Elettrodeposizione di catalizzatori a base di Rh su schiume e fibre metalliche di FeCrAlloy per la produzione di syngas

The preparation of structured catalysts active in the catalytic partial oxidation of methane to syngas, was performed by electrosynthesis of hydroxides on FeCrAlloy foams and fibers. Rh/Mg/Al hydrotalcite-type compounds were prepared by co-precipitation of metallic cations on the support and successive calcination. Electrochemical reactions have been studied during the electrodeposition by linear sweep voltammetry. The experiments were performed at supports immersed in KNO3, KCl, Mg2+ and Al3+ aqueous solutions, starting by different precursors (nitrate and chlorides salts) and modifying the Mg/A ratio. Rh/Mg/Al hydrotalcite-type compounds were deposited on metal foams by applying a -1.2V vs SCE potential for 2000s with a nitrate solution of 0.06M total metal concentration. Firstly it was studied the effect of Mg on the coating propierties, modifying the Rh/Mg/Al atomic ratio (5/70/25, 5/50/45, 5/25/70 e 5/0/95). Then the effect of the amount of Rh was later investigated in the sample with the largest Mg content (Rh/Mg/Al = 5/70/25 and 2/70/28).The results showed that magnesium allowed obtaining the most homogeneous and well adherent coatings, wherein rhodium was well dispersed. The sample with the Rh/Mg /Al ratio equal to5/70/25 showed the best catalytic performances. Decreasing the Rh content, the properties of the coating were not modified, but the catalytic activity was lower, due to a not enough number of active sites to convert the methane. The work on metal fibers focused on the effect of precursor concentration, keeping constant composition, potential and synthesis time at the values of Rh/Mg/Al =5/70/25, -1.2V vs SCE and 1000s. However fibers geometry did not allow to obtain a high quality coating, even if results were quite promising.

Co/Mg/Al hydrotalcite-type precursor, promoted with La and Ce, studied by XPS and applied to methane steam reforming reactions

Catalysts` precursor of Co/Mg/Al promoted with Ce and La were tested in the steam reforming of methane (SRM). The addition of promoters was made by anion-exchange. The oxides characterization was made by X-ray Photoelectron Spectroscopy (XPS) analysis that confirmed Co(2+) species in free form on surface and interacted with Mg and Al in the form of solid solution. In the SRM with high fed molar ratio of H(2)O:CH(4) = 4:1, the catalysts showed a great affinity with water and immediately deactivated by oxidation of the active sites. In the stoichiometric ratio of H(2)O:CH(4) = 2: 1 the catalysts were active and presented low carbon deposition during the time reaction tested. Also a test with low fed molar ratio H(2)O:CH(4) = 0.5:1 was carried out to evaluate the stability of the catalysts by CH(4) decomposition and all the catalysts were stable during 6 h of reaction. Promoted catalysts presented lower carbon deposition. (C) 2009 Elsevier B. V. All rights reserved.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

Vanadium and Titanium Mixed Oxide Films: Synthesis, Characterization and Application as Ion Sensor

Vanadium/titanium mixed oxide films were produced using the sol-gel route. The structural investigation revealed that increased TiO2 molar ratio in the mixed oxide disturbs the V2O5 crystalline structure and makes it amorphous. This blocks the TiO2 phase transformation, so TiO2 stabilizes in the anatase phase. In addition the surface of the sample always presents larger amounts of TiO2 than expected, revealing a concentration gradient along the growth direction. For increased TiO2 molar ratios the roughness of the surface is reduced. Ion sensors were fabricated using the extended gate field effect transistor configuration. The obtained sensitivities varied in the range of 58 mV/pH down to 15 mV/pH according to the composition and morphology of the surface of the samples. Low TiO2 amounts presented better sensing properties that might be related to the cracked and inhomogeneous surfaces. Rising the TiO2 quantity in the films produces homogeneous surfaces but diminishes their sensitivities. Thus, the present paper reveals that the compositional and structural aspects change the surface morphology and electrical properties accounting for the final ion sensing properties of the V2O5/TiO2 films. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.053206jes] All rights reserved.

