Tuning strategies and structure effects of electrocatalysts for carbon dioxide reduction reaction

Carbon dioxide emissions have increased due to the consumption of fossil fuels,making the neutralization and utilization of CO_(2) a pressing issue.As a clean and efficient energy conversion process,electrocatalytic reduction can reduce carbon dioxide into a series of alcohols and acidic organic molecules,which can effectively realize the utilization and transformation of carbon dioxide.This review focuses on the tuning strategies and structure effects of catalysts for the electrocatalytic CO_(2) reduction reaction(CO_(2)RR).The tuning strategies for the active sites of catalysts have been reviewed from intrinsic and external perspectives.The structure effects for the CO_(2)RR catalysts have also been discussed,such as tandem catalysis,synergistic effects and confinement catalysis.We expect that this review about tuning strategies and structure effects can provide guidance for designing highly efficient CO_(2)RR electrocatalysts.

The Structure and Size-effect of Calcium Modified Lead Titanate Nanocrystal,Pb_(0.85)Ca_(0.15)TiO_3

Calcium modified lead titanate nanocrystal material Pb0.85Ca0.15TiO3 was synthesized by means of a solgel method.The changes of crystal structure and grainsize of the samples were investigated under different conditions of heat treatment.the results show that the tetragonal symmetry is reduced and the ferroelectricparaelectric phase transformation temperature is decreased with the reduce of the grainsize of the sample.the critical grainsize for the ferroelectricparaelectric phase transformation at room temperature was calculated.The change regularities of the lattice constant and tetragonality with the grainsize are discussed.

Study on the effect of ground motion direction on the response of engineering structure

Due to the randomness of earthquake wave magnitude and direction, and the uncertain direction of strong axis and weak axis in the construction of engineering structures, the effect of the direction of ground motion on a structure are studied herein. Ground motion records usually contain three vertical ground motion data, which are obtained by sensors arranged in accordance with the EW （East -West） direction, NS （South- North） direction and perpendicular to the surface （z） direction, referring to the construction standard of seismic stations. The seismic records in the EW and NS directions are converted to Cartesian coordinates in accordance with the rotation of θ = 0°-180°, and consequently, a countless group of new ground motion time histories are obtained. Then, the characteristics of the ground motion time history and response spectrum of each group were studied, resulting in the following observations： （1） the peak and phase of ground motion are changed with the rotation of direction θ, so that the direction θ of the maximum peak ground motion can be determined; （2） response spectrum values of each group of ground motions change along with the direction θ, and their peak, predominant period and declining curve are also different as the changes occur; then, the angle θ in the direction of the maximum peak value or the widest predominant period can be determined; and （3） the seismic response of structures with different directions of ground motion inputs has been analyzed under the same earthquake record, and the results show the difference. For some ground motion records, such as the Taft seismic wave, these differences are significant. Next, the Lushan middle school gymnasium structure was analyzed and the calculation was checked using the proposed method, where the internal force of the upper space truss varied from 25% to 28%. The research results presented herein can be used for reference in choosing the ground motion when checking the actual damage to structures following earthquakes and explaining the seismic damage. Meanwhile, it also provides a reference value for research into the most severe ground motion.

Electronic Structure Effect on Model Cluster for L1_2 Structure of Al_3Ti Intermetallic Compound with an Addition of Alloying Elements Fe, Ni and Cu

By use of self-consistent field Xα scattered-wave (SCF-Xα-SW) method, the electronic structure was calculated for four models of Ti4Al14X (X=Al, Fe, Ni and Cu) clusters. The Ti4Al14X cluster was developed based on L12 Al3Ti-base intermetallic compound. The results are presented using the density of states (DOS) and one-electron properties, such as relative binding tendency between the atom and the model cluster, and hybrid bonding tendency between the alloying element and the host atoms. By comparing the four models of Ti4Al14X cluster, the effect of the Fe, Ni or Cu atom on the physical properties of Al3Ti-based L12 intermetallic compounds is analyzed. The results indicate that the addition of the Fe, Ni or Cu atom intensifies the relative binding tendency between Ti atom and Ti4Al14X cluster. It was found that the Fermi level (EF) lies in a maximum in the DOS for Ti4Al14Al cluster; on the contrary, the EF comes near a minimum tn the DOS for Ti4Al14X (X=Fe, Ni and Cu) cluster. Thus the L12 crystal structure for binary Al3Ti alloy is unstable, and the addition of the Fe, Ni or Cu atom to Al3Ti is benefical to stabilize L12 crystal structure. The calculation also shows that the Fe, Ni or Cu atom strengthens the hybrid bonding tendency between the central atom and the host atoms for Ti4Al14X cluster and thereby may lead to the constriction of the lattice of Al3Ti-base intermetallic compounds.

