Tailoring the surface and interface structures of photocatalysts to enhance hydrogen production

Photocatalytic water splitting using semiconductor photocatalysts is a promising approach for the production of carbon-neutral,sustainable and clean hydrogen fuel.However,the separation and transport of photoinduced carriers are generally considered to be rate-limiting steps,and their low efficiency remains a major challenge.Therefore,much effort has been devoted to developing new strategies in surface/interface engineering of photocatalysts to improve the dynamics of charge separation/transport.This feature article briefly summarizes recent advances in photocatalyst surface/interface engineering by our research group,which have been achieved through the design of various novel photocatalysts,including interfacial modulation,heterostructure construction,heteroatom doping,single atom and diatom sites.The article is divided into three parts:first,we briefly introduce the three key processes involved in solar water splitting and reveal relationships between the properties of nanostructural photocatalysts and the fundamentals of water splitting;second,we detail methods and strategies for surface and interfacial structures to improve the efficiency of the fundamental processes,especially charge separation;finally,we explore prospects for photocatalytic water splitting applications.This article provides a valuable resource and strategies for researchers currently working in the field of photocatalytic water splitting.

Characterization of Interface State Density of Ni/p-GaN Structures by Capacitance/Conductance-Voltage-Frequency Measurements

For the frequency range of I kHz-lOMHz, the interface state density of Ni contacts on p-GaN is studied using capacitance-voltage （C-V） and conductance-frequency-voltage （G-f-V） measurements at room temperature. To obtain the real capacitance and interface state density of the Ni/p-GaN structures, the effects of the series resistance （Rs） on high-frequency （SMHz） capacitance values measured at a reverse and a forward bias are investigated. The mean interface state densities obtained from the CHF-CLF capacitance and the conductance method are 2 ×1012 e V-1 cm-2 and 0.94 × 1012 eV-1 cm-2, respectively. Furthermore, the interface state density derived from the conductance method is higher than that reported from the Ni/n-GaN in the literature, which is ascribed to a poor crystal quality and to a large defect density of the Mg-doped p-GaN.

FINE STRUCTURES OF BOTH INTERFACES AND INTERFACIAL REACTION PRODUCTS

The characteristic of interface depending on the atomic structure exerts an inportant,and sometime controlling,influence on performance of the interacial materials. The present paper reviews the main studies on fine structure of both the materials inter- faces and interfacial reaction products in semiconductor uperlattice,metal multilayer ceram- ics and composite materials by mean of selected area electron doffraction patterns and high resolution electron microscopy. The following features of interfaces are reviewed:the orientation relationships;the char- acteristic of steps,facets and ronghness of interfaces;atomic bonding across the interface;the degree of coherency,the structure of misfit dislocations and elastic relaxations at the inter- faces:the presence of defects at the onterfaces:the structure of the interfacial reaction prod- ucts as well as the reaction kinetics and reaetion mechanism.

Segregation of Si and Mg at Fe(110)/Al(110) Interface

The interface structure and electronic properties of Fe(110)/Al(110) are investigated by the first-principles plane-wave pseudopotential method. The interface segregation position of Si and Mg is determined, and the effect of Mg and Si on the interface binding of Fe(110)/Al(110) is analyzed by combining the work of separation and charge density. The results show that the Fe(110)/Al(110) interface energy of FeHollow coordination is smaller and the interface structure is more stable. The Fe(110)/Al(110) interface separation surface in the form of Fe-Hollow coordination appears at the sub interface layer on the side of Al(110)near the interface. The interface structure of Mg and Si segregation is similar to that of undoped alloy elements.The calculations also suggest that Mg and Si segregate on the Al(110) side of the interface and occupy the Al lattice on the Al(110) side. The segregation of Mg and Si elements will reduce the interface binding, primarily because the Fe-Si bond and Fe-Mg bond are weaker than Fe-Al bond.

