表面相结结构在促进光催化电荷分离中的应用（英文）

二十世纪八十年代以来,特别是近十年,光催化研究在利用可再生能源太阳能的道路上飞速发展.越来越多的研究表明,相结结构的构筑是有效提高半导体光催化剂性能的重要策略.其中,TiO2作为重要的模型光催化剂,其相关研究成果呈现出指数增长的趋势.本综述围绕TiO2模型光催化剂,主要介绍TiO2表面相结的研究成果,包括TiO2表面相的表征、锐钛矿:金红石TiO2相结用于光催化产氢研究、TiO2相结在光催化中作用的最新认识等.在表征方面,通过表面灵敏的紫外拉曼光谱研究了TiO2相变过程中表面相结构的变化,结合可见拉曼以及XRD表征揭示了TiO2独特的相变过程,即相变始于锐钛矿粒子的界面处,小粒子逐渐团聚为大粒子,致其相变从大粒子体相开始最终扩展到整个粒子.使用CO,CO2探针红外光谱,根据锐钛矿和金红石表面吸附物种的差异,进一步证实了锐钛矿:金红石表面相结结构,为紫外拉曼光谱的表面表征特性提供坚实证据.同时,利用发光光谱观察到锐钛矿晶相的可见发光带和金红石晶相的近红外发光带,并基于此给出了TiO2材料表面相结结构的荧光表征新方法.此外荧光光谱还提供了锐钛矿、金红石相中载流子动力学信息,揭示了束缚态在光催化中的作用.在光催化应用方面,观察到混相结构TiO2较单独锐钛矿及金红石相具有更高的光催化产氢活性,通过在较大金红石颗粒上担载纳米锐钛矿粒子,证明了相结结构在提高光催化活性中的核心作用,并首次提出了锐钛矿:金红石表面异相结结构概念,推断其对电荷分离的促进作用是最终提高反应活性的原因.之后将此概念应用到改善商品TiO2(P25)光催化活性中,通过可控热处理精细调控P25的表面相结构,在光催化重整生物质衍生物产氢实验中,成功将P25光催化产氢活性提高3-5倍.之后发展了新的TiO2表面控制方法,通过加入Na2SO4等相变控制剂,延缓了TiO2从锐钛矿向金红石的相变过程,在较高温度下实现TiO2相结结构的调控,最终可将P25光催化重整甲醇制氢的活性提高6倍,同时通过高分辨电镜清晰观察到锐钛矿:金红石相结的原子层生长接触.在相结作用机理方面,多种时间分辨光谱技术以及理论计算被用作探索锐钛矿:金红石相结处的电子转移机理.通过时间分辨红外光谱对TiO2表面相结结构作用的研究,特别是利用锐钛矿、金红石不同的瞬态吸收光谱特征,证明了锐钛矿:金红石相结处的载流子转移过程,存在锐钛矿向金红石的电子转移过程.模型光催化剂TiO2相结的研究成果,加深了对光催化机理的认识,促进新型高效光催化体系的设计合成.

Low temperature solid-phase sintering of sintered metal fibrous media with high specific surface area

A procedure of low temperature solid-phase sintering（LTSS） was carried out to fabricate sintered metal fibrous media（SMFM） with high specific surface area.Stainless steel fibers which were produced by cutting process were first plated with a coarse copper coating layer by electroless plating process.A low-temperature sintering process was then completed at about 800 °C for 1 h under the protection of hydrogen atmosphere.The results show that a novel SMFM with complex surface morphology and high specific surface area（0.2 m2/g） can be obtained in this way.The effect of sintering temperature on the surface morphology and specific surface area of SMFM was studied by means of scanning electron microscopy and Brunauer-Emmett-Teller.The damage of micro-structure during the sintering process mainly contributed to the loss of specific surface area of SMFM and the optimal sintering temperature was 800 °C.

Fabrication of TiO_2(B)/anatase heterophase junctions in nanowires via a surface-preferred phase transformation process for enhanced photocatalytic activity

Heterojunction fabrication is one of the most effective strategies for enhancing the photocatalytic performance of semiconductor photocatalysts. Here, TiO2（B）/anatase nanowires with interfacial heterostructures were prepared through a three-step synthesis method, including hydrothermal treatment, H＋ exchange, and annealing. The phase structures of the nanowires in the bulk and on the surface during the annealing process were monitored by XRD and UV-Raman spectroscopy, respectively. SEM and TEM results indicate that the TiO2（B） nanowires partially collapse and transform into anatase during the annealing process and the heterophase junction structure is formed simultaneously. On the basis of the phase structure together with morphology data, a phase-transformation mechanism was proposed. Photocatalytic activity was evaluated by hydrogen production and pollutant-degradation assays. The optimized structure of the photocatalyst contains 24% TiO2（B） in the bulk and 100% anatase on the surface. The charge-carrier behavior during the photocatalytic process was investigated by photocurrent, electrochemical impedance spectroscopy（EIS）, and photoluminescence（PL） spectroscopy, which revealed that the heterophase-junction structure in the bulk was responsible for the highly efficient charge separation and transportation, etc.; the anatase on the surface took control of the high surface-reaction activity.

Phase Separation and Microstructure of Mixed Surfactants Solution Containing Cationic Geminis and Traditional Anionic Surfactant

The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-1,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.

