO2 layer during the deposition and annealing process has been calculated using the Si 2p XPS spectra to exclude its influence on the electrical parameter of Dy2O3 films. XPS analyses for all the samples have shown the abrupt growth of the Dy-silicate for 700°C-annealed sample, which is identified as the primary reason for the dramatic reduction in its electrical performance. In addition, optimized Dy2O3 sample with annealed temperature at 600 °C exhibits the lowest equivalent oxide thickness of 1.6 nm, the highest dielectric constant 16.8, the lower leakage current density 4.45 × 10−8 A/cm2 and the lower frequency dispersion of 6.21%. Based on the experimental analysis, the optimized annealing temperature has been obtained to achieve Dy2O3 gate dielectric thin films as deposition of high-k with high-quality on Si substrates.