2p X-ray Photoelectron Spectroscopy Research Articles

Chemical information from XPS: Theory and experiment for Ni(OH)2.

The features and the electronic character of the states for the Ni 2p x-ray photoelectron spectroscopy (XPS) of Ni(OH)2 were analyzed. This detailed analysis is based on abinitio molecular orbital wavefunctions for a cluster model of Ni(OH)2. The theory is validated by comparison with experiment. Then, advanced methods are used to explain and contrast the properties of different groups of ionic states. An important conclusion is that in most cases, the ionic states cannot be described with a single configuration or determinant. Despite this essential many-body character of the XPS, we demonstrate that it is possible to understand the origin of the main and satellite XPS features in terms of their orbital character.

Surface Structure to Tailor the Electrochemical Behavior of Mixed-Valence Copper Sulfides during Water Electrolysis.

The semiconducting behavior of mixed-valence copper sulfides arises from the pronounced covalency of Cu-S bonds and the exchange coupling between CuI and CuII centers. Although electrocatalytic study with digenite Cu9S5 and covellite CuS has been performed earlier, detailed redox chemistry and its interpretation through lattice structure analysis have never been realized. Herein, nanostructured Cu9S5 and CuS are prepared and used as electrode materials to study their electrochemistry. Powder X-ray diffraction (PXRD) and microscopic studies have found the exposed surface of Cu9S5 to be d(0015) and d(002) for CuS. Tetrahedral (Td) CuII, distorted octahedral (Oh) CuII, and trigonal planar (Tp) CuI sites form the d(0015) surface of Cu9S5, while the (002) surface of CuS consists of only Td CuII. The distribution of CuI and CuII sites in the lattice, predicted by PXRD, can further be validated through core-level Cu 2p X-ray photoelectron spectroscopy (XPS). The difference in the electrochemical response of Cu9S5 and CuS arises predominantly from the different copper sites present in the exposed surfaces and their redox states. In situ Raman spectra recorded during cyclic voltammetric study indicates that Cu9S5 is more electrochemically labile compared to CuS and transforms rapidly to CuO/Cu2O. Contact-angle and BET analyses imply that a high-surface-energy and macroporous Cu9S5 surface favors the electrolyte diffusion, which leads to a pronounced redox response. Post-chronoamperometric (CA) characterizations identify the potential-dependent structural transformation of Cu9S5 and CuS to CuO/Cu2O/Cu(OH)2 electroactive species. The performance of the in situ formed copper-oxides towards electrocatalytic water-splitting is superior compared to the pristine copper sulfides. In this study, the redox chemistry of the Cu9S5/CuS has been correlated to the atomic arrangements and coordination geometry of the surface exposed sites. The structure-activity correlation provides in-depth knowledge of how to interpret the electrochemistry of metal sulfides and their in situ potential-driven surface/bulk transformation pathway to evolve the active phase.

Analysis of the Lithium Storage Mechanism in the SiOx/C Composite Based on the Performance Variation Applied to a Lithium-Ion Battery

The SiOx/C composite, as a form of silicon-based materials, has been considered as an attractive alternative anode for next-generation lithium-ion batteries. The porous SiO0.71C1.95N0.47 anode material exhibiting robust Si–O skeletons wrapped by carbon layers is successfully prepared and delivers an initial capacity of over 1700 mAh g–1 with an initial coulombic efficiency of 69.4% and favorable cycle life. Both Si (2p) X-ray photoelectron spectroscopy (XPS) and 29Si nuclear magnetic resonance (NMR) demonstrate the existence of SiO4 and SiO3C units as main lithium storage sites in the original state. The XPS curve moved toward the direction of the binding energy decreasing with NMR spectra shifting to a high field after the first lithiation process. The massive capacity loss during the first discharge and charge cycle results from the formation of irreversible Li silicate (Li2SiO4). The fluctuation of the charge and discharge capacity, including a persistent decline during the first 30 cycles and a continuous elevation in the following 400 cycles, could be attributed to the participated degree of reversible Li silicate (Li2SiO3 and Li2Si2O5) in the delithiation process. The Si–O skeletons are gradually corroded and ultimately destroyed in the final 400 cycles, leading to the sharp drop of the cycling performance of the half-cell.

