X-ray Photoelectron Spectroscopy Measurements Research Articles

Synergistic corrosion inhibition of rubber seed extract with KI on cold rolled steel in sulfuric acid solution

BackgroundPlant-based inhibitor has emerged an important topic owing to the combing merits of eco-friendly, low cost, rich natural resources as well as easy preparation. Rubber seed is the agricultural waste, and is mainly composed of oil and fatty acids those contain many polar oxygen atoms, and so it can be extracted to prepare the potential corrosion inhibitor. MethodsRubber seed extract (RSE) is prepared using reflux extraction method with the extracting solvent of ethanol aqueous solution. The synergistic inhibition effect of RSE and potassium iodide (KI) on the corrosion of cold rolled steel (CRS) in 0.50 M H2SO4 solution is firstly studied by weight loss, potentiodynamic polarization (PDP) curves and electrochemical impedance spectroscopy (EIS) methods. CRS surface was thoroughly characterized using metallographic microscope, scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements. FTIR, UV–vis and liquid chromatography mass spectrometry (LC-MS) compositional analysis of RSE were used to analyze the efficient components in RSE. Significant findingsThe results indicate that individual RSE or KI cannot function as a successful inhibitor to prevent CRS corrosion, but the mixture of RSE/KI performs better at inhibiting, with a maximal inhibition efficacy of up to 96.4% of 200 mg L−1 RSE/100 mg L−1 KI. The synergistic coefficient of the mixture is larger than 1, indicating that a true synergism. RSE/KI can drastically retard both cathodic and anodic processes, and interfacial capacitance falls as the charge transfer resistance of CRS/solution rises. It exhibits remarkable inhibition properties when the capacitor arc grows. There is only a small corrosion response in the inhibited media, as evidenced by the variations in electrical conductivity and ultraviolet spectrum before and after immersion. The hydrophilicity and surface roughness of CRS surface is dropped as a result of the introduction of RSE/KI. A series of metallurgical microscopy, AFM, SEM or contact angle tests indicate a synergistic inhibition effect is more pronounced for RSE/KI. XPS results clearly demonstrate that elements including Fe, S, N, and I are bonded to the surface of CRS. The primary ingredients of oleic acid, polyphenols, phenylpropanoids can also produce a strong synergism with KI.

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

Dual functionalization of polyamide reverse osmosis thin film composite membrane for improving chlorine resistance

Contemporary high-efficiency polyamide (PA) membranes are constructed using aliphatic or aromatic amines combined with acyl chlorides. Nevertheless, the aromatic rings attached to the N–H group within the amide linkages are vulnerable to degradation by chlorine. The surface of a PA reverse osmosis (RO) membrane was altered in this work through the dual functionalization of tannic acid (TA) and silver nanoparticles (Ag NPs) to improve separation performance, chlorine resistance, and anti-bacterial capabilities of membranes. This study provides an insight in the role and synergistic effects of TA and Ag NPs for enhancing the chlorine resistance of the modified TFC membranes. The outcome indicated that the RO-TA/Ag modified membrane exhibited the maximum rejection of 98.31%, slightly surpassing the pristine RO membrane, which had a rejection rate of 96.52%. The RO-TA/Ag modified membrane also shown improved chlorine tolerance against 500 ppm sodium hypochlorite solution (NaClO), as evidenced by X-ray photoelectron spectroscopy (XPS) measurement which revealed reduced chlorine content in contrast to pristine RO and RO-TA membrane. The RO-TA/Ag membrane exhibited the largest inhibitory zone for both Gram-positive, S. aureus and Gram-negative, E. coli bacteria. The synergistic effects of the dual functionalization of TA and Ag NPs which render the modified membrane with high anti-chlorine and anti-bacterial capabilities are discussed.

Understanding the Activation Mechanism of RhCrOx Cocatalysts for Hydrogen Evolution with Nanoparticulate Electrodes.