Directional migration behavior of cerium during sintering process of mischmetal doped cemented carbide

Three observation methods were used to investigate the existing form and the behavior of rare earth during the sintering process of high activity mischmetal （RE, with lanthanum and cerium） doped WC-8%Co-0.048%RE（mass fraction） alloy with low carbon-containing level by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDXS）, considering the fact that the addition amount of rare earth in the alloy is very minute. The directional migration process and mechanism of cerium were discussed. First, the sinter skin （surface） is observed. oxide on the sinter skin, and lanthanum in these cerium observed, and lanthanum containing phase/micro-zone in It is shown that there exists a dispersedly distributed cerium containing enrichment positions is very minute. Secondly, the polished section is the alloy is identified. Finally, based on the fact that the fracture of cemented carbide is resulted from the heterogeneous phase or other defects within the microstructure, the fracture surface is observed and cerium containing phase/micro-zone in the fracture source approximately 260 μm from the surface is identified. These combined observations reveal adequately the fact that lanthanum and cerium get separated and cerium predominantly migrates towards the surface during the sintering process.

The effect of heat treatment on the structure and morphology of poly （p-phenylene benzobisoxazole） fiber

The effect of heat treatment on the structure of Poly（p-phenylene benzobisoxazole） （PBO） fiber was studied by wide angle X-ray diffraction （WAXD） and differential scanning calorimetry-（DSC）, which resuits in confirmation of secondary crystallization in the heat treatment process. The effect of heat treatment on the structure and morphology of PBO fiber＇ s surface was investigated with X-ray photoelectron spectroscopic analysis （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The results show that heat treatment not only has an effect on the composition of PBO fiber＇s surface, but also improves the microstmcture of PBO fiber, makes fiber more regular.

Influence of Nitric Acid Concentration on Characteristics of Olive Stone Based Activated Carbon

In this work we investigated the effect of nitric acid concentration on the pore structure,surface chemistry and liquid phase adsorption of olive stone based activated carbon prepared by mixing process using phosphoric acid and steam as activating agents.Chemicals and textural characterization show that the increase of HNO3concentration increases considerably the total acidic groups but decreases specific surface area and pore volume.The study of adsorption in aqueous solutions of two organics,phenol and methylene blue,on raw and oxidized activated carbon indicates that the treatment of mixed activated carbon with different concentrations of nitric acid improves the adsorbent capacity for methylene blue at HNO3concentrations less or equal to 2 mol·L 1,while it has a negative effect on phenol adsorption.

Effect of nanofibers at surface of carbon fibers on microstructure of carbon/carbon composites during chemical vapor infiltration

Before densification by chemical vapor infiltration,carbon or SiC nanofibers were grown on the surface of carbon fibers by catalytic chemical vapor deposition using electroplated Ni as catalyst.The modification and mechanism of nanofibers on the pyrocarbon deposition during chemical vapor infiltration were investigated.The results show that the nanofibers improve the surface activity of the carbon fibers and become active nucleation centers during chemical vapor infiltration.They can induce the ordered deposition of pyrocarbon and adjust the interface bonding between pyrocarbon and carbon fibers during the infiltration.

Engineering the electronic and strained interface for high activity of PdMcore@Ptmonolayer electrocatalysts for oxygen reduction reaction

Alloyed nanoparticles with core-shell structures provide a favorable model to modulate interfacial interaction and surface structures at the atomic level,which is important for designing electrocatalysts with high activity and durability.Herein,core-shell structured Pd3M@Pt/C nanoparticles with binary PdM alloy cores(M=Fe,Ni,and Co)and a monolayer Pt shell were successfully synthesized with diverse interfaces.Among these,Pd3Fe@Pt/C exhibited the best oxygen reduction reaction catalytic performance,roughly 5.4 times more than that of the commercial Pt/C catalyst used as reference.The significantly enhanced activity is attributed to the combined effects of strain engineering,interfacial electron transfer,and improved Pt utilization.Density functional theory simulations and extended X-ray absorption fine structure analysis revealed that engineering the alloy core with moderate lattice mismatch and alloy composition(Pd3Fe)optimizes the surface oxygen adsorption energy,thereby rendering excellent electrocatalytic activity.Future researches may use this study as a guide on the construction of highly effective core-shell electrocatalysts for various energy conversions and other applications.

Peach skin effect:a quasi-superhydrophobic state with high adhesive force

The surface of a peach is known to exhibit spe- cial wettability and adhesion behaviors. We disclose that the peach surface is covered with long and short indumentums. The long indumentums are covered mainly with hydrophobic wax molecules, while the short indumentums are coated mostly with hydrophilic polysaccharides. Thus, the peach surface exhibits a quasi-superhydrophobic property and high adhesive force. A water droplet on the surface of a peach is a quasi-sphere, which is unable to roll off even when the peach is turned upside down. This is defined as the peach skin effect. We present that the quasi-superhydrophobic state with high adhesive force is attributed to the special coexisting Wenzel＇s and Cassie＇s state for water droplets, thus creating the strong interaction between the water droplet and surface.

THE GAUSS MAP OF TIMELIKE SURFACES IN R1^n

Gauss maps of oriented timelike 2-surfaces in are characterized, and it is shown that Gallss maps can determine surfaces locally as they do in case. Moreover, some essential differences are discovered between the properties of the Gauss maps of surfaces in Rn and those of the Gauss maps of timelike surfaces in. In particular, a counterexample shows that a nonminimal timelike surface in cannot be essentially determined by its Gauss map.