提高柴油加氢精制催化剂活性的方法

依据过渡金属硫化物催化剂的活性相理论及加氢脱硫、脱芳反应的历程,综述了各种提高柴油加氢精制催化剂性能的方法--使用高加氢能力的活性组分、引入中等强度酸中心、减弱活性组分与载体间的相互作用以及提高活性组分的分散度;介绍了相关的国内外最新研究进展,指出研究开发高比表面积、中等酸性的介孔载体和既能提高活性组分分散度又不增强活性组分与载体间相互作用的新型催化剂制备方法是提高柴油加氢精制催化剂性能的主要途径.     

利用杂原子调控纳米碳材料催化剂催化能力的初步探索

纳米碳材料已经成为一类重要的非金属催化剂。通过在纳米碳材料催化剂中引入杂原子可以有效地改变催化剂的性能。通过3个研究实例分别说明了杂原子硼和氮在甲烷部分氧化、氧化脱氢反应中乙烯选择性和乙炔卤化反应中的作用和机理。通过研究表明硼和氮杂原子可以优化纳米碳材料的催化效果,改变催化剂的电子结构和酸碱性,揭示了碳材料与金属催化剂的不同作用机理。当前计算结果可为进一步提高纳米碳材料催化剂催化能力奠定基础。     

On the preparation methods for carbon nanofiber-supported Pt catalysts

A study of the suitability of different methods for preparing highly loaded, well dispersed carbon nanofiber (CNF) supported Pt catalysts intended for application in fuel cells is reported. Preparation routes that are successfully applied on conventional carbon supports are hampered by the lower surface area and number of surface groups on CNFs. Ion exchange, homogeneous deposition precipitation and impregnation are all techniques that are limited to low metal loading on this CNF support. The most promising methods are the colloidal methods. By the modified polyol method, a Pt-content of 24 wt% with a particle size of 2–4 nm was achieved. CNFs could also be completely covered by 2–3 nm Pt oxide particles by using the metal–oxide colloid route, reaching a Pt-content of 17 wt%. The merits that make these methods more suitable than the other methods and the mechanism for deposition of Pt particles on CNFs are discussed.     

Engineering interfaces in carbon nanostructured mats for the creation of energy efficient thermal interface materials

One of the few remaining opportunities to increase heat dissipation in IC circuitry is to substantially decrease the thermal interface resistance between solid–solid contacts from source to sink. In this study, heterogeneous nanostructured mats (1–100 μm thick, randomly oriented networks of nanostructures) are synthesized for use as thermal interface materials (TIMs). Recent studies suggest that mats composed entirely of carbon nanotubes (CNTs) or graphite nanofibers (GNFs) can act as thermal insulators due to significant phonon scattering at interfaces. In this work, graphene nanoplatelets (xGnPs) with high surface areas are included in CNT and GNF mats in order to increase the contact area between nanostructures and mitigate phonon scattering. Results indicate that an increase in contact area between nanostructures increases the thermal conductance across nanostructure networks by nearly an order of magnitude. Additionally, a study of the surface topography of CNT and GNF mats using atomic force microscopy (AFM) indicates that they are able to conform well to the asperities between rough, mating surfaces. Thus, an increase in contact area between CNT junctions not only produces a thermally conductive network, but also increases the reliability of a CNT mat TIM by avoiding common issues associated with the use of wetting agents.     

Gas-phase synthesis of single-walled carbon nanotubes on catalysts producing high yield

Composite catalysts are employed for high yield gas-phase synthesis of single-walled carbon nanotubes (SWCNTs). Specifically, silicon is investigated as an additive to iron catalysts for synthesis of SWCNTs in inverse diffusion flames. While silicon is often used as a substrate in supported-catalyst processes to promote nanotube growth, this study demonstrates that it can also be beneficial for gas-phase nanotube synthesis in diffusion flames. An oxy-fuel ethylene inverse diffusion flame is employed to provide a soot-free, carbon-rich environment for nanotube growth. Iron and silicon precursors are added to the fuel stream for nucleation of iron/silicon/oxygen catalyst particles, with the amount of particle oxidation determined by the amount of oxygen-enrichment and fuel dilution at a given temperature. Under optimum conditions, nearly 90% of the catalyst particles produce single-walled carbon nanotubes as compared to less than 10% when the catalyst consists of only iron and oxygen. The effect of silicon addition is investigated through variation of the iron/silicon ratio and measurement of nanotube growth rates. Silicon is shown to primarily affect SWCNT inception with minimal influence on growth rate.     

