Development of various PS-b-P4VP micellar morphologies: fabrication of inorganic nanostructures from micellar templates

A liquid-phase method for preparing uniform-sized silica nanospheres (SNSs) 12 nm in size and their three-dimensionally ordered arrangement upon solvent evaporation have recently been pioneered by us. Here we report the successful control of the sphere sizes in the wide range from 14 to 550 nm by the seed regrowth method. In this method, the dispersion of SNSs 14 nm in size as seeds was prepared in the emulsion system containing Si(OEt)(4) (TEOS), water and arginine under weakly basic conditions (pH 9-10). An appropriate portion of this dispersion is added to the solution containing water, ethanol and arginine, and then TEOS is added. The additional TEOS introduced into the regrowth system contributed only to the resumed growth of the seeds, not to the formation of new silica particles. The size of interparticle pores was finely tuned by changing the size of the spheres. The preparation of three-dimensionally ordered porous carbons by using the colloidal array of silica nanospheres as a template is also reported.     

Mesoporous Pt-SiO2 and Pt-SiO2-Ta2O5 catalysts prepared using Pt colloids as templates.

Sol‐gel synthesis of silica and silica–tantalum oxide embedded platinum nanoparticles is carried out using Pt colloids as templates. These colloids are prepared by reduction with Na[AlEt₃H] and stabilized with different ligands (ammonium halide derivatives, non‐ionic surfactants with polyether chains, and 2‐hydroxy‐propionic acid). The aim of the present study is to prepare mesoporous silica embedded Pt colloids combining the “precursor concept” with the model of catalyst preparation using preformed spheres. Nanoparticles of Pt incorporated in high surface area mesoporous materials are formed after calcination. Further, it is observed that calcination of these catalysts causes partial aggregation and oxidation of the parent colloids, a process that is largely dependent on the nature of the stabilizing ligands. Several methods have been used for characterization of these materials: adsorption‐desorption isotherms at 77 K, H₂ chemisorption, X‐ray diffraction(XRD), ²⁹Si and ¹³C magic angle spinning (MAS) NMR, ammonia diffuse reflectance Fourier transform infrared spectroscopy (NH₃‐DRIFT), transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). It is found that both metal oxide systems exhibit Brønsted acidity (weaker for silica and quite strong for silica–tantalum oxide). In addition, NH₃‐DRIFT experiments demonstrate the oxidative properties of the surface. Part of the adsorbed NH₄⁺ species is oxidized to N₂O. Testing these catalysts in the reduction of NO and NO₂ with isopentane under lean conditions indicate that the activity of these catalysts is indeed dependent on the size of the platinum particles, with those of size 8–10 nm demonstrating the best results. The support likely contributes to this effect, particularly after Ta incorporation into silica.     

Uniformly sized gold nanoparticles derived from PS-b-P2VP block copolymer templates for the controllable synthesis of Si nanowires

A monolayer of gold-containing surface micelles has been produced by spin-coating solution micelles formed by the self-assembly of the gold-modified polystyrene-b-poly(2-vinylpyridine) block copolymer in toluene. After oxygen plasma removed the block copolymer template, highly ordered and uniformly sized nanoparticles have been generated. Unlike other published methods that require reduction treatments to form gold nanoparticles in the zero-valent state, these as-synthesized nanoparticles are in form of metallic gold. These gold nanoparticles have been demonstrated to be an excellent catalyst system for growing small-diameter silicon nanowires. The uniformly sized gold nanoparticles have promoted the controllable synthesis of silicon nanowires with a narrow diameter distribution. Because of the ability to form a monolayer of surface micelles with a high degree of order, evenly distributed gold nanoparticles have been produced on a surface. As a result, uniformly distributed, high-density silicon nanowires have been generated. The process described herein is fully compatible with existing semiconductor processing techniques and can be readily integrated into device fabrication.     

Low-temperature oxidation of carbon monoxide on Pd(Pt)/CeO2 catalysts prepared from complex salts

Catalysts containing cerium oxide as a support and platinum and palladium as active components for the low-temperature oxidation of carbon monoxide were studied. The catalysts were synthesized in accordance with original procedures with the use of palladium and platinum complex salts. Regardless of preparation procedure, the samples prepared with the use of only platinum precursors did not exhibit activity at a low temperature because only metal and oxide (PtO, PtO₂) nanoparticles were formed on the surface of CeO₂. Unlike platinum, palladium can be dispersed on the surface of CeO₂ to a maximum extent up to an almost an ionic (atomic) state, and it forms mixed surface phases with cerium oxide. In a mixed palladium-platinum catalyst, the ability of platinum to undergo dispersion under the action of palladium also increased; as a result, a combined surface phase with the formula Pd _x Pt _y CeO_{2 ? δ}, which exhibits catalytic activity at low temperatures, was formed.     