Mixed oxides of Rh-Cr (RhCrOx), containing Rh3+ and Cr3+ cations, are commonly used as cocatalysts for the hydrogen evolution reaction (HER) on particulate photocatalysts. The precise physicochemical mechanisms of the HER at the catalytic sites of these oxides are not well understood. In this study, model cocatalyst electrodes, composed of nanoparticulate RhCrOx, were fabricated to investigate the physicochemical mechanisms of the HER. Electroanalytical and X-ray photoelectron spectroscopic measurements revealed that nanoparticulate RhCrOx produces reduced Rh (Rh0) species by maintaining an electrode potential more negative than 0.03 V versus the reversible hydrogen electrode (VRHE). This results in significant enhancement of the HER activity. The catalytic activity for the HER stems from the reduced Rh species, and the inclusion of Cr3+ (CrOx) aided in the electron transfer process at the solid/liquid interface, resulting in a higher current density during the HER. To achieve a solar-to-hydrogen efficiency of over 3%, the conduction band minimum of the particulate photocatalyst should be positioned more negatively than -0.10 VRHE. Moreover, the formation of electron trap states at potentials more positive than 0.03 VRHE should be avoided. This study highlights the importance of understanding the catalytic sites on metal oxide cocatalysts. Moreover, it offers a design strategy for enhancing the efficiency of photocatalytic water splitting.

Visualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis

Methanol formation over Cu/ZnO catalysts is linked with a catalytically active phase created by contact between Cu nanoparticles and Zn species whose chemical and structural state depends on reaction conditions. Herein, we use variable-temperature scanning tunneling microscopy at elevated pressure conditions combined with X-ray photoelectron spectroscopy measurements to investigate the surface structures and chemical states that evolve when a CuZn/Cu(111) surface alloy is exposed to reaction gas mixtures. In CO2 hydrogenation conditions, Zn stays embedded in the CuZn surface, but once CO gas is added to the mixture, the Zn segregates onto the Cu surface. The Zn segregation is CO-induced, and establishes a new dynamic state of the catalyst surface where Zn is continually exchanged at the Cu surface. Candidates for the migrating few-atom Zn clusters are further identified in time-resolved imaging series. The findings point to a significant role of CO affecting the distribution of Zn in the multiphasic ZnO/CuZn/Cu catalysts.

Structure – Catalytic Behavior Relationships in TiO2-Carbon Composite Supported Pt Electrocatalysts: A Case Study

Composite types of supports made of TiO2 and carbonaceous materials provide higher stability for the Pt electrocatalysts under the working conditions of polymer electrolyte membrane fuel cells than the traditional carbon supports. We have demonstrated in our previous work that composites with general formula of 75 wt.% Ti(1-x)MoxO2-25 wt.% C (x = 0–0.2; C = traditional Black Pearls (BP) carbon) were promising supports which provided increased stability for the Pt electrocatalysts. In this study, the effect of nitrogen doping of the carbonaceous component of the composite was explored. 75 wt.% TiO2-25 wt.% carbon composite supports were prepared using graphite oxide (GO), N-doped GO and N-doped multilayer graphene. Electrocatalysts were made by loading the supports with 20 wt.% Pt. The systems were compared based on their physicochemical properties determined by low-temperature nitrogen adsorption, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and conductivity measurements. The activity of the catalysts was investigated by conventional methods in a 3-electrode electrochemical cell. The results of various characterization methods contributed to the understanding of the difference in the electrochemical properties of N-free and N-containing catalyst samples. While GO was favorable for this composite supported catalyst, its N-doping strongly influenced the growth of TiO2, forming an almost continuous coating of small TiO2 crystals. This quasi-insulating TiO2 layer between the Pt catalytic sites and the conductive part of the composite resulted in poor electrochemical activity. Mixing the sample with carbon improved its conductivity, which resulted in a significant increase in the oxygen reduction activity.