Cholesterol-substituted 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and Poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol)

Cholesterol is a rigid, crystalline, non-polar natural substance that exists in animal blood and cell membranes. Some of its derivatives are known to form ordered liquid crystalline mesophases under suitable conditions. In this work, we carefully examined the influence of cholesterol substitution on the characteristics of 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and its corresponding polymer poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol) synthesized by both chemical and electrochemical polymerization. We found evidence for an ordered lamellar (smectic-like) structure in the EDOT-MA-cholesterol monomer by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction techniques. The ordered phase was observed to form on cooling from the isotropic melt at about 80 °C. Due to the insulating and bulky cholesterol side group on the EDOT monomer, we found that there was a maximum charge density for electrodeposition at ∼ 0.155 C.cm−2. A series of electrodepositions were performed from 0 to 0.155 C.cm−2 for probing the change of the charge transport with more charges used for the electrodeposition. We found that the impedance increased in the high-frequency range (above 104 Hz) and decreased in the low-frequency range (below 102 Hz). Three equivalent circuit models were proposed for fitting impedance data at different charge densities for a better understanding of the film growth process. The suppressed cyclic voltammogram (CV) of PEDOT-MA-cholesterol showed that the charge storage capability was essentially eliminated in the thickest films. The limited doping of the films was corroborated by their diminished electrochromic behavior, polaron-dominating absorption in UV-vis, overoxidized S 2p X-ray Photoelectron Spectroscopy (XPS) signal of electrodeposited films, and proton Nuclear Magnetic Resonance (1H NMR) of chemically polymerized samples. Dense film morphologies were confirmed by scanning electron microscopy (SEM). Grazing incident X-ray diffraction (GIWAXS) indicated the disrupted stacking of conjugated chains, which correlated with the decreased conductivity of the PEDOT-MA-cholesterol films. The measurement of the electrical conductivity gave a value of around 3.30 × 10−6 S.cm−1 which is about six orders of magnitude lower than has been seen in PEDOT (∼3 S.cm-1).

Ultra-Violet-Assisted Scalable Method to Fabricate Oxygen-Vacancy-Rich Titanium-Dioxide Semiconductor Film for Water Decontamination under Natural Sunlight Irradiation

This work reports the fabrication of titanium dioxide (TiO2) nanoparticle (NPs) films using a scalable drop-casting method followed by ultra-violet (UV) irradiation for creating defective oxygen vacancies on the surface of a fabricated TiO2 semiconductor film using an UV lamp with a wavelength oof 255 nm for 3 h. The success of the use of the proposed scalable strategy to fabricate oxygen-vacancy-rich TiO2 films was assessed through UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The Ti 2p XPS spectra acquired from the UV-treated sample showed the presence of additional Ti3+ ions compared with the untreated sample, which contained only Ti4+ ions. The band gap of the untreated TiO2 film was reduced from 3.2 to 2.95 eV after UV exposure due to the created oxygen vacancies, as evident from the presence of Ti3+ ions. Radiation exposure has no significant influence on sample morphology and peak pattern, as revealed by the SEM and XRD analyses, respectively. Furthermore, the photocatalytic activity of the fabricated TiO2 films for methylene-blue-dye removal was found to be 99% for the UV-treated TiO2 films and compared with untreated TiO2 film, which demonstrated only 77% at the same operating conditions under natural-sunlight irradiation. The proposed UV-radiation method of oxygen vacancy has the potential to promote the wider application of photo-catalytic TiO2 semiconductor films under visible-light irradiation for solving many environmental and energy-crisis challenges for many industrial and technological applications.

Combined ICP-OES and XPS analysis to evaluate the [AlO4]0 concentration in quartz: limiting the formation temperature of quartz.

A proposed quartz thermometer is based on the concentration of [AlO4]0 tetrahedra determined by combining inductively coupled plasma optical emission spectrometry (ICP-OES) with X-ray photoelectron spectroscopy (XPS) data. The concentration of [AlO4]0 tetrahedra in the quartz lattice (C[AlO4]0/ppm) and the formation temperatures of quartz (TQ/°C) from agate, gold deposits, and granodiorite are calculated by C[AlO4]0 = CAl total (ppm) × k and TQ (°C) = 3.6 × CAl total (ppm) × k + 33.0, respectively. Where CAl total is the total Al concentration of quartz measured by ICP-OES and k is the relative percentage of [AlO4]0 tetrahedra in the quartz lattice and can be obtained by fitting the Al(2p) XPS spectrum. The obtained formation temperatures of quartz (TQ) agree well with the equilibrium formation temperature (TE) calculated by oxygen isotope data. By comparing the relative positions of the two temperature curves of quartz (TQ and TE), the composition of the mineral-forming fluid can be inferred. The proposed quartz thermometer can be applied to quartz formed under equilibrium conditions and in Al-saturated environments over a wide temperature range (152-566 °C). The use of the quartz thermometer effectively eliminates interference from different fluid compositions and satisfies the requirements of convenience and economy.

Spin-Enhanced C–C Coupling in CO 2 Electroreduction with Oxide-Derived Copper

Spin-Enhanced C–C Coupling in CO ₂ Electroreduction with Oxide-Derived Copper

Main and Satellite Features in the Ni 2p XPS of NiO.

