The effect of the support on the surface composition of PtCu alloy nanocatalysts: In situ XPS and HS-LEIS studies

Supported PtCu alloys have been broadly applied in heterogeneous catalysis and electrocatalysis owing to their excellent catalytic performance and high CO tolerance. It is important to analyze the outermost surface composition of the supported alloy nanoparticles to understand the nature of the catalytically active sites. In this paper, homogeneous face-centered cubic PtCu nanoparticles with a narrow particle size distribution were successfully fabricated and dispersed on a high-surface-area Ti〇2 powder support. The samples were oxidized and reduced in situ and then introduced into the ultrahigh vacuum chamber to measure the topmost surface composition by high-sensitivity low-energy ion scattering spectroscopy, and to determine the oxidation states of the elements by X-ray photoelectron spectroscopy. The surface composition and morphology, elemental distribu-tion, and oxidation states of the components were found to be significantly affected by the support and treatment conditions. The PtCu is de-alloyed upon oxidation with CuO wetting on the TiO2 sur-face and re-alloyed upon reduction. Phase diagrams of the surface composition and the bulk com-position were plotted and compared for the supported and unsupported materials.

Construction of a macromolecular structural model of Chinese lignite and analysis of its low-temperature oxidation behavior

The aim of this paper is to analyze the change in the active structure of lignite during the process of lowtemperature oxidation by constructing a molecular structure model for lignite. Using quantum computation combined with experimental results of proximate analysis, ultimate analysis, Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS), a structural model for the large molecular structure was constructed. By analyzing the bond lengths in the model molecule, the evolution law for the active structure of lignite was predicted for the process of low-temperature oxidation. In low-temperature oxidation,alkanes and hydroxyls are the primary active structures observed in lignite, though ether may also react. These active functional groups react with oxygen to release heat, thereby speeding up the reaction between coal and oxygen. Finally, the content of various functional groups in the process of lignite low-temperature oxidation was analyzed by infrared analysis, and the accuracy of the model was verified.

Understanding fundamentals of electrochemical reactions with tender X-rays:A new lab-based operando X-ray photoelectron spectroscopy method for probing liquid/solid and gas/solid interfaces across a variety of electrochemical systems

Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrolyte/electrode interfaces is essential for developing advanced renewable energy technologies.However,the direct probing of real-time interfacial changes,i.e.,the surface intermediates,chemical environment,and electronic structure,under operating conditions is challenging and necessitates the use of in situ methods.Herein,we present a new lab-based instrument commissioned to perform in situ chemical analysis at liquid/solid interfaces using ambient pressure X-ray photoelectron spectroscopy(APXPS).This setup takes advantage of a chromium source of tender X-rays and is designed to study liquid/solid interfaces by the“dip and pull”method.Each of the main components was carefully described,and the results of performance tests are presented.Using a three-electrode setup,the system can probe the intermediate species and potential shifts across the liquid electrolyte/solid electrode interface.In addition,we demonstrate how this system allows the study of interfacial changes at gas/solid interfaces using a case study:a sodium–oxygen model battery.However,the use of APXPS in electrochemical studies is still in the early stages,so we summarize the current challenges and some developmental frontiers.Despite the challenges,we expect that joint efforts to improve instruments and the electrochemical setup will enable us to obtain a better understanding of the composition–reactivity relationship at electrochemical interfaces under realistic reaction conditions.

Hard X-ray Photoelectron Spectroscopy Study of Electron Spectral Structure beyond the Known Signal Electron Peak

HAXPES （hard X-ray photoelectron spectroscopy） is a powerful emerging instrument in surface analysis. It extended the photoelectron energy range up to 15,000 eV and opened the possibility to study much thicker films, buried layers and bulk electronic properties. In order to study these features, data for the electron IMFP （inelastic mean free path） at these energies is needed. To date, only calculated IMFP are available at energies above 5,000 eV and therefore experimental validation of these calculations are essential. In this paper, a new approach for using the HAXPES spectra is presented. This approach, treats the attenuated part of the electron spectrum as a whole to calculating the average electron energy loss. This average electron energy loss is the result of inelastic collisions in the material and hence, carry with it information about the electron transport poses. Carbon layers with thicknesses between 20 and 75 nanometer deposited over copper substrate were used to test this approach at the Spanish beam-line （Spline） in the ESRF （European synchrotron radiation facility）. The measured results showed good agreement with the predictions of the multiple inelastic scattering theory. In addition, an algorithm for the experimental evaluation of electron IMFP, using the measured energy loss, is proposed.

