Design strategies and structure‐performance relationships of heterogeneous catalysts for selective hydrogenation of 1,3‐butadiene

Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.

Impacts of Changes in Structure of Rural Land Property Rights on Agricultural Performance

In the reform process of the rural land property rights system,the incentive mechanism of the rural land property rights system has a crucial impact on the production activities of rural economic entities.Due to the different rights structures of the property rights system in different social and economic development stages,the land rights and interests enjoyed by rural economic subjects are different,and the degree of incentives for farmers is also different.This difference in incentives affects farmers investment in agricultural production factors,which in turn affects agricultural performance.This paper analyzes the incentive impacts of the structure of rural land property rights on the changes of farmers land rights and agricultural performance since the founding of the People s Republic of China,in order to further deepen the reform of the land system,protect the rights and interests of farmers,promote the modernization of agriculture and rural areas,and explore the realization form and operation mechanism of the rural collective land system in the new era.

A Quantitative Structure Property Relationship for Prediction of Flash Point of Alkanes Using Molecular Connectivity Indices

Many structure-property/activity studies use graph theoretical indices, which are based on the topological properties of a molecule viewed as a graph. Since topological indices can be derived directly from the molecular structure without any experimental effort, they provide a simple and straightforward method for property prediction. In this work the flash point of alkanes was modeled by a set of molecular connectivity indices （Х）, modified molecular connectivity indices （ ^mХ^v ） and valance molecular connectivity indices （ ^mХ^v ）, with ^mХ^v calculated using the hydrogen perturbation. A stepwise Multiple Linear Regression （MLR） method was used to select the best indices. The predicted flash points are in good agreement with the experimental data, with the average absolute deviation 4.3 K.

Quantitative Structure-Property Relationship on Prediction of Surface Tension of Nonionic Surfactants

A quantitative structure-property relationship (QSPR) study has been made for the prediction of the surface tension of nonionic surfactants in aqueous solution. The regressed model includes a topological descriptor, the Kier & Hall index of zero order (KH0) of the hydrophobic segment of surfactant and a quantum chemical one, the heat of formation (fHD) of surfactant molecules. The established general QSPR between the surface tension and the descriptors produces a correlation coefficient of multiple determination, 2r=0.9877, for 30 studied nonionic surfactants.

STUDY ON THE STRUCTURE AND PROPERTIES OF HIGH CHROMIUM WHITE CAST IRON AND ITS TEMPERING STANDARD

The structure and properties of high chromium white cast iron in different treatment states were studied. Using X ray diffraction method, observing their metallograph and measuring their microhardness, the phases involved in the iron were determined. The notch toughness, macrohardness and the fractograph of the samples are compared and their performance was determined, which mainly depends on the matrix structure. Relatively good comprehensive properties can be obtained in the tempering state. Improvements have been made on the commonly used tempering standard. Tempering for a short period at low temperature can improve the materials′ service performance obviously.

Fragility Curves of Existing RC Buildings Based on Specific Structural Performance Levels

In seismic risk mitigation policies, fragility functions of existing buildings play a fundamental role. In this paper, a procedure to develop analytical fragility curves for Moment Resisting Frame Reinforced Concrete buildings is presented. The design of the selected building typologies was performed according to the codes at the time of construction using force-based methods and the state of the practice at the time of construction. A total of 216 building classes were defined, considering different ages, number of storeys, infill panels, plan dimensions, beam stiffness, and concrete strength. The investigated buildings can be considered low-engineered buildings, using no seismic codes or old seismic codes. The seismic capacity of the selected models representing the existing RC buildings has been evaluated through non-linear dynamic simulations. Seismic response has been analyzed, considering various peak and integral intensity measures and various response parameters, such as ductility demands and Interstorey Drift Ratio (IDR). A new relationship among structural performance, damage levels and interstorey drift ratios for each studied type is introduced, which is calibrated using the damage levels described in EMS98. It is important to highlight that in this study, different thresholds of IDR have been associated with different typologies, considering their different ductility member levels after their different structural responses. Fragility Curves (FCs) for the studied structural types are set up, developed and discussed.

Structures and Properties of Hygroscopic Thermal Fiber—EKS

EKS fiber,as a new type of hygroscopic thermal fiber,whose properties meet the requirement of warm clothing with environmental,healthy,and fashionable traits,attains more and more attention. The chemical composition and morphological structure of EKS fiber were confirmed by infrared spectrum,pyrolysis gas chromatography-mass spectrometry( Py-GC-MS),and microscope respectively. In addition, burning performance,dissolving property,and tensile properties were tested respectively.It fills in the gaps in characterization of EKS structure and properties.