含铈氧化物储氧材料的合成方法研究进展

含铈氧化物由于其独特的氧化还原性能及较强的储氧能力成为汽车尾气催化净化三效催化剂的关键材料。气相合成法中的气相凝结法和溅射法是制备具有低起燃温度和无团聚的纳米级非化学计量比催化材料最有效的方法;液相化学法有共沉淀法、溶胶-凝胶法、水(溶剂)热法、微乳液法、溶液燃烧法和溶液聚合配合法等,其中共沉淀法是湿化学过程通用的方法,溶胶-凝胶法能在低温条件下合成出均相多组分复合材料,水(溶剂)热晶化法是合成特定纳米晶体催化材料的最好方法;固相法中的高能球磨法可实现多组分的均匀混合,形成高浓度晶格缺陷的固溶体。综述了含铈储氧材料的气-固、液-固和固-固三大类合成技术的进展,探讨了制备方法和材料特性的关系。     

Polymeric nanostructured materials for biomedical applications

Polymeric nanostructured materials (PNMs), which are polymeric materials in nanoscale or polymer composites containing nanomaterials, have become increasingly useful for biomedical applications. In specific, advances in polymer-related nanoscience and nanotechnology have brought a revolutionary change to produce new biomaterials with tailored properties and functionalities for targeted biomedical applications. These materials, including micelles, polymersomes, nanoparticles, nanocapsules, nanogels, nanofibers, dendrimers and nanocomposites, have been widely used in drug delivery, gene therapy, bioimage, tissue engineering and regenerative medicine. This review presents a comprehensive overview on the various types of PNMs, their fabrication methods and biomedical applications, as well as the challenges in research and development of future PNMs.     

Use of a pulsating combustion apparatus to obtain a catalyst for the synthesis of nanostructured carbon materials

The preparation of highly efficient catalysts for the synthesis of nanostructured carbon-based nanostructured materials is considered. Catalysts of the NiO/MgO type with nanosized active sites can be obtained by burning the initial aqueous solution of nickel and magnesium nitrates with glycine in a pulsating combustion apparatus. Based on an analysis of features of the pulsating gas flow in elements of such apparatuses, a scheme has been developed and a setup has been created for the continuous synthesis of catalysts. Results of investigation of a carbon-based material synthesized on the proposed catalyst are presented.     

Platinum-alloy nanostructured thin film catalysts for the oxygen reduction reaction

In an effort to study advanced catalytic materials for the oxygen reduction reaction (ORR), a number of metallic alloy nanostructured thin film (NSTF) catalysts have been characterized by rotating disk electrode (RDE). Optimal loadings for the ORR and activity enhancement compared to conventional carbon supported nanoparticles (Pt/C) were established. The most efficient catalyst was found to be PtNi alloy with 55 wt% of Pt. The enhancement in specific activity is more than one order of magnitude, while the improvement factor in mass activity is 2.5 compared to Pt/C. Further lowering of the platinum to nickel ratio in NSTF catalysts did not lead to increased mass activity values.     

Design and synthesis of nanostructured catalysts

Advanced catalysts have been designed in the forms of nanocrystalline and nanoporous materials. These nanostructured catalysts are derived with superior control in crystallite size, pore structure, pore size, surface area, compositional flexibility, and component dispersion. They are tailored with excellent activity, selectivity and stability for a wide variety of catalytic reactions.     

Investigation into the effect of the intermediate carbon carrier on the catalytic activity of the HDS catalysts prepared using heteropolycompounds

The effect of the intermediate activated carbon covering the alumina carrier on catalytic activity of the supported transition metal sulfides (TMS) prepared from heteropolycompounds (HPCs) in thiophene hydrodesulfurization (HDS), benzene hydrogenation (HYD) and hydrotreating (including HDS of S-containing and HYD of polyaromatic compounds) of diesel oil fractions was investigated. Carbon content on the alumina carrier varied from 0 to 3.8 wt.%. It was found that the structure of carbon coating the alumina surface changes depending on the presence/absence of the active phase on the intermediate activated carbon. Total catalytic activity of the catalysts in HDS and HYD reactions was maximal for carbon content of 1–2 wt.% and fell down for catalysts with 3.8 wt.% of carbon. The specific catalytic activity grew proportionally to the carbon content on the catalyst. The experimental data showed that a rise of the reaction temperature leads to a decrease in the amount of adsorbed hydrogen whose deficiency limits the formation of H₂S. It was supposed that the intermediate carbon placed between the alumina carrier and the active phase accumulates hydrogen inside carbon pores. Besides, the intermediate C-carrier of the catalysts synthesized from Co(Ni) salts of heteropolycompounds promotes rising of stacking number in nanoslabs of the active CoMoS phase of the second type.     

酯交换法制备生物柴油的催化剂研究进展

在酯交换反应制备生物柴油的工艺过程中,可以选用的催化剂有酸/碱均相催化剂、生物酶催化剂和固体催化剂3大类.本文对这几类催化剂在该工艺过程中的应用情况进行介绍,并就各自的成本、活性、稳定性和可回收性等相关因素进行了对比分析,指出利用固体催化剂是该领域的发展方向,对固体催化剂的研究前景做出了展望.     