Effects of Sintering Atmosphere on the Microstructure and Surface Properties of Symmetric TiO2 Membranes

The effects of sintering atmosphere on the properties of symmetric TiO2 membranes are studied with regard to sintering behavior, porosity, mean pore size, surface comPosition. and surface charge properties. The exerimental results show that the symmetric TiO2 membranes display better sintering activity in the air than in argon, and the mean pore diameters and porosities of the membrane sintered in argon are higher than those of the membrane sintered in the air at the same temperature. The surface compositions of the symmetric TiO2 membrane sintered in the air and in argon at different temperatures, as studied by X-ray photoelectron spectroscopy, are discussed in terms of their chemical composition, with particular emphasis on the valence state of the titanium ions. The correlation between the valence state of the titanium ions at the surface and the surface charge properties is examined.It is found that the presence of Ti^3＋, introduced at the surface of the symmetric TiO2 membranes by sintering in a lower partial pressure of oxygen, is related to a significant decrease in the isoelectric point. TiO2 with Ti^4＋ at the interface has an isoelectric point of 5.1, but the non-stoichiometric TiO2-x with Ti^3＋ at the interface has a lower isoelectric point of 3.6.

Selective removal of heavy metal ions from aqueous solutions with surface functionalized silica nanoparticles by different functional groups

The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.

Comparison of Structures and Properties between Wool and Ramie Fibers Treated by Atmospheric Pressure Ar and Ar/O_2 Plasma

The technique of atmospheric pressure plasma is of value in textile industry.In this paper,argon(Ar)and argon/oxygen(Ar/O2)atmospheric pressure plasma were used to treat wool and ramie fibers.The structures and properties of treated fibers were investigated by means of SEM,XPS,single fiber tensile tester and so on.The results proved that the effects of plasma treatments depended on structural characteristics of fibers to a great extent,besides conditions of plasma treatment.By atmospheric pressure plasma treatment,wool fiber had significant changes in morphology structure,surface chemical component,mechanic properties and dyeability,while ramie fiber just showed a little change.In additional,Ar/O2 plasma showed more effective action than argon.And at the beginning of treatment,plasma brought about remarkable effects,which did not increase with prolonging of treat time.

Simultaneous N-intercalation and N-doping of epitaxial graphene on 6H-SiC（0001） through thermal reactions with ammonia

Surface functionalization of epitaxial graphene overlayers on 6H-SiC（0001） has been attempted through thermal reactions in NH3. X-ray photoelectron spectroscopy and micro-region low energy electron diffraction results show that a significant amount of N is present at the NHB-treated graphene surface, which results in strong band bending at the SiC surface as well as decoupling of the graphene overlayers from the substrate. The majority of the surface N species can be removed by annealing in vacuum up to 850 ~C, weakening the surface band bending and resuming the strong coupling of graphene with the SiC surface. The desorbed N atoms can be attributed to the intercalated species between graphene and SiC. Low temperature scanning tunneling spectroscopy and density functional theory simulations confirm the presence of N dopants in the graphene lattice, which are in the form of graphitic substitution and can be stable above 850 ~C. This is the first report of simultaneous N intercalation and N doping of epitaxial graphene overlayers on SiC, and it may be employed to alter the surface physical and chemical properties of epitaxial graphene overlayers.