The origin and assignment of the complex main and satellite X-ray photoelectron spectroscopy (XPS) features of the cations in ionic compounds have been the subject of extensive theoretical studies using different methods. There is agreement that within a molecular orbital model, one needs to take into account different types of configurations. Specifically, those where a core electron is removed, but no other configuration changes are made and those where in addition to ionization, there are also shake or charge-transfer changes to the ionic configuration. However, there are strong disagreements about the assignment of XPS features to these configurations. The present work is directed toward resolving the origin of main and satellite features for the Ni 2p XPS of NiO based on ab initio molecular orbital wave functions (WFs) for a cluster model of NiO. A major problem in earlier ab initio XPS studies of ionic compounds has been the use of a common set of orbitals that was not able to properly describe all the ionic configurations that contribute to the full XPS spectra. This is resolved in the present work by using orbitals that are optimized for averages of the occupations of the different configurations that contribute to the XPS. The approach of using state-averaged (SA) orbitals is validated through comparisons between different averages and through use of higher order excitations in the WFs for the ionic states. It represents a major extension of our earlier work on the main and satellite features of the Fe 2p XPS of Fe2O3 and proves the reliability and the generality of the assignments of the character and origin of the different features of the XPS obtained with orbitals optimized for SAs. These molecular orbital methods permit the characterization of the ionic states in terms of the importance of shake excitations and of the coupling of ionization of 2p1/2 and 2p3/2 spin-orbit split sub shells. The work lays the foundation for definitive assignments of the character of main and satellite XPS features and points to their origin in the electronic structure of the material.

Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N 5 Site for Enhanced Electrocatalytic Reaction

Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N ₅ Site for Enhanced Electrocatalytic Reaction

Solution deposition conditions influence the surface properties of 3-mercaptopropyl(trimethoxysilane) (MPTS) films

The deposition of organosilanes onto semiconducting and metal oxide surfaces is a versatile approach to impart corrosion resistance or provide a site for the subsequent immobilization of a range of molecules. Organosilane deposition is however, quite a complex process, with many factors influencing the film properties. Here, we investigated the deposition of 3-mercaptopropyl(trimethoxysilane) (MPTS) in organic solvents on Si substrates with various post-deposition treatments and subsequently characterize film properties using surface analytical techniques including ellipsometry, X-ray photoelectron spectroscopy (XPS), static water contact angles, and attenuated total reflection Fourier transform infra-red (ATR-FTIR) spectroscopy. Condensation of MPTS onto Si surfaces was most efficient in more anhydrous and hydrophobic solvents such as toluene, with monolayer thickness values (≈0.77 nm) being observed at MPTS concentrations of 0.08–1% (v/v), whereas all thickness values were seen to be below monolayer coverage when deposition was carried out in ethanol, regardless of the concentration used. It was found that the shortcomings of ethanol deposition can be overcome by applying a pre-hydrolysis period at low pH to achieve similar film thicknesses and properties compared to toluene at shorter deposition times - which is important when functionalization needs to be carried out in plastic consumables. Moreover, with minimal post-deposition treatments it was found that controllable film thicknesses can also be achieved with a high-retention of thiol functional groups which is evidenced by a clear S 2p XPS peak at a binding energy of 164.0 eV. However, these films will only be loosely bound to the surface and be lost upon further treatments. Overall, the procedures developed are important for many applications such as biomolecule immobilization, and the functionalization of planar substrates and nanoparticles, where the organosilane thickness, degree of order, reactivity and surface concentration of thiols influence film functionality.

Boosting Electrocatalytic CO 2 Reduction with Conjugated Bimetallic Co/Zn Polyphthalocyanine Frameworks

Boosting Electrocatalytic CO ₂ Reduction with Conjugated Bimetallic Co/Zn Polyphthalocyanine Frameworks

Controlled Growth Interface of Charge Transfer Salts of Nickel-7,7,8,8-Tetracyanoquinodimethane on Surface of Graphdiyne

Controlled Growth Interface of Charge Transfer Salts of Nickel-7,7,8,8-Tetracyanoquinodimethane on Surface of Graphdiyne

Strain-Assisted Single Pt Sites on High-Curvature MoS 2 Surface for Ultrasensitive H 2 S Sensing

Strain-Assisted Single Pt Sites on High-Curvature MoS ₂ Surface for Ultrasensitive H ₂ S Sensing

Corrosion inhibition in acidic environments: key interfacial insights with photoelectron spectroscopy.