PS-b-P4VP/CoSm杂化材料的制备及其磁性能

用溶液相金属盐沉积法在苯乙烯与4-乙烯基吡啶嵌段共聚物(PS-b-P4VP) 胶束中制备了平均直径为12 nm的PS-6-P4VP/Co、PS-b-P4VP/CoSm(nCo:nSm=3.8:1,13.0:1)、PS-b-P4VP/Sm纳米粒子.胶束溶液通过高温回流使磁性成核粒子和磁性金属原子的流动能力和扩散能力提高而获得尺寸均一的颗粒.傅里叶红外分析表明.当只有CoCl2加入时,Co2将与多个4-乙烯基吡啶基团配位,而CoCl2和SmCl3同时加入时,由于Sm-4VP配体的屏蔽使Co2 与4-乙烯基吡啶基团的配位数减少.振动样品磁强计对上述样品磁性能的分析表明:随着Sm含量的增加,样品的饱和磁化强度和剩余磁化强度减少,而矫顽力增加.     

Formation of Pt/C catalysts on various carbon supports

Platinum catalysts with the active component content of 5–40 wt % on various carbon supports have been synthesized by the reductive hydrolysis of platinum chloro complexes. The degree of dispersion of the supported platinum decreases with an increasing weight percentage of the metal in the catalyst. The following mechanism of Pt/C catalyst formation is deduced from experimental data: H₂PtCl₆ adsorption on the support surface generates platinum nuclei, which then grow owing to the deposition of platinum ions under the action of an alkali and a reductant.     

Electrocatalytic O2 reduction at glassy carbon electrodes modified with dendrimer-encapsulated Pt nanoparticles

Platinum dendrimer-encapsulated nanoparticles (DENs) were prepared within fourth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers and immobilized on glassy carbon electrodes using an electrochemical coupling strategy. X-ray photoelectron spectroscopy, electron microscopy, and electrochemical experiments confirmed that the Pt DENs were about 1.4 nm in diameter and that they remained within the dendrimer following surface immobilization. The resulting Pt DEN films were electrocatalytically active for the oxygen reduction reaction. The films were also robust, surviving up to 50 consecutive cyclic voltammograms and sonication.     

Transport effects in the oxygen reduction reaction on nanostructured, planar glassy carbon supported Pt/GC model electrodes

The role of transport and re-adsorption processes on the oxygen reduction reaction (ORR), and in particular on its selectivity was studied using nanostructured model electrodes consisting of arrays of Pt nanostructures of well-defined size and separation on a planar glassy carbon (GC) substrate. The electrochemical measurements were performed under controlled transport conditions in a double-disk electrode thin-layer flow-cell configuration; the model electrodes were fabricated by colloidal lithography techniques, yielding Pt nanostructures of well defined and controlled size and density (diameter: 140 or 85 nm, height: 20 or 10 nm, separation: from 1-2 to more than 10 diameters). The nanostructured model electrodes were characterized by scanning electron microscopy and electrochemical probing of the active surface area (via the hydrogen adsorption charge). The electrocatalytic measurements revealed a pronounced variation of the hydrogen peroxide yield, which increases by up to two orders of magnitude with increasing separation and decreasing size of the Pt nanostructures. Similar, though less pronounced effects were observed upon varying the electrolyte flow and thus the mass transport characteristics. These effects are discussed in a reaction model which includes (i) direct reduction to H(2)O on the Pt surface and (ii) additional H(2)O(2) formation and desorption on both Pt and carbon surfaces and subsequent partial re-adsorption and further reduction of the H(2)O(2) molecules on the Pt surface.     

芦丁在铂纳米/碳纳米管修饰电极上电化学行为研究

通过电沉积的方式在多壁碳纳米管(MWCNTs)修饰玻碳电极表面上沉积铂(pt)纳米粒子,并运用循环伏安法(CV)、示差脉冲伏安法(DPV)探讨了芦丁在铂纳米/碳纳米管/玻碳电极上的电化学行为.实验结果表明,芦丁在该修饰电极上呈现一对良好氧化还原峰,其氧化峰电流与浓度在3.2×10(-8)～1.2×10(-5)mol/L...     