Catalysts for H2 production

The research of new catalysts for the hydrogen production described in this thesis was inserted within a collaboration of Department of Industrial Chemistry and Materials of University of Bologna and Air Liquide (Centre de Recherche Claude-Delorme, Paris). The aim of the work was focused on the study of new materials, active and stable in the hydrogen production from methane, using either a new process, the catalytic partial oxidation (CPO), or a enhanced well-established process, the steam methane reforming (SMR). Two types of catalytic materials were examined: 1) Bulk catalysts, i.e. non-supported materials, in which the active metals (Ni and/or Rh) are stabilized inside oxidic matrix, obtained from perovskite type compounds (PVK) and from hydrotalcite type precursors (HT); 2) Structured catalysts, i.e. catalysts supported on materials having high thermal conductivity (SiC and metallic foams). As regards the catalytic partial oxidation, the effect of the metal (Ni and/or Rh), the role of the metal/matrix ratio and the matrix formulation of innovative catalysts obtained from hydrotalcite type precursors and from perovskites were examined. In addition, about steam reforming process, the study was carried out first on commercial type catalysts, examining the deactivation in industrial conditions, the role of the operating conditions and the activity of different type of catalysts. Then, innovative materials bulk (PVK and HT) and structured catalysts (SiC and metallic foam) were studied and a new preparation method was developed.

Development of Optically Based pH Sensing Hydrogel and Controlled Nitric Oxide Release Polymer

Nitric oxide has the potential to greatly improve intravascular measurements by locally inhibiting thrombus formation and dilating blood vessels. pH, the partial pressure of oxygen, and the partial pressure of carbon dioxide are three arterial blood parameters that are of interest to clinicians in the intensive care unit that can benefit from an intravascular sensor. This work explores fabrication of absorbance and fluorescence based pH sensing chemistry, the sensing chemistries' compatibility with nitric oxide, and a controllable nitric oxide releasing polymer. The pH sensing chemistries utilized various substrates, dyes, and methods of immobilization. Absorbance sensing chemistries used sol-gels, fumed silica particles, mesoporous silicon oxide, bromocresol purple, phenol red, bromocresol green, physical entrapment, molecular interactions, and covalent linking. Covalently linking the dyes to fumed silica particles and mesoporous silicon oxide eliminated leaching in the absorbance sensing chemistries. The structures of the absorbance dyes investigated were similar and bromocresol green in a sol-gel was tested for compatibility with nitric oxide. Nitric oxide did not interfere with the use of bromocresol green in a pH sensor. Investigated fluorescence sensing chemistries utilized silica optical fibers, poly(allylamine) hydrogel, SNARF-1, molecular interactions, and covalent linking. SNARF-1 covalently linked to a modified poly(allylamine) hydrogel was tested in the presence of nitric oxide and showed no interference from the nitric oxide. Nitric oxide release was controlled through the modulation of a light source that cleaved the bond between the nitric oxide and a sulfur atom in the donor. The nitric oxide donor in this work is S-nitroso-N-acetyl-D-penicillamine which was covalently linked to a silicone rubber made from polydimethylsiloxane. It is shown that the surface flux of nitric oxide released from the polymer films can be increased and decreased by increasing and decreasing the output power of the LED light source. In summary, an optical pH sensing chemistry was developed that eliminated the chronic problem of leaching of the indicator dye and showed no reactivity to nitric oxide released, thereby facilitating the development of a functional, reliable intravascular sensor.

Chemical sensor measurements at the sediment surface of the Håkon Mosby mud volcano (LOOME)

Six sensor units each having a pH, dissolved oxygen (DO) and oxidation reduction potential (ORP) sensor, plus a central logger, and connection cables were purchased from RBR (Ottawa). The sensing loggers were placed at a transect across the hot spot. Unfortunately, 5 of the 7 loggers were drowned. Only the central logger, that collected the data from the 6 sensor loggers, and one of the sensor loggers remained dry and functional. The sensor was positioned at 50 m south of the frame, in the center of the hot spot. The ORP did not show interpretable signals. The DO and pH signals showed good correlation (. At the end of October 2009 both signals decreased, the pH became as low as 4, possibly indicating increased seepage, or burial in expelled sediments. In December both sensors regained seawater values and then decreased again until the end of May 2010. A pH of 4 can only be reached by very high carbondioxide levels. The dynamics of the signals indicate eruptions and sediment movements from October 2009 till the end of the deployment.