EFFECT OF STRUCTURE OF FUNCTIONAL POLYMER ACTIVE MATERIALS ON PROPERTIES OF GADOLINIUM ION SELECTIVE ELECTRODE

In this paper,the functional polymeric active materials were prepared by the grafting copolymerization and their structure and properties were studied.The results show that the structure and properties of these ac- tive materials have the relative large effects on the properties of gadolinium ion selective electrodes.

CRYSTAL STRUCTURE AND SHG EFFECT OF COMPLEX [Zn(POM)_2Br_2]

[Zn(POM)_2Br_2](POM is 3-Methyl-4-Nitropyridine-1-Oxide),C_(12)H_(12)Br_2N_4O_6Zn, Mr=533.44,triclinic,P1,a=11.450(3),b=13.027(2),c=6.605(1),α=101.25(1),β=96.96(2), γ=108.06(2)°,V=901.2(4)~3,Z=2,D_c=1.97g·cm^(-3),(MoK_α)=0.71069,F(000)=520, μ=58.21cm^(-1),final R=0.040 for 2192 observed reflections,T=296K.The compound is a mononuclear complex,containing a tetrahedrally coordinated zinc atom.

The Effect of Spatial Structure Character of Heat Source on the Ray Path and the Evolution of Wave Energy of Meridional Wave Train

This paper studies correlations between the spatial structure character of thermal forcing and deformation and the amplitude of rays of meridional wave train. It is shown that if thermal forcing appears a meridional linear variation the rays of quasi-stationary planetary wave may propagate along oblique lines and if the meridional variability of heat source has second order term the rays show distinct deformation as a great circular route. Additionally, the inhomogeneous distribution may cause lower frequency oscillations in mid- and low-latitudes. The combination of zonal and meridional wave numbers and distributive character of heat source may form an inverse mechanism of variational trend of generized wave energy, reflecting in some degree the physical process of transition between meridional and zonal flow patterns.

Steric Effect Modulating the Structures of Trinuclear Zinc Carboxylate Frameworks

By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks, [Zn3（BDC）3（EtOH）2]（1）, [Zn3（BDC）3（py）2]·2DMF（2）, and [Zn3（NH2-BDC）3（H2O）2]·5DMF（3） which are constructed on the same linear trinuclear Zn3（RCOO）6 secondary building units, have been synthesized and characterized by X-ray diffraction analyses. Structural analyses showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2-amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type.

Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films （Cr/a-C：H） are deposited successfully by using a dc reactive mag- netron sputtering system. The structure and mechanical properties of the as-deposited Cr/a-C：H films are characterized systematically by field-emission scanning electron microscope, x-ray diffraction, Raman spectra, nanoindentation and scratch. It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness, toughness and adhesion strength in the amorphous carbon matrix, which possesses relatively higher nano-hardness of 15. 7 CPa, elastic modulus of 126.8 GPa and best adhesion strength with critical load （Lc） of 36 N for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm. The friction and wear behaviors of as-deposited Cr/a-C：H films are evaluated under both the ambient air and deionized water conditions. The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm under the ambient air condition, and the friction coetllcient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film. Superior combination of mechanical and tribological properties for the Cr/a-C：H film should be a good candidate for engineering applications.

THE EFFECT OF DLSPERSED MoO_3 ON STRUCTURE OF ZEOLITE ZSM-11

The dispersion behavior of MoO_3 on ZSM-11 and effect of dispersed MoO_3 on the fram ework structure of ZSM-11 have been studjed using X-ray diffraction and infrared spectroscopy

The effect of the horizontal structure for symmetric tropical cyclones on their movement

In this paper, using Holland's method, the effect of the horizontal structure of tropical cyclones on their motion is investigated. The 'characteristic radius', r0 characterized as the horizontal structure of a tropical cyclone,in which m and p are the parameters of the vortex, has been found by the author. And then it has been shown that there is but one 'characteristic radius' for each cyclone with horizontal structure. Two direct analytic solutions for the uniform and non-uniform basic flows in steady situations are presented with rc Results show that the change in the horizontal structure of the tropical cyclone itself will have obvious effect on the cyclone motion, on both its direction and speed. Therefore it must be considered in the research on the tropical cyclone motion.

Structure Dependence of Excitonic Effects in Chiral Graphene Nanoribbons

We explore the excitonic effects in chiral graphene nanoribbons (cGNRs), whose edges are composed alternatively of armchair-edged and zigzag-edged segments. For cGNRs dominated by armchair edges, their energy gaps and exciton energies decrease with increasing chirality angles, and they, as functions of widths, oscillate with the period of three, while the exciton binding energies do not have such distinct oscillation. On the other hand, for cGNRs dominated by zigzag edges, all the energy gaps, exciton energies, and exciton binding energies show oscillation properties with their widths, due to the interactions between the edge states localized at the opposite zigzag edges. In addition, the triplet excitons are energy degenerate when the electrons are spin-unpolarized, while the degeneracy split when the electrons are spin-polarized. All the studied cGNRs show strong excitonic effects with the exciton binding energies of hundreds of meV.