Temperature dependence of oxygen reduction activity at Nafion-coated bulk Pt and Pt/carbon black catalysts

Oxygen reduction reaction (ORR) activity and H(2)O(2) formation at Nafion-coated film electrodes of bulk-Pt and Pt nanoparticles dispersed on carbon black (Pt/CB) were investigated in 0.1 M HClO(4) solution at 30 to 110 degrees C by using a channel flow double electrode method. We have found that the apparent rate constants k(app) (per real Pt active surface area) for the ORR at bulk-Pt (with and without Nafion-coating) and Nafion-coated Pt/CB (19.3 and 46.7 wt % Pt, d(Pt) = 2.6 to 2.7 nm) thin-film electrodes were in beautiful agreement with each other in the operation conditions of polymer electrolyte fuel cells (PEFCs), i.e., 30-110 degrees C and ca. 0.7 to 0.8 V vs RHE. The H(2)O(2) yield was 0.6-1.0% at 0.7-0.8 V on all Nafion-coated Pt/CB and bulk-Pt and irrespective of Pt-loading level and temperature. Nafion coating was pointed out to be a major factor for the H(2)O(2) formation on Pt catalysts modifying the surface property, because H(2)O(2) production was not detected at the bulk-Pt electrode without Nafion coating.     

聚苯乙烯-聚4-乙烯基吡啶两亲嵌段共聚物在CO2膨胀液体中的组装行为

嵌段共聚物的自组装行为和其组装形成的胶束聚集体的形貌因在生物医学、药物传输和催化等方面的潜在应用而引起了科学家们的极大兴趣。本工作报道了利用二氧化碳膨胀液体(CXLs)对嵌段共聚物聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)的自组装聚集体(SAA)进行组装结构调控的初步探索。研究发现利用CXLs的抗溶剂效应可以成功调节共聚物PS-b-P4VP的自组装行为。研究结果表明,CXLs的压力及共聚物的组成是影响SAA结构的主要外部因素,CXLs的抗溶剂效应及其对共聚物溶剂化构型的影响是控制SAA形貌转变的主要内在因素。不同组成的共聚物,在CXLs中其SAA的结构形貌均表现出了对压力的显著响应特性。共聚物PS₁₆₈-b-P4VP₄₂₀的自组装聚集体的结构由常压(0.1 MPa)下以球形胶束为主转变为高压下(6.35 MPa)以互联棒状胶束结构为主,而PS₇₉₀-b-P4VP₂₆₃的SAA结构则由常压下的小型囊泡过渡到6.35 MPa下的大复合囊泡(LCVs)。但是对于PS₁₅₃-b-P4VP₁₅₃₀,随着压力的调节,其SAA的结构由常压(0.1 MPa)下的大复合胶束(LCMs)转变为6.35 MPa下的大复合囊泡(LCVs)。特别是,我们发现在本工作考察的实验条件下,在常规溶剂甲苯中控制SAA结构的主要因素是共聚物的组成;而在CXLs条件下,PS壳链与溶剂CXLs间的接触面积随压力调节而发生的改变,可能是控制SAA形貌转变的主要因素。此外,随着CXLs压力升高而引起的PS与P4VP嵌段间双亲性差别的减小,会引起P4VP核-PS壳的界面间的表面张力发生改变,这也是触发SAA形貌转变的诱因之一。本工作充分显示了CXLs方法有助于可控调节自组装聚集体(SAA)的形貌和组装行为,为研发复合纳米材料开辟了一条崭新的绿色途径。     

