Structural and Kinetics Understanding of Support Effects in Pd-Catalyzed Semi-Hydrogenation of Acetylene

In this study,the support effects on the Pd-catalyzed semi-hydrogenation of acetylene have been investigated from the structural and kinetic perspectives.According to the results of kinetic analysis and X-ray photoelectron spectroscopy,hydrogen temperature-programmed reduction,temperature-programmed hydride decomposition,and in situ X-ray diffraction measurements,using carbon nanotubes as support for Pd nanocatalysts with various sizes instead of a-Al_(2)O_(3) decreases the Pd^(0)3d binding energy and suppresses the formation of undesirable palladium hydride species,thus increasing the ethylene yield.Furthermore,X-ray absorption spectroscopy,high-resolution transmission electron microscopy,and C_(2)H_(4) temperature-programmed desorption studies combined with density-functional theory calculations reveal the existence of a unique Pd local environment,containing subsurface carbon atoms,that produces positive geometric effects on the acetylene conversion reaction.Therefore,tailoring the Pd local environment and electronic properties represents an effective strategy for the fabrication and design of highly active and selective Pd semi-hydrogenation catalysts.

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au/Ce1xZrxO2 catalysts (x=0-0.8) were prepared by a deposition-precipitation method using Ce1xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). These Au catalysts possessed similar sizes and crystalline phases of Ce1xZrxO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au 0 especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303 333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Ce1xZrxO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Ce1xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.

POLYMER SUPPORT EFFECTS OF METAL COMPLEXES FOR CATALYSIS

In the course of investigating the catalytic behavior of metal complexes forring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation andselective hydrogenation of olefins experimental results time and again indicate the pres-ence of effects of macromolecular supports -the utilization of macromolecular supportsincreases obviously the activity, selectivity, and stability of the catalysts and so as to in-crease the conversion of substrates, yields of reactions, properties of formed polymers andso on. Discussed these effects on the basis of the authors’ experiments.

Design of Support Effect in the Catalytic Application of Ligand-Protect Gold Clusters

Ligand-protected gold(Au_(n))clusters sometimes need the removal of organic ligands to expose more active sites and reduce steric hindrance in catalytic reactions,and large amount of organic and inorganic materials usually need to be employed as supports to anchor Aun clusters through different interaction mechanisms.Whereas,less comprehensive summaries have been provided about the crucial contribution of various supports to the catalytic performance of the supported Aun clusters.Herein,this review firstly summarizes synthesis methods(e.g.,impregnation and encapsulation processes)for the supported Aun cluster catalysts,and then mainly points out specific contributions of support effect in a great diversity of catalytic reactions,as well as deep interaction mechanisms.Besides,opportunities and challenging issues will be stated towards supported Aun clusters,in terms of improving catalytic performance and structural stability of Aun clusters inthedemand of catalysis.

Aqueous-phase reforming of hydroxyacetone solution to bio-based H_(2)over supported Pt catalysts

Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.

Gold/Mg-Al mixed oxides catalysts for oxidative esterification of methacrolein:Effects of support size and composition on gold loading

Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.

Data Do Not Support Effectiveness of Acupuncture for Improving Live Birth Rate in Women with Polycystic Ovary Syndrome

Recently,the arguments raised by Gang and Jing have been published in Chinese Journal of Integrative Medicine,(1)concerning the randomized controlled trial(RCT)of our team published in JAMA.(2)The conclusions of Gang and Jing(1)result not only from misunderstanding of the aims of our study,(2)but also a lack of basic knowledge for the design of RCT and the limitations on the content,and hence the length,of the primary outcome article in high-impact journals(i.e.2。

Numerical simulation of the effect of coupling support of bolt-mesh-anchor in deep tunnel

The mechanical effects of bolt-mesh-anchor coupling support in deep tunnels were studied by using a numerical method, based on deep tunnel coupling supporting techniques and non-linear deformation mechanical theory of rock mass at great depths.It is shown that the potential of a rigid bolt support can be efficiently activated through the coupling effect between a bolt-net support and the surrounding rock.It is found that the accumulated plastic energy in the surrounding rock can be sufficiently transformed by the coupling effect of a bolt-mesh-tray support.The strength of the surrounding rock mass can be mobilized to control the deforma-tion of the surrounding rock by a pre-stress and time-space effect of the anchor support.The high stress transformation effect can be realized by the mechanical coupling effect of the bolt-mesh-anchor support, whereby the force of the support and deformation of the surrounding rock tends to become uniform, leading to a sustained stability of the tunnel.