The role of melt cooling rate on the interface between 18R and Mg matrix in Mg_(97)Zn_(1)Y_(2) alloys

The role of melt cooling rate on the interface morphology and dislocation configuration between 18R long-period stacking ordered(LPSO)structure and Mg matrix in Mg_(97)Zn_(1)Y_(2)(at.%)alloys was investigated by atomic-scale HAADF-STEM imaging.The 18R/Mg interface is step-like both in the near-equilibrium alloy and non-equilibrium alloy.Lower cooling rate makes the step size more regular and larger.Only 54R structure can be observed at the interface in the near-equilibrium alloy,and the dislocations are highly ordered.54R and 54R′structure sandwiched by b1 and b2+b3 dislocation arrays,and new dislocation configuration can be detected at the interface in the non-equilibrium alloy,but the dislocations are less ordered.18R/Mg interface containing 54R or 54R′in equilibrium width,parallel to the(010)plane,should be most stable based on elastic calculation.The segregation of solute atoms and its strong interaction with dislocations dominate the LPSO/Mg interface via diffusion-displacive transformation.

A Modified Model for Soil–Structure Interface Considering Random Damage of Mesoscopic Contact Elements

The interaction between soil and marine structures like submarine pipeline/pipe pile/suction caisson is a complicated geotechnical mechanism process.In this study,the interface is discretized into multiple mesoscopic contact elements that are damaged randomly throughout the shearing process due to the natural heterogeneity.The evolution equation of damage variable is developed based on the Weibull function,which is able to cover a rather wide range of distribution shapes by only two parameters,making it applicable for varying scenarios.Accordingly,a statistical damage model is established by incorporating Mohr–Coulomb strength criterion,in which the interfacial residual strength is considered whereby the strain softening behavior can be described.A concept of“semi-softening”characteristic point on shear stress–displacement curve is proposed for effectively modeling the evolution of strain softening.Finally,a series of ring shear tests of the interfaces between fine sea sand and smooth/rough steel surfaces are conducted.The predicted results using the proposed model are compared with experimental data of this study as well as some results from existing literature,indicating that the model has a good performance in modeling the progressive failure and strain softening behavior for various types of soil–structure interfaces.

Interface structure and formation mechanism of diffusion-bonded joints of TiAl-based alloy to titanium alloy

Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15～120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al rich α(Ti)layer adjacent to TC2,and the other is (Ti 3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti 3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three stage mechanism,namely(a)the occurrence of a single phase α(Ti)layer;(b)the occurrence of a duplex phase(Ti 3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti 3Al+TiAl)layers.

Theoretical Studies on the Si(001)-SiO_2 Interface Structure

Novel models （2× 1） of Si（001）-SiO2 interface structure have been established. The method of the first-principle General Gradient Approximation （GGA） is employed to structurally optimize the established theoretical models under the K-point space of periodic boundary condition. The structures after optimization have been analyzed, and the results show that the interfaces present in disordered state and both Si-O-Si and Si=O structures exist. Meanwhile, the bonding of surface structure is analyzed via the graphics of electron localization function（ELF）.

Effect of In Composition on Two-Dimensional Electron Gas in Wurtzite AlGaN/InGaN Heterostructures

The effect of In composition on two-dimensional electron gas in wurtzite AlGaN/InGaN heterostructures is theoretically investigated. The sheet carrier density is shown to increase nearly linearly with In mole fraction x, due to the increase in the polarization charge at the AlGaN/InGaN interface. The electron sheet density is enhanced with the doping in the AlGaN layer. The sheet carrier density is as high as 3.7×1013 cm^-2 at the donor density of 10×1018 cm^-3 for the HEMT structure with x=0.3. The contribution of additional donor density on the electron sheet density is nearly independent of the In mole fraction.

Dye-sensitized solar cells: Atomic scale investigation of interface structure and dynamics

Recent progress in dye-sensitized solar cells （DSC） research is reviewed, focusing on atomic-scale investigations of the interface electronic structures and dynamical processes, including the structure of dye adsorption onto Ti02, ultrafast electron injection, hot-electron injection, multiple-exciton generation, and electron-hole recombination. Advanced exper- imental techniques and theoretical approaches are briefly summarized, and then progressive achievements in photovoltaic device optimization based on insights from atomic scale investigations are introduced. Finally, some challenges and oppor- tunities for further improvement of dye solar cells are presented.