Size Effect on the Raman Spectra and Electronic Structure of the Glycine-alanine Oligopeptide Chains

A theoretical study on oligopeptide chains of glycine-alanine by density functional theory（DFT） is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G（d） level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues（glycine or alanine） at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.

Damage Effects of Overload Axes on Pavement Structures

This paper established the axle load distribution model of overload axes by practical axle-meter investigations. To study the effects of overload axes on pavement distress, deflection and deflection basin tests with axle load from 60kN to 190kN were conducted on different pavement structures. The relationship between axle load and its deflection as well as its deflection basin curvature was obtained by statistical analyses. A methodology for deriving the equivalent conversion factors of overload axes to equivalent standard axle loads (ESAL) of 100kN is developed, obtaining the relationship between the equivalent conversion factors and the axle loads. Comparing the calculated defiections with the measured deflections, that elastic layered system theory is suitable for analyzing overload vehicles was verified. Consequently, the stresses and strains caused by overload axes were calculated by elastic layered system theory. The results showed that overload axes led to greater stresses and strains causing premature pavement fatigue distress. To guarantee the expected performance in overload axes pavement, the structure thickness needed increasing was obtained. The results are of referential values in the control of semi-rigid pavement overloadings.

Drivers for Inter-city Innovation Networks Across Chinese Cities:Modelling Physical Versus Intangible Effects

Cross-region innovation is widely recognized as an important source of the long-term regional innovation capacity.In the recent past,a growing number of studies has investigated the network structure and mechanisms of cross-region innovation collaboration in various contexts.However,existing research mainly focuses on physical effects,such as geographical distance and high-speed railway connections.These studies ignore the intangible drivers in a changing environment,the more digitalized economy and the increasingly solidified innovation network structure.Thus,the focus of this study is on estimating determinants of innovation networks,especially on intangible drivers,which have been largely neglected so far.Using city-level data of Chinese patents(excluding Hong Kong,Macao,and Taiwan Province of China),we trace innovation networks across Chinese cities over a long period of time.By integrating a measure on Information and Communications Technology(ICT)development gap and network structural effects into the general proximity framework,this paper explores the changing mechanisms of Chinese innovation networks from a new perspective.The results show that the structure of cross-region innovation networks has changed in China.As mechanisms behind this development,the results confirm the increasingly important role of intangible drivers in Chinese inter-city innovation collaboration when controlling for effects of physical proximity,such as geographical distance.Since digitalization and coordinated development are the mainstream trends in China and other developing countries,these countries'inter-city innovation collaboration patterns will witness dramatic changes under the influence of intangible drivers.

THE EFFECTS OF VELOCITY RATIO ON THE LARGE SCALE COHERENT STRUCTURES IN FREE SHEAR LAYERS

The velocity ratio of a free shear layer has an important influence on the spatial development of the large scale coherent structures in the layer. In this study, numerical simulations are performed to get an insight into this problem. The obtained numerical results agree quite well with those of a linear inviscid stability theory and the available experimental data.

The effect of internal tides on the vertical structure of tidal current in the North Huanghai Sea

The tidal current is generally predominant in China's offshore areas. The vertical structure of the observedtidal current is quite complicated with the presence of seasonal thermocline. The observed tidal current may be divided into two parts, an averaged barotropic tide current and a variation tide current. A method for studying the vertical structure of tidal current is developed from the constitution and distribution of energy, and the vertical structure of the observed tide current in the North Huanghai Sea is studied on the basis of the method. The result shows that the reason why the energy of the tidal current is concentrated on the neighbourhood of the thermocline mainly lies in the internal tides i under certain conditions, the fact that the direction of the internal tide current above the thermocline is opposite to the one below the thermocline will be able to cause the rotary directions of the observed tidal current above and below the thermocline to be in opposite. The interaction between the averaged barotropic and the variation tide current plays an important role in forming the vertical structure of the tidal current, and it is mainly the interaction that results in the inho-mogeneous distribution of the tide current energy in the entire water column ; the ratio between the total energies of the internal tide current above the thermocline and the variation tide current in the entire water column is greater than the ratio between the total energies of that below the thermocline and the variation's. In a strong internal tide area such as the neighbourhood of Station L4, at diurnal tide frequency, the above-mentioned corresponding ratios are about 38. 82% and 29. 88%, respectively, and the energy of the internal tide current is about 68. 70%of the energy of the variation tide current; at semidiurnal tide frequency, the above-mentioned corresponding ratios are about 26. 61 % and 19. 73% , respectively, and the total internal tide current energy is about 46. 36% of the total variation tide current energy.