Structure-activity correlationship and folding of recombinant Escherichia coli dihydro folate reductase (DHFR) enzyme through biochemical and biophysical approaches

The design of any antagonist or inhibitor for any enzyme requires the knowledge of structure- function relationship of the protein and the optimum conformational states for maximum and minimum activities. Furthermore, designing of the inhibitors or drugs against an enzyme becomes easier if there is information available about various well characterized intermediate conformation of the molecule. In vivo folding pathway of any recombinant protein is an important parameter for understanding its ability to fold by itself inside the cell, which always dictates the downstream processing for the purification. In the present manuscript we have discussed about the in vivo and in vitro folding, and structure-function relationship of Dihydrofolate reductase enzyme. This is an important enzyme involved in the cell growth and hence inhibition or inactivation of the enzyme may reduce the cell growth. It was observed that the equilibrium unfolding transition of DHFR proceeds through the formation of intermediates having higher exposed surface hydrophobicity, unchanged enzymatic activity and minimum changes in the secondary structural elements. Because of enhanced surface hydrophobicity, and unchanged enzymatic activity, these intermediates could be a nice target for designing drugs against DHFR.

Clathrate structure of YB_(3)C_(3) for high-performance thermoelectrics with superior mechanical properties

Exploring high-performance thermoelectric materials with improved mechanical properties is important for broadening the application scope and the assembly requirement of stable devices.This work presents an effective strategy to discover hard thermoelectric material by inserting foreign atoms in the rigid covalent framework.We demonstrate this in boron-carbon clathrate VII structure,showing a promising candidate for highly efficient thermoelectric energy conversion,especially with Y atom filled in the cage,with a peak zT of 0.73 at 1,000 K.The ab initio calculations indicate that YB_(3)C_(3) system has low lattice thermal conductivity of 4.5 W/(m·K)at 1,000 K due to the strong rattling of encaged Y atom.The strongly covalent framework provides highly degenerate band structures consisting of heavy and light electron pockets,which can maintain high carrier mobility arising from small effective mass and thus large group velocity.Consequently,high power factor can be achieved in YB_(3)C_(3) for both electron and hole doping.In addition,it exhibits well mechanical properties and a Vickers hardness of 23.7 GPa because of the strong covalent boron-carbon framework.This work provides a novel avenue for the search of high-performance thermoelectric materials with excellent mechanical properties,based on boron-carbon clathrate structure.

The electrochemical characteristics of AB_(4)-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery

Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.

Influence of Network Embedding on the Transformation Performance of Original Equipment Manufactures

Based on the embeddedness theory,this paper analyzes the impact of network embedding features and types on the transformation performance of foundry enterprises.Through the investigation and analysis of more than 200 foundry enterprises in Zhejiang Province,it is found that network relationship embedding and structure embedding have positive impacts on transformation of foundry enterprises.Professional embedding and technical embedding have a positive effect in the transformation of foundry enterprises,and knowledge absorption ability has a positive adjustment role in the transformation performance of network embedding foundry enterprises.

Quantitative Models for the Structure and Photodegradation of Polycyclic Aromatic Hydrocarbons

Based on the quantum chemical descriptors,quantitative structure-property relationship（QSPR） models have been developed to estimate and predict the photodegradation rate constant（logK） of polycyclic aromatic hydrocarbons（PAHs） by use of linear method（multiple linear regression,MLR） and non-linear method（back propagation artificial neural network,BP-ANN）.A BP-ANN with 3-3-1 architecture was generated by using three quantum chemical descriptors appearing in the MLR model.The standard heat of formation（HOF）,the gap of frontier molecular orbital energies（ΔELH） and total energy（TE） were inputs and its output was logK.Leave-One-Out（LOO） Cross-Validated correlation coefficient（R^2CV） of the established MLR and BP-ANN models were 0.6383 and 0.7843,respectively.The nonlinear BP-ANN model has better predictive ability compared to the linear MLR model with the root mean square error（RMSE） for training and validation sets to be 0.1071,0.1514 and the squared correlation coefficient（R^2） of 0.9791,0.9897,respectively.In addition,some insights into the molecular structural features affecting the photodegradation of PAHs were also discussed.

Effect of PdOx structure properties on catalytic performance of Pd/Ce0.67Zr0.33O2 catalyst for CO,HC and NOx elimination

Pd/Ce0.67Zr0.33O2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdOx species on the catalytic performance for CO, HC and NOx elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdOx and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NOx elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.