CRYSTAL DEFECTS AND GRAIN INTERFACE STRUCTURE OF ION-NITRIDED LAYERS

Observation under high resolution electron microscope shows that the continuous bombing of high speed ions produces a great amount of vacant site defects.The assembly of vacancies forms vacant dish,and the collapase of vacant dish forms stacking fault tetrahedrons and oth- er crystal defects.The interfaces between phase ε(Fe_(2-3)N)and phase γ'(Fe_4N)are smooth, straight and coherent,and they have the orientation relationships of(11)//(0001)and [110]/[110] .

Fine structure characterization of an explosively-welded GH3535/316H bimetallic plate interface

An explosion-welded technology was induced to manufacture the GH3535/316H bimetallic plates to provide a more cost-effective structural material for ultrahigh temperature,molten salt thermal storage systems.The microstructure of the bonding interfaces were extensively investigated by scanning electron microscopy,energy dispersive spectrometry,and an electron probe microanalyzer.The bonding interface possessed a periodic,wavy morphology and was adorned by peninsula-or island-like transition zones.At higher magnification,a matrix recrystallization region,fine grain region,columnar grain region,equiaxed grain region,and shrinkage porosity were observed in the transition zones and surrounding area.Electron backscattered diffraction demonstrated that the strain in the recrystallization region of the GH3535 matrix and transition zone was less than the substrate.Strain concentration occurred at the interface and the solidification defects in the transition zone.The dislocation substructure in 316H near the interface was characterized by electron channeling contrast imaging.A dislocation network was formed in the grains of 316H.The microhardness decreased as the distance from the welding interface increased and the lowest hardness was inside the transition zone.

Basement interface structural characteristics beneath Jiashi strong earthquake swarm area in Xinjiang, China

The seismic data obtained from high resolution seismic refraction profile in Jiashi strong earthquake swarm area in Xinjiang, China were further processed with ray hit analysis method and more complete basement interface structural characteristics beneath Jiashi strong earthquake swarm area were determined. The results show that there are two clear basement interfaces at the upper crust in Jiashi strong earthquake swarm area. The first one with buried depth ranging from 2.6 km to 3.3 km presents integral and continuous structure, and it appears an inclined plane interface and smoothly rises up toward Tianshan Mountain. The second basement interface with buried depth from 8.5 km to 11.8 km, is the antiquated crystalline basement of Tarim basin. Near the post number of 37 km, the buried depth of the crystalline basement changed abruptly by 2.5 km, which maybe result from an ultra crystalline basement fault. If taking this fault as a boundary, the crystalline basement could be divided into two parts, i.e. the southwestern segment with buried depth about 11.5 km, and the northeastern segment with buried depth approxi-mately from 8.5 km to 9.0 km. That is to say, in each segment, the buried depth changes not too much. The northeast segment rises up as a whole and upheaves slightly from southwest to northeast, which reflects the upper crustal deformation characteristics under the special tectonic background at the northwestern edge of Tarim basin.

STRUCTURE AND INTERFACE PROPERTIES OF Fe/C MULTILAYERS

Fe/C multilayer thin films were deposited by magnetron sputtering. Small angle X-ray diffraction measurements show very well periodicity of the samples. The modulation period determined from a modified Bragg equation agrees well with that determined from deposition rate. The interfacial roughness parameter ξof several samples calculated by X-ray diffraction is between 3.5(?) and 5.6(?).

Earth Ecosystem Theory: Ⅲ Structure and Interface

By applying the segmentation and composition principles of ecosystem,the structure and interface of earth ecosystem are fully elaborated,and corresponding model diagrams are established to display its composition and interconversion. The research finds that earth ecosystem includes three sub-ecosystems： terrestrial ecosystem,marine ecosystem and atmospheric ecosystem. The impact sequence of sub-ecosystems on earth ecosystem is atmospheric ecosystem 〉 marine ecosystem 〉 terrestrial ecosystem. Based on the segmentation and composition principles of ecosystem and the application of earth ecosystem structure and interface,we give new explanations to Taoism and Taiji with the eight diagrams,which contributes to theoretical research of natural science.