Effects of carrier and Mn loading on supported manganese oxide catalysts for catalytic combustion of methane

支持的锰氧化物催化剂被早期的湿受精方法为甲烷作好准备支持的催化燃烧，和效果(艾尔 2 装载的 O 3, SiO 2 和 TiO 2) 和 Mn 被调查。这些催化剂与 N 2 吸附， X 光检查衍射， X 光检查光电子光谱学和规划温度的减小技术被描绘。甲烷变换在取决于支持或 Mn 装载的一个大范围变化了。艾尔 2 O 3 支持了更好展出的 15% Mn 催化剂向甲烷的活动催化氧化。锰状态和氧种类在催化表演起了一个重要作用。

Size and support effects for CO oxidation on supported Pd catalysts

Supporting Pd catalysts characterized significant different size distribution were obtained using PdCl2,[Pd(NH3)4](NO3)2 and Pd(acac)2 as precursors.High-resolution transmission electron microscopy(TEM),X-ray diffraction(XRD),in-situ Fourier transform infrared spectroscopy(FTIR) and Raman spectroscopy were used to examine the dispersion of Pd.Catalytic performance measurements show that the activities for CO oxidation increase as the Pd particle size decreases and the O2/CO ratio increases.The activities under oxygen rich conditions are significantly higher than those at near the stoichiometric conditions.Pd on TiO2 prepared by the Pd(acac)2 precursor is highly dispersed,leading to a considerable activity for CO oxidation at near room temperature.CO oxidation on the 1 wt% Pd/TiO2 and under an O2/CO ratio of 1 characterized an apparent activation energy of 36.7 kJ/mol,which is closed to those reported for CO oxidation on the supported Au catalysts.The present work demonstrates a high catalytic activity of highly dispersed noble metals,and suggests a promising approach of using noble metals as catalysts with exceeding high efficiency.

Study on Distance Learning Support Services Strategy Based on Effective Interaction

Achieving effective interaction can the students get good learning results,and enhance the quality of distance learning.The paper firstly analyzes the research on distance learning support services and the problems of distance learning interaction in order to clarify the significance of implementing effective interaction.Then it puts forward the learning support services strategies based on effective interaction,which means to promote distance learning interaction and enhance the students'self-learning ability.

Effect of Mixed Oxide Support for Ni/ZnO in Reactive Adsorption Desulfurization

The effect of mixed oxide support on the performance of Ni/ZnO in the reactive adsorption desulfurization(RADS) reaction was investigated in a fixed bed reactor by using thiophene as the sulfur-containing compound in the model gasoline. A series of oxide supports for Ni/ZnO were synthesized by the co-precipitation method and characterized by XRD, N_2-adsorption, TPR and NH_3-TPD techniques. It was found that the desulfurization capacity of Ni/ZnO was enhanced greatly when active components were supported on the proper mixed oxide. Ni/ZnO supported on oxides exhibited much higher desulfurization efficiency and sulfur adsorption capacity than the unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibited the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO_2-Al_2O_3 with small particle size, high specific surface area and large pore volume could promote the high dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al_2O_3 species could weaken the interaction of active phases and SiO_2 as well as could increase greatly the amount of weak acids. Therefore, these oxides could impose a great influence on the structure and chemical properties of the catalyst.

Electronic Effect of Carbon Support on Pt Catalyst Supported on Graphite Intercalation Compound

Graphite intercalation compounds(GIC) were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.