Exchange biased FeNi/FeMn bilayers with coercivity and switching field enhanced by FeMn surface oxidation

FeNi/FeMn bilayers were grown in a magnetic field and subjected to heat treatments at temperatures of 50 to 350 degrees C in vacuum or in a gas mixture containing oxygen. In the as-deposited state, the hysteresis loop of 30 nm FeNi layer was shifted. Low temperature annealing leads to a decrease of the exchange bias field. Heat treatments at higher temperatures in gas mixture result in partial oxidation of 20 nm thick FeMn layer leading to a nonlinear dependence of coercivity and a switching field of FeNi layer on annealing temperature. The maximum of coercivity and switching field were observed after annealing at 300 degrees C.

Chemistry of low-valent platinum dimers

Physical and chemical properties of low-valent platinum dimers, namely [Pt_2(P_2O_5H_2)4]^(4-) and Pt_2(µ-dppm)_2Cl_2, have been investigated using a variety of structural and spectroscopic techniques.

Platinum(II) d^8-d^8 dimers have been shown to exhibit much thermal and photochemical reactivity. Chapter 2 describes studies aimed at elucidating the excited state reduction potenetial of [Pt_2(P_2O_5H_2)4]^(4-), Pt_2, in organic media. By conducting excited state electron transfer studies using derivatized pyridiniums and benzophenones, the excited state reduction potential has been estimated to be ~2 V. The Pt_2 complex undergoes partial oxidation to form Pt(II,III) linear chains. Chapter 3 describes the structural and spectroscopic techniques used to determine the translational symmetries of these [Pt_2(P_2O_5H_2)4]^(4-) (X = Cl, Br), Pt_2X, chains. Pt_2Br has been found to be intermediate between (AAB)_n and (AABCCB)_n, while, Pt_2Cl is of (AABCCB)_n translational symmetry. Investigations into the electronic transitions of Pt_2Cl and Pt_2Br were conducted using high pressure techniques and are presented in Chapter 4. The Pt_2X electronic spectrum exhibits bands attributable to the reduced Pt2 complex and the oxidized Pt_2X_2 complex [Pt_2(P_2O_5H_2)4]^(4-) along with an intervalence charge-tranfer band characteristic of a mixed-valence solid.

Photophysical investigations of a new luminescent chromophore, Pt_2(µ-dppm)_2Cl_2, a d^9-d^9 dimer, and its analogs are described in Chapter 5. The absorption band directly responsible for the observed emission is believed to be very weak and, as of yet, unobserved. Attempts to determine the spin multiplicty and approximate energy of this unobserved transition are described in Chapter 6. Excited-state energy transfer studies indicate that this absorption band is a triplet transition at -13,000 cm^(-1). Although, the Pt_2(µ-dppm)_2Cl_2 excited state is non-luminescent in fluid solution, it has been shown to undergo thermal electron transfer to tetracyanoethylene and photoinduced electron transfer to methylviologen. These experiments are presented in Chapter 7. Preliminary studies, described in Chapter 8, of non-bridged d^9-d^9 platinum(I) dimers have shown that [Pt_2(CNCH_3)_6]^(2+) serves as a versatile precursor in the synthesis of new d^8-d^8 A-frame complexes.

Iridium and rhodium analogues of the Shilov cycle catalyst; and the investigation and applications of the Reduction-Coupled Oxo Activation (ROA) mechanistic motif towards alkane upgrading

This dissertation will cover several disparate topics, with the overarching theme centering on the investigation of organometallic C-H activation and hydrocarbon transformation and upgrading. Chapters 2 and 3 discuss iridium and rhodium analogues of the Shilov cycle catalyst for methane to methanol oxidation, and Chapter 4 on the recently discovered ROA mechanistic motif in catalysts for various alkane partial oxidation reactions. In addition, Chapter 5 discusses the mechanism of nickel pyridine bisoxazoline Negishi catalysts for asymmetric and stereoconvergent C-C coupling, and the appendices discuss smaller projects on rhodium H/D exchange catalysts and DFT method benchmarking.

The pyrolysis of n-butane

A study of the pyrolysis of n-butane was carried out using an all-gold tubular reactor. The initial rate of decomposition of the n-butane was of 1.50-order with respect to the partial pressure of the n-butane. A free radical mechanism, similar to that originally proposed by Rice, accounted satisfactorily for the distribution of products. Oxygen was rigorously excluded from the pyrolysis gases. The surfaces of the gold reactor had been acid-treated to remove oxide impurities. Some preliminary experiments were performed in the partial oxidation of n-butane.