Preparation, characterization and photocatalytic studies of defect pyrochlore, KMn0·33Te1·67O6 and its composite with g-C3N4

Skeletal materials belonging to the defect pyrochlore family have been the subject of considerable interest due to their remarkable properties. In this work, a highly efficient, stable and visible light active composite photocatalytic system consisting of defect pyrochlore of composition KMn0·33Te1·67O6 (KMnTeO) and g-C3N4 (g-CN) has been successfully prepared by simple physical mixing of pre-prepared KMnTeO and g-CN components synthesized in solid state and thermal treatment of low-cost melamine, respectively. Structural, morphological and optical properties of as-prepared catalysts were deduced from powder X-ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), Raman, Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (FESEM-EDX), Transmission Electron Microscopy-High Resolution Transmission Electron Microscopy (TEM-HRTEM), Ultraviolet–Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS), X-ray Photoelectron Spectroscopy (XPS) and Photoluminescence (PL) measurements. The lattice parameter “a” of parent KMnTeO was obtained from Rietveld refinement of its powder XRD pattern. The FT-IR and Raman spectra of KMnTeO gave characteristic bands belonging to the defect pyrochlore structure. The photocatalytic activities of KMnTeO and composite KMnTeO-g-CN were evaluated by the degradation of methylene blue (MB). Scavenger experiments were carried out to identify the reactive species responsible for the degradation of MB. Furthermore, the reusability and stability of the photocatalysts were explored. The probable photocatalytic mechanism for MB degradation over the composite KMnTeO-g-CN was surmised according to the scavenger experiments. The work provides a new approach for the development of novel defect pyrochlore based composite photocatalysts to treat industrial wastewater containing organic pollutants.

Flotation separation of chalcopyrite from galena based on selective adsorption of pyrogallic acid: Experiments and MD simulations

Novel eco-friendly organic depressants with high selectivity are attracting ever-growing interests. The selective inhibition effect of pyrogallic acid (PA) on galena in chalcopyrite flotation was investigated in this study. Flotation trials showed that PA markedly depressed galena with only a small effect on chalcopyrite, which contributed to the separation of chalcopyrite and galena by flotation after adding a low dosage of PA. Surface hydrophobicity tests suggested that PA strongly adsorbed on galena but not on chalcopyrite, which attenuated the adsorption activity of collector on galena, thus rendering galena highly hydrophilic. Conversely, chalcopyrite still retained favorable floatability. These findings were corroborated by the results obtained from infrared and surface adsorption measurements. Results of time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy measurements also validated the strong adsorption of PA on galena. This behavior promoted the generation of other hydrophilic species on galena. In addition, molecular dynamic simulations demonstrated that PA tended to adsorb on galena, and water molecules accumulated on galena following PA adsorption, which would decrease the floatability of galena.

Metallization of polypropylene substrates through surface functionalization and physical vapor deposition of chromium coatings

Physical vapor deposition (PVD) of chromium coatings represents an interesting alternative to electroplating to obtain metallized plastic parts for a variety of manufacturing sectors. This process is however hampered by the limited adhesion of the metallic layer on the underlying polymeric substrates. Within this context, PVD metallization of polypropylene substrates has so far been particularly challenging given the low surface energy and poor wettability of this commodity plastics. To address this issue, a comprehensive approach is proposed here to enable the production of PVD-metallized PP substrates with excellent and stable interlayer adhesion. The adhesive properties of the PP substrate are modified by a selective UV-induced photografting process in which vinyl-, glycidyl- or 2-hydroxyethyl methacrylate species are covalently attached to the PP surface, as confirmed by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and surface wettability measurements. Based on the chemistry of the photografted functionality, different resin systems are selected and investigated for use as primers to enable subsequent chromium deposition, including acrylic, epoxy and polyurethane systems. The effect of the photografting process on the adhesion between PP and the primers is systematically assessed by means of pull-off tests, highlighting a significant improvement of the adhesion force after surface functionalization with appropriate grafting agents. Finally, functionalized PP substrates are chromated through PVD, obtaining homogeneous and crack-free chromium surfaces upon judicious selection of suitable primer-grafting agent combinations. This also led to outstanding interlayer adhesion and micromechanical performance. This work provides the first demonstration of chromium-metallization of PP substrates via PVD for metallized plastic components with excellent surface characteristics, and paves the path for the design of mechanically durable and aesthetically-compliant PVD-metallized PP components.