An improved model for predicting effective Young's modulus of the twisted structure under cyclic loading:taking into account the untwisting effect

Twist structures have diverse applications, ranging from dragline, electrical cable, and intelligent structure. Among these applications, tension deformation can＇t be avoided during the fabrication and working processes, which often leads to the twist structure rotation （called untwisting effect） and twist pitch increasing. As a consequence, this untwisting behavior has a large effect on the effective Young＇s modulus. In this paper, we present an improved model based on the classical Costello＇s theory to predict the effective Young＇s modulus of the basic structure, twisted by three same copper strands under cyclic loading. Series of experiments were carried out to verify the present model taking into account the untwisting effect. The experimental results have better agreements with the presented model than the common Costello＇s model.

Morphology effect of zirconia support on the catalytic performance of supported Ni catalysts for dry reforming of methane

An immature pinecone shaped hierarchically structured zirconia （ZrO2-ipch） and a cobblestone-like zirconia nanoparticulate （ZrO2-cs）, both with the monoclinic phase （m-phase）, were synthesized by the facile hydrothermal method and used as the support for a Ni catalyst for the dry reforming of methane （DRM） with CO2. ZrO2-ipch is a much better support than ZrO2-cs and the traditional ZrO2 irregular particles made by a simple precipitation method （ZrO2-ip）. The supported Ni catalyst on ZrO2-ipch （Ni/ZrO2-ipch） exhibited outstanding catalytic activity and coke-resistant stability compared to the ones on ZrO2-cs （Ni/ZrO2-cs） and ZrO2-ip （Ni/ZrO2-ip）. Ni/ZrO2-ip exhibited the worst catalytic performance. The origin of the significantly enhanced catalytic performance was revealed by characterization including XRD, N2 adsorption measurement （BET）, TEM, H2-TPR, CO chemisorption, CO2-TPD, XPS and TGA. The superior catalytic activity of Ni/ZrO2-ipch to Ni/ZrO2-cs or Ni/ZrO2-ip was ascribed to a higher Ni dispersion, increased reducibility, enhanced oxygen mo- bility, and more basic sites with a higher strength, which were due to the unique hierarchically structural morphology of the ZrO2-ipch support. Ni/ZrO2-ipch exhibited better stability for the DRM reaction than Ni/ZrO2-ip, which was ascribed to its higher resistance to Ni sintering due to a strengthened metal-support interaction and the confinement effect of the mesopores and coke deposition resistance. The higher coking resistance of Ni/ZrO2-ipch for the DRM reaction in comparison with Ni/ZrOz-ip orignated from the coke-removalabitity of the higher amount of lattice oxygen and more basic sites, confirmed by XPS and CO2-TPD analysis, and the stabilized Ni on the Ni/ZrO2-ipch catalyst by the confinement effect of the mesopores of the hierarchical ZrO2-ipch sup- port. The superior catalytic performance and coking resistance of the Ni/ZrO2-ipch catalyst makes it a promising candidate for synthesis gas production from the DRM reaction.

Hydrodeoxygenation of Phenolic Model Compounds over MoS2 Catalysts with Different Structures

Several MoS2 catalysts of different structure, prepared by in situ decomposition of ammonium heptamolybdate （AHM） and molybdenum naphthenate （MoNaph）, and by MoS2 exfoliation （TDM）, were characterized by BET, X-ray diffraction （XRD）, Energy Dispersive X-ray （EDX） and transmission electron microscopy （TEM）. The analysis showed that MoS2 structure was dependant upon the preparation procedure. The activity of the catalysts was determined by measuring the hydrodeoxygenation （HDO） of phenol, 4-methylphenol and 4-methoxyphenol using a batch autoclave reactor operated at 2.8 MPa of hydrogen and temperatures ranging from 320-370℃. By comparing the conversion, the reactivity order of the catalysts was： AHM〉TDM-D〉MoNaph〉thermal〉MoS2 powder〉 TDM-W. Also, the effect of reaction temperature on the HDO conversion was explained in terms of equilibrium of reversible reaction kinetics. The main products of the HDO for phenolic compounds were identified by gas chromatography/mass spectrometry （GC/MS）. The results showed that the product distribution and the HDO selectivity were correlated with the reaction temperature. Two parallel reaction routes, direct hydrogenolysis and combined hydrogenation-hydrogenolysis, were confirmed by the analysis of the product distribution. High temperature favored hydrogenolysis over hydrogenation for HDO of phenol and 4-methoxyphenol, whereas for 4-methylphenol the reverse was true.