EMI shielding effectiveness of carbon based nanostructured polymeric materials: A comparative study

The microstructure, electromagnetic interference (EMI) shielding effectiveness (SE), DC electrical conductivity, AC electrical conductivity and complex permittivity of nanostructured polymeric materials filled with three different carbon nanofillers of different structures and intrinsic electrical properties were investigated. The nanofillers were multiwall carbon nanotubes (MWCNT), carbon nanofibers (CNF) and high structure carbon black (HS-CB) nanoparticles and the polymer was acrylonitrile-butadiene-styrene (ABS). In addition, the EMI SE mechanisms and the relation between the AC electrical conductivity in the X-band frequency range and the DC electrical conductivity were studied. The nanocomposites were fabricated by solution mixing and characterized by uniform dispersion of the nanofillers within the polymer matrix. It was found that, at the same nanofiller loading, the EMI SE, permittivity and electrical conductivity of the nanocomposites decreased in the following order: MWCNT > CNF > CB. MWCNT based nanocomposites exhibited the lowest electrical percolation threshold and the highest EMI SE owning to the higher aspect ratio and electrical conductivity of MWCNT compared to CNF and HS-CB. The AC conductivity in the X-band frequency range was found to be independent of frequency.     

Repeated use of molten carbonate catalysts for gasification of carbonaceous materials by carbon dioxide

Reactions of carbonaceous materials (activated carbon, graphite, and lignin) with carbon dioxide were carried out at 973 K using alkali metal carbonates (m.p. 891～1164 K) and eutectic mixtures of these compounds (m.p. 669～787 K) as catalysts. The reaction occurred when the carbonate catalysts were physically mixed with carbonaceous materials and the melting points of the catalysts were lower than the reaction temperature. However, the reaction did not proceed with physically mixed catalysts when the melting points of the catalysts were higher than the reaction temperature. Repeated use of the molten catalyst was also studied to investigate the possibility of continuous gasification of carbonaceous materials. After the activated carbon (or lignin) was consumed in a batch reactor, the same amount was added in the reactor containing the catalyst and the reaction started again. It was found that the eutectic molten catalyst could be reused without any loss of its catalytic activity by repeating this operation.     

Effect of carbon deposition on the activity of steam reforming catalysts

The activity of supported nickel used to catalyse the steam reforming of propylene has been found to be both increased and decreased by carbonisation of the catalyst. Increased activity is observed at temperatures between ca 650 and 375°C, and is suggested to result from the mechanism of carbonisation, which causes increased metal area and increased activity. At high temperatures (> ～ 650°C) and at low temperatures (< ～ 375°C), where a different mechanism of carbonisation results in encapsulation of metal, carbon formation poisons the catalyst. The kinetics of reaction have been measured over a catalyst which has attained steady-state: they indicate that the overall kinetics are influenced by carbon deposition on the catalyst.     

A review of methods for improving the interfacial adhesion between carbon fiber and polymer matrix

The interfacial properties between carbon fibers and surrounding matrix of a composite are drastically affected by interfacial structure. This structure mainly relates to the surface physico-chemistry of the fiber, which includes its surface chemical groups and microstructure, morphology, surface area, and surface free energy. These properties can be changed by various surface treatments, including various dry and wet oxidation steps, plasma treatment, electrodischarge, and fiber sizing or coating. These methods improve the interfacial properties significantly and synergistically, although each treatment has its specific application area.     

CeO2-doped nanostructured materials as a support of Pt catalysts: chemoselective hydrogenation of crotonaldehyde

An improvement of the catalytic activity and selectivity for the selective hydrogenation of the carbonyl bond in crotonaldehyde has been observed by addition of a dopant cation (Zn²⁺, Tb³⁺, Ti⁴⁺, Nb⁵⁺) to Pt/CeO₂ mesostructured catalysts. A linear correlation between the yield to crotyl alcohol and the polarizability of the doping cation is reported. The formation of new catalytic active sites at the metal-support interphase favoring the polarization of the C = O bond of crotonaldehyde has been observed by FTIR spectroscopy. A correlation between the amount of these sites and the initial selectivity to crotyl alcohol is discussed.     

The catalytic activity of Ni/W bimetallic sulfide nanostructured catalysts in the hydrodesulfurization of dibenzothiophene

Two types of catalysts containing NiW bimetallic sulfide nanostructures were prepared by a chemical method employing ammonium thiotungstate and nickel nitrate as metal-sulfide precursors followed by sulfidation in H₂S/H₂ at 400 °C. The nanostructures were grown with excess of Ni, at atomic ratio R = 0.75, 0.85 (R = Ni/Ni + W). High resolution electron microscopy (HRTEM) micrographs revealed the formation of two types of nanostructures, nickel sulfide nanoparticles and long nanorods of tungsten suboxide, both coated by WS₂ layers. The Ni/W catalyst containing mostly nanorods presented twice the catalytic activity (pseudo-zero order constant rate k = 12 × 10⁻⁷ mol/s.g) of the Ni/W catalyst containing nanoparticles (k = 6.3 × 10⁻⁷ mol/s.g) with a low selectivity for tetrahydrodibenzothiophene (THDBT) and high selectivity to cyclohexylbenzene (CHB, 50 mol%). In turn the Ni/W catalyst containing nanoparticles presented a catalytic activity comparable to a Ni/Mo catalyst without inorganic fullerene (IF) nanostructures (k = 7.2 × 10⁻⁷ mol/s.g) but with higher selectivity for hydrogenation to THDBT, (14 mol%) than the sample with nanorods.