Anatase TiO2/Defective UiO-66 porous octahedral S-scheme heterojunctions toward optimized photocatalytic performance

Photocatalysis is an alternative for antibiotics removal from wastewater for the sustainable development of human society. However, applying photocatalysts for antibiotics (e.g., tetracycline) degradation under practical conditions is highly restricted by the low reaction efficiency due to the prompt charge recombination. Constructing porous heterojunctions is an efficient way to regulate the electron transfer path and accelerate charge migration efficiency. Herein, TiO2/defective UiO-66 porous octahedral S-scheme heterojunctions are successfully fabricated through an in-situ growth strategy. The strong interaction and charge migration behavior between TiO2 and defective UiO-66 have been studied using X-ray photoelectron spectroscopy and electron paramagnetic resonance measurements. The photocatalytic removal efficiency of tetracycline is notably improved by forming TiO2/defective UiO-66 porous heterojunctions. The promoted photocatalytic performance can be ascribed to the strong interaction between TiO2 and defective UiO-66, and the accelerated charge separation and transfer efficiency due to the formation of S-scheme heterojunctions, thus generating abundant reactive oxygen species, including O2− and OH. The optimized 38-TiO2/UiO-66-300 can eliminate 97.9 % of tetracycline in 60 min with a reaction constant rate of 0.0425 min−1, which is approximately 4 and 10 times that of pristine TiO2 and UiO-66-300, respectively. This work provides an alternate strategy for preparing highly active heterojunction photocatalysts for environmental applications.

Oxidative corrosion resistance of a CrxFeyNi1-x-y composition spread alloy film (CSAF) in dry air

Composition Spread Alloy Films (CSAFs) were used to study the resistance to oxidative corrosion of CrxFeyNi1-x-y alloys in dry air and determine the critical Cr composition, xCr∗, necessary to prevent bulk oxidation. CrxFeyNi1-x-y CSAFs were made using physical vapor deposition (PVD) and then oxidized in dry air between 100 – 500 °C for periods of 1 h. A sharp passivation boundary was observed at 300 °C separating alloys showing evidence of heavy oxidation from Cr-rich alloys that were passivated. X-ray photoelectron spectroscopy (XPS) depth profiling was used to measure the extent of oxidation and penetration depth of the oxide layer on either side of the passivation boundary. XPS measurements confirmed the presence of a critical Cr composition, xCr∗, ranging from 18 to 26 at.%. For alloys with xCr≥xCr∗, a sufficiently thick passivating layer of oxidized Cr, Cr(ox), had formed on the top surface preventing the oxidative corrosion of either Fe or Ni. On the other hand, when xCr<xCr∗, bulk oxidation was observed, with appreciable Fe(ox) and/or Ni(ox) measured on the surface and often penetrating through the entire alloy film thickness. The trajectory of xCr∗ plotted within CrxFeyNi1-x-y composition space supports the trend towards using higher Cr-content stainless steel grades in harsh oxidative environments.

Selective growth and unveiling semiconductor nanostructured based La,Mo and O elements: Structural, morphological, and optical investigations

La2Mo2O9 ternary compound thin film has been prepared by the chemical spray pyrolysis technique on glass substrates at 460°C. Characterization via X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray, X-ray photoelectron spectrometry (XPS) and spectrophotometry through reflectance and transmittance measurements were performed. X-ray analysis shows that La2Mo2O9 material crystallizes in cubic structure belonging to the P 213 space group with a preferred orientation of the crystallites along (210) direction parallel to the substrate plane. Raman spectroscopy witnesses the presence of bonds like La-O and Mo-O. SEM observation shows that the prepared film exhibits a uniform grain of regular sizes in the range of 70–120 nm and some chains. EDX spectroscopy highlights the presence of La, Mo and O elements with a slight non-stoichiometry reflecting the oxygen deficiency. XPS measurements reveal the well defined states O 1s, Mo 3d5/2, Mo 3d3/2, La 3d5/2 and La 3d3/2 of oxygen, molybdenum and lanthanum elements. Optical measurements show a high transparency in the visible range. These measurements were used to deduce the optical band gap and Urbach energy.