Pb-Pt/AC催化甘油一步法制备丙酮酸

生物质能具有绿色环保、可再生、来源广泛和安全性高等优点,成为当前的研究热点.作为生物柴油的主要副产物,甘油是一种重要的生物质平台化合物.甘油的高效利用,不仅能够获得重要的精细化学品及聚合物,也可以延长生物柴油的产业链,降低其生产成本,增加其市场竞争力.丙酮酸是一种弱有机酸,为生物体内葡萄糖分解代谢的中间产物,在生物能量代谢和物质代谢过程中起着重要的枢纽作用.同时,由于它同时含有羧基和酮羰基,具有很强的反应性,可参与多种化学反应,在化学工业中有广泛应用.目前,工业上主要采用酒石酸脱水脱羧法生产丙酮酸,丙酮酸收率可达50–55%,但生产过程需要消耗大量的KHSO4粉末,生产成本高,且高耗能高污染,不符合可持续发展的要求.因此,利用可再生资源甘油在温和条件下生产丙酮酸显现出良好的应用前景.目前,由甘油一步法获得丙酮酸仅可通过发酵法实现,但是其规模化生产存在效率低、废弃物污染等问题.因此,研究化学方法由甘油一步制备丙酮酸可行也十分必要.本课题组以Pt/AC或Cu-Pt/AC为催化剂进行甘油氧化制备乳酸的研究,所得产物中几乎未检出丙酮酸;当以Pb-Pt/C为催化剂进行乳酸脱氢氧化制备丙酮酸,可获得较高选择性的丙酮酸.因此,本文通过向Pt/AC催化剂中引入Pb助剂,以期调变甘油氧化的产物分布,从而获得相对高的丙酮酸选择性.通过浸渍-沉积沉淀法(Im-DP)制备了一系列不同Pb载量(1–7.0 wt%)的xPb-5Pt/AC-Im-DP催化剂,并采用不同方法制备了一系列5Pb-5Pt/AC催化剂,用于在温和条件下甘油选择性氧化制备丙酮酸反应中.结果表明,Pb载量和催化剂制备方法都对其催化活性有显著影响.当xPb-5Pt/AC-Im-DP催化剂中Pb载量为1%时,甘油转化率和丙酮酸选择性均较单金属5Pt/AC催化剂高,但当Pb载量继续升高至3%及以上时,甘油转化率明显下降.我们推测这与Pb3(CO3)2(OH)2物种的形成有关.采用该方法制备催化剂时,Pb载量宜为5.0 wt%.保持Pt和Pb载量均为5.0 wt%,采用共沉积沉淀(Co-DP)、共浸渍(Co-Im)、以及对催化剂进行500oC氩气焙烧等,制备了具有Pb3(CO3)2(OH)2物种、铂铅合金物种(PtPb和PtxPb)和两物种均没有的5Pb-5Pt/AC催化剂.通过评价它们的催化性能,进一步探究了Pb3(CO3)2(OH)2物种、铂铅合金物种、表面金属价态与催化剂活性的关系.实验表明,Pb3(CO3)2(OH)2和表面Pb0物种不利于甘油的转化,铂铅合金对甘油转化有一定的促进作用,对丙酮酸生成显现出明显促进作用.通过对Co-DP、Im-DP催化剂进行500oC氩气焙烧,能够除去Pb3(CO3)2(OH)2物种,同时形成铂铅合金.综上,本文在温和条件下,采用Pb-Pt/AC催化剂进行甘油选择性氧化制备丙酮酸反应.采用优化的方法制备的5Pb-5Pt/AC催化剂在90oC条件下反应10 h,丙酮酸收率可达18.4%,这是目前甘油一步法氧化制备丙酮酸的最高值.进一步优化反应条件、催化剂组成与结构,探索反应机理仍十分必要.     

Effect of metal loading and carbon support microstructure on the dispersion of Pt/C catalysts prepared viaadsorption of chloroplatinic acid

Summary Adsorption of<span lang=EN-US style='mso-ansi-language:EN-US'>H₂PtCl₆onto a carbon support followed by reduction of the adsorbed platinum species with H₂at 250°C leads to<span lang=EN-GB style='mso-ansi-language:EN-GB'>Pt/C catalysts, which show universal volcano-like dependence of platinum dispersion on the metal loading in the range from 0.01 to 0.55mmol (Pt)/m²(S_BET)<span lang=EN-GB style='mso-ansi-language:EN-GB'>when highly disordered carbons, namely, active carbons and carbon blacks, are used as supports. The maximal dispersion D(CO/Pt) = 0.8 is attained at<span lang=EN-US style='mso-ansi-language:EN-US'>0.18mmol (Pt)/m² (S_BET). With<span lang=EN-GB style='mso-ansi-language:EN-GB'>other factors being equal, the dispersion of platinum supported on carbons with a more regular crystal structure, especially Sibunit-type supports, proves to be the highest and independent of the metal loading.The differences between the two groups of carbon supports are explained by the differences in the state of the adsorbed platinum precursors.     