Study on the Strategies of Distance Learning Support Services Based on Effective Interaction

The paper firstly analyzes the problems of distance learning interaction in order to clarify the significance of implementing effective interaction.Then it puts forward the learning support services strategies based on effective interaction,which means to design strategies from the perspective of effective interaction to improve the effect of distance learning.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅱ. Effect of the Ionic Size of Supporting Electrolytes

The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was

含氟材料助燃硼粉研究进展

系统综述了含氟材料助燃硼粉的研究进展,并分析了助燃机制。研究表明,不论无机含氟材料、有机含氟材料还是自组装含氟材料,对硼粉燃烧都有一定的助燃效果。但是,不同含氟材料对硼粉的助燃效果有很大差异,新兴的自组装含氟材料结构规整,可能极具应用价值,值得深入研究。分析表明,含氟材料的助燃机制为氟自由基或含氟基团的自由基的催化作用,该发现对材料的应用场景具有重要参考意义。综合大量文献研究,作者首次提出,氢含量低、易于热解且热解时易产生氟原子及含氟烷烃、含氟烯烃的自由基的材料,对硼粉会具有更好的助燃效果。研究结果预计对火炸药行业从业者会有重要的参考价值。

政府扶持能改善企业投资效率吗?——基于政府采购的经验证据

政府采购作为政府在需求端的市场化扶持手段引起了学界广泛关注。本文以2015—2020年沪深A股上市公司为研究对象,实证检验了政府采购对企业投资效率的影响。研究发现,政府采购能够提高企业投资效率,且能够同时抑制企业过度投资和投资不足;区分订单特征发现,仅异地政府采购能提高企业投资效率。机制检验表明,政府采购能够通过降低企业经营不确定性和信息不对称程度提高企业投资效率,且上述作用在产品市场竞争更为激烈的企业、处于政府审计监督力度较强地区的企业、非国有企业以及处于法治环境较差地区的企业中更加显著。本文的研究结论不仅为如何通过政府扶持提高企业投资效率提供了经验证据,也对如何积极开展政企互动和促进经济高质量发展具有重要启示。

Multiple mediation effects of health locusof control and hope on the relationshipbetween stroke patients’ social supportand self-management

Objective:This study aimed to identify the mediation effects of health locus of control(HLC)and hope between stroke patients’social support and self-management.Methods:A cross-sectional study was conducted.A total of 300 Chinese stroke patients were recruited by convenient sampling from the acupuncture department of two Chinese Traditional Medical Hospitals in Tianjin Province from June to September 2018.The self-report questionnaires include Social Support Assessment Scale,Herth Hope Index,Mental Health Locus of Control Scale,Stroke Self-management Behavior Scale,and personal information questionnaires.All the survey data were entered in Excel and analyzed using the SPSS 24.0 program.Mediation was tested with Bootstrapping in AMOS 23.0 program.Results:The result showed that internal health locus of control(IHLC),chance health locus of control(CHLC)and hope were the mediators between social support and self-management.The direct,indirect,and total effects of social support on self-management behavior were 0.306 (P<0.01),0.109(P<0.01),and 0.415(P<0.01),respectively.Conclusions:Social support can directly influence self-management,and it can also indirectly influence self-management through IHLC,CHLC,and hope.

煤巷支护效果智能预测系统及应用

针对深埋复杂地质条件下煤巷支护设计难题,基于巷道支护、计算机开发、数值模拟二次开发等开展了交叉融合技术的研究。通过文献收集、问卷调查及现场调研的方法,建立了煤巷支护知识库,通过库内数据查找和规则推理机制为用户提供岩石力学参数和支护方案参数;构建能满足多种地质条件、多种巷道类型、多种支护方案的数值模拟脚本,基于FLAC^(3D)内置语言开展二次开发技术的研究,建立了煤巷支护效果预测模型;运用计算机高级编程语言开发煤巷支护效果预测系统,实现了煤巷支护效果预测的可视化、智能化;利用该系统对经典案例进行测试,并用决定系数R2和平均绝对百分比误差MAPE对该系统预测效果进行了评价,结果显示其各指标的R^(2)均在0.8以上,MAPE值均在20%以下,都在合理范围之内该系统在巷道位移预测方面效果良好;系统在信湖煤矿818外风巷的工程实例的验证结果显示,其预测精度达到84%以上,能够为现场施工提供准确指导。