WLI, XPS and SEM/FIB/EDS Surface Characterization of an Electrically Fluted Bearing Raceway

Electrical bearing currents may disturb the performance of the bearings via electro-corrosion if they surpass a limit of ca. 0.1 to 0.3 A/mm2. A continuous current flow, or, after a longer time span, an alternating current or a repeating impulse-like current, damages the raceway surface, leading in many cases to a fluting pattern on the raceway. Increased bearing vibration, audible noise, and decreased bearing lubrication as a result may demand a replacement of the bearings. Here, an electrically corroded axial ball bearing (type 51208) with fluting patterns is investigated. The bearing was lubricated with grease lubrication and was exposed to 4 A DC current flow. It is shown that the electric current flow causes higher concentrations of iron oxides and iron carbides on the bearing raceway surface together with increased surface roughness, leading to a mixed lubrication also at elevated bearing speeds up to 1500 rpm. The “electrically insulating” iron oxide layer and the “mechanically hard” iron carbide layer on the bearing steel are analysed by WLI, XPS, SEM, and EDS. White Light Interferometry (WLI) is used to provide an accurate measurement of the surface topography and roughness. X-ray Photoelectron Spectroscopy (XPS) measurements are conducted to analyze the chemical surface composition and oxidation states. Scanning Electron Microscopy (SEM) is applied for high-resolution imaging of the surface morphology, while the Focused Ion Beam (FIB) is used to cut a trench into the bearing surface to inspect the surface layers. With the Energy Dispersive X-ray spectrometry (EDS), the presence of composing elements is identified, determining their relative concentrations. The electrically-caused iron oxide and iron carbide may develop periodically along the raceway due to the perpendicular vibrations of the rolling ball on the raceway, leading gradually to the fluting pattern. Still, a simulation of this vibration-induced fluting-generation process from the start with the first surface craters—of the molten local contact spots—to the final fluting pattern is missing.

Rapid CO2 laser treatment of Pt–Fe MOF for efficient electrochemical hydrogen evolution reaction

The quest for efficient hydrogen production via electrochemical water splitting has led to extensive research on catalytic materials. This work focuses on enhancing the catalytic functionality of metal-organic frameworks (MOFs) by incorporating platinum (Pt) to improve the performance of the hydrogen evolution reaction (HER). Fe-based MOFs mixed with platinum precursors were altered through laser treatment, which caused considerable changes in their structure and catalytic activity in just 3 min. This was achieved without the need for vacuum or an inert atmosphere. Characterization techniques including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and electrochemical measurements were used to characterize the synthesized materials. The laser-treated Pt–Fe MOF demonstrated outstanding HER performance with 3.5 wt% Pt content, outperforming commercial 20 wt% Pt/C catalysts, and exhibiting good stability even after prolonged cycling. These results highlight the potential of laser-treated MOFs for efficient and cost-effective electrochemical hydrogen generation.