Transformation of n-hexane on Al2O3and SiO2supported Pt, Pt+Ga and Ir+Pt+Ga catalysts prepared by anchoring methods

Summary Transformation of n-hexane over Al₂O₃and SiO₂supported Pt, Pt+Ga and Ir+Pt+Ga catalysts was studied in a continuous-flow reactor operated under slug-pulse mode at 520°C. Bimetallic catalysts were prepared by introducing first Ga(OEt)₃and then diallylplatinum as precursor compounds. Iridium was then introduced viadecomposition of Ir₄(CO)₁₂adsorbed onto Pt+Ga catalysts. The addition of Ga to Pt/SiO₂catalyst decreased hydrogenation, aromatization and hydrogenolysis selectivity. Over Pt/Al₂O₃catalyst Ga increased hydrogenolysis selectivity and decreased isomerization and C₅-cyclization. The main effect of Ir was to increase hydrogenolysis selectivity and the stability of catalysts.</o:p>     

Enhanced methane production from methanol decomposition over Pt/TiO2 catalysts

The promoting effect of TiO₂ on CH₄ formation from CH₃OH decomposition has been investigated. Hydrogen and CO are products of CH₃OH decomposition which can subsequently react to produce CH₄. We observe an enhancement in this secondary reaction when the support is TiO₂. This enhancement is lost after a high temperature reduction.

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TiO₂ CH₄ CH₃OH. CH₃OH CO, , CH₄. TiO₂ . , , .

     

Surfactant effects on methanol oxidation at Pt–Ru/C coated glassy carbon electrode

The role of surfactants, cetyl trimethyl ammonium bromide (CTAB), sodium dodecyl sulphate (SDS) and Triton X-100 (in the catalyst), on methanol oxidation at commercial 50:50 Pt–Ru/C catalyst-coated glassy carbon has been studied using cyclic voltammetry, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Surfactant containing catalysts showed a considerable reduction in the methanol oxidation potential. In terms of oxidation potential, better results (lower methanol oxidation potential) were observed in the order SDS > Triton X-100 > CTAB > no surfactant. SEM studies on the catalyst ink showed better homogeneity in the sample prepared using surfactant. This indicates better Pt Pt contact, which is likely to favour methanol adsorption and its oxidation. Hence, lowering of oxidation potentials for methanol oxidation could be seen with use of surfactants. Results of FT-IR on the catalyst ink showed definite changes in the frequencies in the case of Pt–Ru/C containing surfactants indicating definite interaction between catalyst and surfactant. Catalysts, with and without surfactants, yielded linear plots of concentration vs peak currents for methanol oxidation (0–2 M). With surfactant containing catalysts, reduction in methanol oxidation current was observed, and the order followed was the reverse of the above.     

Electrodeposition of Pt ultramicroparticles in Nafion films on glassy carbon electrodes

The electrodeposition of platinum particles into Nafion films on a glassy carbon electrode is described. The particles are dispersed three-dimensionally throughout the polymer layer. The active platinum surface area is determined by the charge required for the adsorption of hydrogen. The mass specific surface area of the particles grown in the Nafion film is surprisingly large, suggesting that the platinum particles are highly dispersed in the Nafion film. The average crystal size of the platinum clusters is in the range 10–20 nm. The exchange current density of the hydrogen evolution reaction has been determined in an acidic solution.     

Carbon monoxide oxidation on Pt/TiO2 sol-gel catalysts

Comparative results (specific area, metallic dispersion, and activity in the carbon monoxide oxidation) on sol-gel and impregnated Pt/TiO₂ catalysts are presented. In order to explain the important differences between the two preparations, among them high resistivity of sol-gel catalyst to sintering, the formation of anchored and/or partially buried particles into the support is proposed.     

Structural and electrocatalytic properties of Pt/C and Pt-Ni/C catalysts prepared by electrochemical dispersion

The structural and electrocatalytic properties of Pt/C and Pt-Ni/C catalysts prepared by the electrochemical dispersion of metals under the action of pulse alternating current in a solution of NaOH were studied. Using X-ray diffraction analysis and scanning and transmission electron microscopy, it was found that the synthesized Pt/C catalysts contained active constituent particles with the average size D ₁₁₁ = 10.6 nm with a predominantly cubic shape. Upon the dispersion of a Pt₃Ni alloy, the Pt-Ni/C catalyst containing the particles of a stoichiometric metal phase of Pt₃Ni (D ₁₁₁ = 9.6 nm) and also Pt _x Ni particles (x > 3) enriched in platinum (D ₁₁₁ = 8.1 nm). The synthesized catalysts possessed high electrocatalytic activity and stability in the reaction of methanol oxidation. The characteristics of these catalysts as anodes in the membrane-electronic unit of a hydrogen-air solid-polymer fuel cell were studied.