Effect of Sodium on the Structure-Performance Relationship of Co/SiO2 for Fischer-Tropsch Synthesis

A series of Co/SiO2 catalysts with different sodium （Na）loadings （0, 0.1, 0.2, 0.5 and I wt%） were prepared and evaluated for Fischer-Tropsch reaction to study the effect of Na on the catalyst structure and catalytic performance. The addition of Na was found to decrease the catalytic activity and hydrocarbon selectivity, but increase CO2 selec- tivity due to the enhanced WGS activity. The addition of Na also resulted in higher selectivity to oxygenates （alco- hols and aldehydes） and O/P ratio as well as the shift of hydrocarbons to lower carbon numbers. Structure charac- terization revealed a decrease in the surface area and particles size for the calcined samples with the addition of Na. CozC was formed during the reaction process for the Na-promoted catalysts. As a result, a new Co/Co2C bifunc- tional active sites were generated for oxygenates formation leading to increasing oxygenates selectivity. In addition, the Co2C nanoparticles alone may also act as dual active sites for oxygenate formation at high reaction pressure over the promoted catalysts with high Na loading.

Investigation of retention and chiral recognition mechanism using quantitative structure-enantioselectivity retention relationship in high performance liquid chromatography

The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkle-type chiral stationary phase. Seven molecular descriptors were calculated and four significant descriptors were chosen to correlate against the experimental lnk' values in order to form the quantitative structure-enantioselectivity retention relationships (QSERRs). Through the QSERRs, the retention and enantioselectivity mechanism were examined.

Hall-Petch relationship in selective laser melting additively manufactured metals:using grain or cell size?

The mechanical properties of many materials prepared by additive manufacturing technology have been greatly improved.High strength is attributed to grain refinement,formation of high density dislocation and existence of cellular structures with nanoscale during manufacturing.In addition,the super-saturated solid solution of elements in the matrix and the solid solution segregation along the wall of the cellular structures also promote the improvement of strength by enhancing dislocation pinning.Hence,the existence of cellular structure in grains leads to differences in the prediction of material strength by Hall-Petch relationship,and there is no unified calculation method to determine the d value as grain size or cell size.In this work,representative materials including austenite 316L SS were printed by selective laser melting(SLM),and the strength was predicted.The values of cell size and grain size were substituted into Hall-Petch formula,and the results showed that the calculation error for 316L is increased from 4.1%to 11.9%.Therefore,it is concluded that the strength predicted by grain size is more accurate than that predicted by cell size in additive manufacturing materials.When calculating the yield strength of laser additive manufacturing metal materials through the Hall-Petch formula,the grain size should be used as the basis for calculation.

Structural Characterization and Octanol/water Partition Coefficients(LogP) Prediction for Oxygen-containing Organic Compounds

New descriptors were constructed and structures of some oxygen-containing organic compounds were parameterized. The multiple linear regression（MLR） and partial least squares regression（PLS） methods were employed to build two relationship models between the structures and octanol/water partition coefficients（LogP） of the compounds. The modeling correlation coefficients（R） were 0.976 and 0.922, and the ＂leave one out＂ cross validation correlation coefficients（R（CV）） were 0.973 and 0.909, respectively. The results showed that the structural descriptors could well characterize the molecular structures of the compounds; the stability and predictive power of the models were good.

Quantitative Correlation of Chromatographic Retention and Acute Toxicity for Alkyl(1-phenylsulfonyl) Cycloalkane Carboxylates and Their Structural Parameters by DFT

Twenty eight alkyl(1-phenylsulfonyl) cycloalkane carboxylates were computed at the B3LYP/6-31G* level. Based on linear solvation energy theory, two quantitative correlation equations of the molecular structures of alkyl(1-phenylsulfonyl) cycloalkane carboxylate com- pounds to their chromatographic retention (capacity factor lgKW) and the toxicity for photo- bacterium phosphoreum (–lgEC50) were developed by using the molecular structural parameters as theoretical descriptors (r2 = 0.9501, 0.9488). The two quantitative correlation equations were consequently cross validated by leave-one-out (LOO) validation method with q2 of 0.9113 and 0.9281, respectively. The result showed that the two equations achieved in this work by B3LYP/6-31G* are both more advantageous than those from AM1, and can be used to predict the lgKW and –lgEC50 of congeneric organics.

QSAR of Estrogen of Bisphenol A with 3D Vector of Atomic Property Correlation

Considering atomic property vector and atomic correlative function, the 3-dimensional structural vector of atomic property correlation （3D-VAPC）, a novel descriptor,is defined to characterize a 3-dimensional molecular structure by introducing self-adaptability regulation mechanism and the idea of orientating to customers. Characterizing the structures of 25 bisphenol A compounds by this vector, the QSAR models of three kinds of estrogen activities （ER affinities, gene induction and cell proliferation） have high multiple correlation coefficient （Rcum^2=0.933, 0.813, 0.959） and cross verification coefficient （Qcum^2=0.847, 0.953, 0.798） by support vector machine （SVM）, which suits for nonlinear circumstances. The above results show that the models successfully express the correlation between structure and three kinds of estrogen activities. Therefore, 3D-VAPC exactly reflects the molecular structural information and SVM method correctly describes the correlation between information and property of the compounds.