Synergistic role of Co and CoP on highly dispersed cobalt nanoparticles embeded in porous carbon for efficient PH3 decomposition

Efficient resourceful treatment of phosphine tail gas is a huge challenge. In this study, a series of cobalt nanoparticles embeded in porous carbon (Co@C) catalysts were obtained via pyrolysis of Co-based MOF as precursor for catalytic decomposition of phosphine (PH3) by regulating the ratio of reactants of MOFs. The composition, morphology and structure of the catalysts were characterized by inductively coupled plasma, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and BET measurement. The effect of Co@C catalysts with different reactant ratio on the catalytic decomposition of PH3 was tested, and the catalysts before and after the reaction were compared. It was found that the catalyst with MOF as the precursor after pyrolysis can still retain the porosity and large specific surface area of MOF. The metal cobalt nanoparticles and its oxides can be uniformly distributed in time under high loading, which is conducive to the reaction with phosphine to form metal phosphide (CoP), and the rapid and efficient decomposition of PH3 was completed under the synergistic effect of the two kinds of active sites of Co and CoP. The best catalytic decomposition efficiency is Co@C-5 catalyst, which can achieve 100 % decomposition efficiency at 350 °C and has good stability.

XPS guide for insulators: Electron flood gun operation and optimization, surface charging, controlled charging, differential charging, useful FWHMs, problems and solutions, and advice

Current day x-ray photoelectron spectroscopy (XPS) instrument makers have made significant advances in charge compensation systems over the last 20 years, which makes it easier to analyze insulators, but samples still have many differences in chemistry, dielectric properties, sizes, surface roughness, etc. that force instrument operators to tweak flood gun settings if they want or need to obtain high quality chemical state spectra that provide the most information. This guide teaches which flood gun variables to check, and how to optimize electron flood gun settings by presenting high energy resolution, chemical state spectra that show the result of using a poorly aligned flood gun on modern XPS instruments equipped with a monochromatic aluminum Kalpha x-ray source. This guide is focused on the XPS measurement of insulators—nonconductive metal oxides and polymers. This guide shows that by measuring commonly available polymers (polypropylene and polyethylene terephthalate) or ceramic materials (SiO2 and Al2O3), the operator can easily characterize the good and bad effects of XY position settings and other settings provided by modern electron flood gun systems. This guide includes many original, never-before-published XPS peak full width at half maximum (FWHM) that will greatly assist peak-fitting efforts. This guide reveals a direct correlation between electron count-rate and best charge-control settings. This guide discusses sample and instrument issues that affect surface charging and explains how to check the quality of charge control by measuring the FWHM and binding energy of C (1s) or O (1s) spectra produced from the sample currently being analyzed. A list of other charge-control methods is provided, along with advice and a best-known method. The availability of large extensive databases of actual spectra is extremely beneficial to users who need real-world examples of high quality chemical state spectra to guide their in-house efforts to collect high quality spectra and to interpret valuable information from the peak-fits of those spectra.

Tailored Local Electronic Environment of Co-N4 Sites in Cobalt Phthalocyanines for Enhanced CO2 Reduction Reaction.

Atomically dispersed Co-N4-based catalysts have been recently emerging as one of the most promising candidates for facilitating CO2 reduction reaction (CO2RR). The local electronic environment of Co-N4 sites in these catalysts is considered to play a critical role in adjusting the catalytic performance, the effort of which however is not yet clearly verified. Herein, a series of cobalt phthalocyanines with different peripheral substituents including unsubstituted phthalocyanine Co(II) (CoPc), 2,9,16,23-tetramethoxyphthalocyaninato Co(II) (CoPc-4OCH3), and 2,9,16,23-tetranitrophthalocyaninato Co(II) (CoPc-4NO2) are supported onto the surface of the multi-walled carbon nanotubes (CNTs), affording CoPc@CNTs, CoPc-4OCH3@CNTs, and CoPc-4NO2@CNTs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure measurements disclose the influence of the peripheral substituents on the local electronic structure of Co atoms in these three catalysts. Electrochemical tests indicate the higher CO2RR performance of CoPc-4OCH3@CNTs compared to CoPc@CNTs and CoPc-4NO2@CNTs as exemplified by the higher Faraday efficiency of CO, larger part current densities, and better stability displayed by CoPc-4OCH3@CNTs at the applied voltage range from -0.6 to -1.0V versus RHE in both H-cell and flow cell. These results highlight the effect of the electron-donating -OCH3 substituent on the enhanced catalytic activity of CoPc-4OCH3@CNTs, which will help develop Co-N4-based catalysts with promising catalytic performance toward CO2RR.