Synthesis and electrocatalytic activity of Au@Pd coreshell nanothorns for the oxygen reduction reaction

Bimetallic core-shell nanostructures with porous surfaces have drawn considerable attention due to their promising applications in various fields, including catalysis and electronics. In this work, Au@Pd core-shell nanothorns （CSNTs） with rough and porous surfaces were synthesized for the first time through a facile co-chemical reduction method in the presence of polyallylamine hydrochloride （PAH） and ethylene glycol （EG） at room temperature. The size, morphology, and composition of Au@Pd CSNTs were investigated by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, energy dispersive spec- troscopy （EDX）, EDX mapping, and X-ray photoelectron spectroscopy （XPS）. The electrochemical properties of as-synthesized Au@Pd CSNTs were also studied by various electrochemical techniques. Au@Pd CSNTs exhibited remarkably high electrocatalytic activity and durability for the oxygen reduction reaction （ORR） in the alkaline media, owing to the unique porous structure and the synergistic effect between the Au core and Pd shell.

Fe/Al_2O_3/Fe隧道结特性分析

用离子束溅射方法制备磁性隧道结 (MTJ) .研究MTJ样品的隧道结磁电阻 (TMR)效应 .用X射线光电子能谱分析了MTJ的软、硬磁层和非磁层及其界面的化学组成与微结构 .研究了MTJ的微结构对氧化铝势垒高度与有效宽度和TMR效应的影响 .

Effect of defects on photocatalytic activity of rutile TiO2 nanorods

To further understand the effect of structural defects on the electrochemical and photocatalytic properties of TiO2, two synthetic approaches based on hydrothermal synthesis and post-synthetic chemical reduction to achieve oxygen defect- implantation were developed herein. These approaches led to the formation of TiO2 nanorods with uniformly distributed defects in either the bulk or on the surface, or the combination of both, in the formed TiO2 nanorods （NRs）. Both approaches utilize unique TiN nanoparticles as the reaction precursor. Electron microscopy and Brunauer-Emmett-Teller （BET） analyses indicate that all the studied samples exhibit similar morphology and similar specific surface areas. X-ray photoelectron spectroscopy （XPS） and electron paramagnetic resonance （EPR） data confirm the existence of oxygen defects （Vo）. The photocatalytic properties of TiO2 with different types of implanted Vo were evaluated based on photocatalytic H2 production. By optimizing the concentration of Vo among the TiO2 NRs subjected to different treatments, significantly higher photocatalytic activities than that of the stoichiometric TiO2 NRs was achieved. The incident photon-to-current efficiency （IPCE） data indicate that the enhanced photocatalytic activity arises mainly from defect-assisted charge separation, which implies that photo-generated electrons or holes can be captured by Vo and suppress the charge recombination process. The results show that the defective TiO2 obtained by combining the two approaches exhibits the greatest photocatalytic activity enhancement amon~ all the samples.

Optimization of the thermoelectric properties of poly(nickel-ethylenetetrathiolate) synthesized via potentiostatic deposition

The coordination polymer poly（nickel-ethylenetetrathiolate） （poly（Ni-ett））, formed by nickel（Ⅱ） and 1,1,2,2-ethenetetrathiolate （ett）, is the most promising N-type organic thermoelectric material ever reported; it is synthesized via potentiostatic deposition, and the effect of different applied potentials on the optimal performance of the polymers is investigated. The optimal thermoelectric property ofpoly（Ni-ett） synthesized at 0.6 V is remarkably greater than that of the polymers synthesized at 1 and 1.6 V, exhibiting a maximum power factor of up to 131.6μW/mK2 at 360 K. Furthermore, the structure-property correlation ofpoly（Ni-ett） is also extensively investigated. X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS） analyses revealed that the larger size of crystalline domains and the higher oxidation state of poly（Ni-ett） synthesized at 0.6 V possibly results in the higher bulk mobility and carrier concentration in the polymer chains, respectively, accounting for the enhanced power factor.

Effects of Co doping on electronic structure and electric/magnetic properties of La_(0.1)Bi_(0.9)FeO_3 ceramics

In this work,we report the influence of Co-doping on the electronic band structure,dielectric and magnetic properties of La0.1Bi0.9Fe1-xCoxO3 ceramics.X-ray photoelectron spectroscopy investigation shows that Co dopant can shift the valence band spectrum and core-level lines of constituent elements towards higher bind energy regions simultaneously increase the concentration of oxygen vacancies in ceramics.The effects of dopant are discussed with focus given to the Co-doping induced enhancement of electrical conductivity and resistive switching phenomena.