Influences of Interface States on Resistive Switching Properties of TiOx with Different Electrodes

Different TiOx thin films prepared by graded or sufficient oxidization of Ti are applied with Pt or Ag electrode in metal？insulator-metal （MIM） structures for studying the properties and mechanisms of resistive switching. The differences on the mobile oxygen vacancies in TiOx films and different work functions of the electrode films result in different insulator-metal interface states, which are displayed as ohmic-like or non-ohmic contact. Based on the interface states, the electrical models for MIM devices are analyzed and extracted. The electrode-limited effect and the bulk-limited effect can be unified to explain the mechanisms for resistive switching behavior as the dominant effect respectively in various conditions. All the current-voltage curves of the four kinds of specimens measured in the experiments can be explained and proved in accordance with the theory.

Superb creep lives of Ni-based single crystal superalloy through size effects and strengthening heterostructure γ/γ' interfaces

This study presents a design strategy to enhance the high-temperature creep resistance of Ni-based superalloys.This strategy focuses on two principles:(1)minimizing the dimensions ofγ/γ′interfaces andγchannels by reducing the size of theγ′phase;(2)key alloy composition control to strengthen the heterostructureγ/γ′interfaces.This strategy proved very effective by the designed three superalloys'prolonged creep lives.An alloy exhibits ultra-long creep life by 388 h at 1100°C/137 MPa,which runs at the highest level among those alloys without Ru addition.With Ru addition,an alloy that lasted for 748 h with a creep strain of~6%at 1110°C/137 MPa is developed.This study provides a new route of high-temperature creep lives through heterostructure interfacial design with size effects and key alloying elements.

Microstructure and shear strength of the brazed joint of Ti(C,N)-based cermet to steel

Firm joins were obtained between Ti（C,N）-based cermet and steel with Ag-Cu-Zn-Ni filler metal by vacuum brazing. The effects of technological parameters such as brazing temperature, holding time, and filler thickness on the shear strength of the joints were investigated. The microstructure of welded area and the reaction products of the filler metal were examined by scanning electron microscopy （SEM）, metallographic microscope （OM）, energy-dispersive X-ray analysis （EDS）, and X-ray diffraction （XRD）. The brazing temperature of 870℃, holding time of 15 min, and filler thickness of 0.4 mm are a set of optimum technological parameters, under which the maximum shear strength of the joints, 176.5 MPa, is achieved. The results of microstructure show that the wettability of the filler metal on Ti（C,N）-based cermet and steel is well. A mutual solution layer and a diffusion layer exist between the welding base materials and the filler metal.

Microstructure and strength of brazed joints of TiB_2 cermet to TiAl-based alloys

In this study, TiB 2 cermet and TiAl based alloy are vacuum brazed successfully by using Ag Cu Ti filler metal. The microstructural analyses indicate that two reaction products, Ti(Cu, Al) 2 and Ag based solid solution (Ag(s.s)), are present in the brazing seam, and the interface structure of the brazed joint is TiB 2/TiB 2+ Ag(s.s) /Ag(s.s)+Ti(Cu, Al) 2/Ti(Cu, Al) 2/TiAl. The experimental results show that the shear strength of the brazed TiB 2/TiAl joints decreases as the brazing time increases at a definite brazing temperature. When the joint is brazed at 1 223 K for 5 min , a joint strength up to 173 MPa is achieved.

Preparation of High-Density Nanocrystalline Bulk Selenium by Rapid Compressing of Melt

The melt＇s solidification behavior of elemental selenium is investigated by a series of experiments including rapid compressing to 2.8 and 3.5 GPa within 20ms respectively, slow compressing to 2.8 GPa for 20 min and natural cooling at ambient pressure. Based on the x-ray diffraction, scanning electron microscope and transmission electron microscope results of the recovered samples, it is clearly shown that homogenous nanostructures are formed only by the rapid compression processes, and that the average crystal sizes are about 18.7 and 19.0 nm in the samples recovered from 2.8 and 3.5 GPa, respectively. The relative density of the nanocrystalline bulk reaches 98.17% of the theoretical value. It is suggested that rapid compression could induce pervasive nucleation and restrain grain growth during the solidification, which is related to fast supercooling, higher viscosity of the melt and lower diffusivity of atoms under high pressure.