Nanoporous Au Behavior in Methyl Orange Solutions.

Nanoporous (NP) gold, the most extensively studied and efficient NP metal, possesses exceptional properties that make it highly attractive for advanced technological applications. Notably, its remarkable catalytic properties in various significant reactions hold enormous potential. However, the exploration of its catalytic activity in the degradation of water pollutants remains limited. Nevertheless, previous research has reported the catalytic activity of NP Au in the degradation of methyl orange (MO), a toxic azo dye commonly found in water. This study aims to investigate the behavior of nanoporous gold in MO solutions using UV-Vis absorption spectroscopy and high-performance liquid chromatography. The NP Au was prepared by chemical removal of silver atoms of an AuAg precursor alloy prepared by ball milling. Immersion tests were conducted on both pellets and powders of NP Au, followed by examination of the residual solutions. Additionally, X-ray photoelectron spectroscopy and electrochemical impedance measurements were employed to analyze NP Au after the tests. The findings reveal that the predominant and faster process involves the partially reversible adsorption of MO onto NP Au, while the catalytic degradation of the dye plays a secondary and slower role in this system.

Promoting the optoelectronic and nonlinear optics properties of MoS2 nanosheets via metal Al anchoring

Molybdenum disulfide (MoS2) has attracted much attention in the field of optoelectronic materials due to its stability and adjustable bandgap structure. However, improving the optoelectronic properties of MoS2 is still a challenging research. Herein, Al doped MoS2 (AMS) films were prepared by a simple single-step magnetron sputtering method. The bonding modes of Al implantation and auxiliary MoS2 were investigated by adjusting metal Al anchoring. The successful synthesis of AMS films was confirmed by the analysis of X-ray diffraction and X-ray photoelectron spectroscopy measurements to investigate the diffraction peaks of Al and Al2S3 and the valence electron structures of Al3+. Compared to MoS2, the A1g Raman peaks of AMS films are slightly blue-shifted, and the peak positions of both Mo3d and S2p are slightly shifted towards higher binding energies. This is attributed to the surface plasmon resonance effect produced by Al doping resulting in a large amount of electron transfer to the conduction band (CB) of MoS2. In addition, the density functional theory calculations reveal that Al doping of MoS2 results in a higher concentration of electrons in CB of MoS2, the band gap of MoS2 can be adjusted by changing the doping concentration of Al. The Z-scan results illustrated that MoS2 was converted from saturable absorption to reverse saturable absorption (RSA) by adjusting the sputtering power of Al. This is attributed to the fact that Al doping increases the electron concentration in the CB of MoS2, which promotes the RSA of the excited states and doping energy levels of AMS films. The values of the nonlinear absorption coefficients of AMS films are 2–5 times higher than those of MoS2, which significantly improves the nonlinear absorption performance of MoS2. The carrier relaxation process and kinetic mechanism of AMS films were investigated by transient absorption spectroscopy, moderate doping of Al can effectively improve the carrier lifetime. This implies that AMS films have good optoelectronic properties and have a wide application potential in optoelectronic devices.

Enhancing Oxygen Evolution Reaction with Two-Dimensional Nickel Oxide on Au (111)

The nature of the active sites of transition metal oxides during the oxygen evolution reaction (OER) has attracted much attention. Herein, we constructed well-defined nickel oxide/Au (111) model catalysts to study the relationship between the structures and their OER activity using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), electrochemical measurements, and density functional theory (DFT) calculations. The deposited nickel oxides on Au (111) were found to exhibit a two-dimensional (2D)/three-dimensional (3D) structure by regulating the annealing temperature. Combining STM, XPS and electrochemical measurements, our results demonstrated an optimal OER reactivity could be achieved for NiOx with a 2D structure on Au and provided a morphological description of the active phase during electrocatalysis.