In many engineering scenarios, surface-active organic species are added to acidic solutions to inhibit the corrosion of metallic components. Given suitable selection, such corrosion inhibitors are highly effective, preventing significant degradation even in highly aggressive environments. Nevertheless, there are still considerable gaps in fundamental knowledge of corrosion inhibitor functionality, severely restricting rational development. Here, we demonstrate the capability of X-ray photoelectron spectroscopy (XPS), supported by ab initio modelling, for revealing key details of inhibited substrates. Attention is focussed on the corrosion inhibition of carbon steel through the addition of an exemplar imidazoline-based corrosion inhibitor (OMID) to aqueous solutions of both HCl and H2SO4. Most notably, it is demonstrated that interfacial chemistry varies with the identity of the acid. High resolution Fe 2p, O 1s, N 1s, and Cl 2p XPS spectra, acquired from well-inhibited carbon steel in 1 M HCl, show that there are two different singly protonated OMID species bound directly to the metallic carbon steel substrate. In sharp contrast, in 0.01 M H2SO4, OMID adsorbs onto an ultra-thin surface film, composed primarily of a ferric sulfate (Fe2(SO4)3)-like phase. Such insight is essential to efforts to develop a mechanistic description of corrosion inhibitor functionality, as well as knowledge-based identification of next generation corrosion inhibitors.

The Electrochemical Behaviour of Quaternary Amine-Based Room-Temperature Ionic Liquid N4111(TFSI)

In this study, we used the in situ X-ray photoelectron spectroscopy (XPS), in situ mass spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy methods, for the first time, in a detailed exploration of the electrochemical behaviour of a quaternary amine cation-based room-temperature ionic liquid, butyl-trimethyl-ammonium bis(trifluoromethylsulfonyl)imide (N4111(TFSI)), at the negatively and positively polarised molybdenum carbide-derived micro-mesoporous carbon (mmp-C(Mo2C)) electrodes that can be used as high surface area supporting material for electrocatalysts. The shapes of the C 1s, N 1s, O 1s, F 1s and S 2p XPS spectra were stable for N4111(TFSI) within a very wide potential range. The XPS data indicated the non-specific adsorption character of the cations and anions in the potential range from −2.00 V to 0.00 V. Thus, this region can be used for the detailed analysis of catalytic reaction mechanisms. We observed strong adsorption from 0.00 V to 1.80 V, and at E > 1.80 V, very strong adsorption of the N4111(TFSI) at the mmp-C(Mo2C) took place. At more negative potentials than −2.00 V, the formation of a surface layer containing both N4111+ cations and TFSI− anions was established with the formation of various gaseous compounds. Collected data indicated the electrochemical instability of the N4111+ cation at E < −2.00 V.

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Boosting the Rate Performance of Li–S Batteries via Highly Dispersed Cobalt Nanoparticles Embedded into Nitrogen-Doped Hierarchical Porous Carbon

Boosting the Rate Performance of Li–S Batteries via Highly Dispersed Cobalt Nanoparticles Embedded into Nitrogen-Doped Hierarchical Porous Carbon

High-conversion reduction synthesis of porous silicon for advanced lithium battery anodes

For practical implementation of high-capacity silicon anodes, porous silicon (pSi) structures have demonstrated outstanding cycling stability against the large volume changes typical of solid silicon particles. The conventional magnesiothermic reduction (MR) of silica under static conditions limits the yield of pSi and sometimes produces low-purity of pSi owing to limited mass transfer and many side reactions. Hence, we devise a rotational MR (R-MR) system with rapid magnesium transport in which a uniform Mg/SiO2 molar ratio is readily achievable, and a short reaction time can be applied. Compared to conventional MR, the R-MR process has an extremely high yield (∼90 wt%) of pSi at almost complete conversion of precursor, whereas side reactions are substantially suppressed. Mg 2p X-ray photoelectron spectroscopy analysis of the reduction product reveals that pSi yield is well correlated with the conversion of Mg to MgO. The carbon-coated pSi/C samples and their hybrids with graphite (pSi/C@Gr) composites demonstrate stable cycling performance for 300−600 cycles at high capacity with high cycling efficiency (∼99.9%). Therefore, high-conversion R-MR can be a very efficient and scalable process for obtaining pSi for use in carbon composites (such as pSi/C and pSi/C@Gr) that offer outstanding cycling performance in high-capacity anodes for high-energy LIBs.

Operando leaching of pre-incorporated Al and mechanism in transition-metal hybrids on carbon substrates for enhanced charge storage

Operando leaching of pre-incorporated Al and mechanism in transition-metal hybrids on carbon substrates for enhanced charge storage

Dynamic electrochromic play via “mix-and-match” reversible metal-ligand interactions

In this issue of Chem, Zhang and co-workers report on the development of a novel methodology for creating electrochromic materials based on dynamic metal-ligand interactions. The proposed approach for the search of new systems is interesting and could allow fast developments in the area of electrochromic materials for non-emissive displays.