Fluorescence pH probe based on microstructured polymer optical fiber

A kind of optical pH sensor was demonstrated that is based on a pH-sensitive fluorescence dye-doped (eosin) cellulose acetate (CA) thin-film modified microstructured polymer optical fiber (MPOF). It was obtained by directly inhaling an eosin-CA-acetic acid mixed solution into array holes in a MPOF and then removing the solvent (acetic acid). The sensing film showed different fluorescence intensities to different pH solutions in a pH range of 2.5-4.5. Furthermore, the pH response range could be tailored through doping a surfactant, hexadecyl trimethyl ammonium bromide (CTAB), in the sensing film. (c) 2007 Optical Society of America.

光导纤维pH传感器的光化学pH敏感高分子膜及pH响应性能

pH指示剂在高分子载体上的固定化研究是应光导纤维pH传感器的发展要求而发展起来的新的研究领域。pH指示剂在高分子固态载体上的固定直接决定着光导纤维pH传感器的灵敏度、响应时间、寿命等性能。迄今，吸附、包埋和化学键合三利，固定方法已得到广泛应用。吸附法与包埋法简单易行，但因指示剂易于逸出而无法保证试剂相的使用稳定性及寿命；化学键合法目前仅限于对含氨基等高反应活性基团的指示剂固定。另外，这三种固定技术均存在试剂相与分析对象呈现固／液两相分离的问题，它严重制约了传感器响应性能，成为pH指示剂固定技术发展的“瓶颈”。改善、发展与寻找新的指示剂／载体固定配对体系已成为本领域的研究焦点。本论文针对上述问题，开拓与发展了一系列指示剂固定于固态高分子载体上的新体系。（一）首先开拓与发展了酚红／交联聚乙烯醇与邻甲酚红／交联聚乙烯醇固定对的新体系。在酸性条件下，以甲醛做交联剂，通过在玻璃板上倾涂聚乙烯醇甲醛的凝胶溶液制备了高亲水性的交联聚乙烯醇载体膜；然后采用接枝共聚反应将丙烯酞胺单体与通过酸碱反应接枝有酚红或邻甲酚红的丙烯酞胺混合物接枝固定到交联聚乙烯醇薄膜上，首次将不含氨基的酚红、邻甲酚红在高亲水性的聚乙烯醇载体上固定。利用紫外可见光光谱仪测试了其响应性能。结果表明，固定化指示剂的光谱行为与其相应的水溶液的光谱行为不一致，这可能是固定化过程中新的化学键生成以及载体与指示剂之间的相互作用如氢键的作用等引起的。这也导致了其pH响应范围与相应指示剂水溶液的响应范围的差异。固定酚红交联聚乙烯醇pH敏感膜的pH响应范围为pH=6.72～8.49；固定邻甲酚红交联聚乙烯醇pH敏感膜的两个响应范围分别为［H~+］=0.1mol／L～5mol／L和pH7.97～12.26。这种方式制备的这两种pH敏感薄膜均表现出优异的可重复使用性、可逆性、稳定性及易于制备的特点。更突出的优点在于，与以聚丙烯酰胺为基质直接固定酚红的薄膜（PAM-PR）相比，这种固定技术制备的敏感膜，当其与分析剂溶液接触时，其接枝于表面的水溶性高分子溶解，呈现“液态”，在固态基质表面形成一“液膜”层，从而消除了试剂相与分析剂之间的相界面，克服了指示剂固定化技术中的“瓶颈”问题，大幅度地提高了其响应速度与灵敏度，使响应时间从PAM-PR的数十分钟降至30秒以下。（二）开拓了刚果红醋酸纤维素包埋对的pH敏感膜（CCM）及刚果红／环氧氯丙烷交联聚乙烯醇（PECM）和甲醛交联聚乙烯醇（PFCM）的三种pH敏感膜新体系，测试并比较了三种膜的响应性能。结果表明，固定化刚果红的光谱性质和响应范围与刚果红水溶液不一致，而且用不同载体固定的刚果红的光谱特征与响应范围也各不相同。CCM的响应范围为pH＝2.5～4.5，PECM的响应范围在［H~+］=2mol/L～pH＝6.8之间，PFCM响应范围为pH＝2.90～5.48。这也可能是固定化过程中的氢键效应、空间位阻、指示剂与载体间发生的化学反应不同及载体本身结构的差异等引起的。这三种膜也具有良好的重现性、可逆性及响应迅速（平均响应时间低于25秒）的特点。另外发现醋酸纤维素包埋刚果红的敏感膜具有特殊的稳定性。对这种特殊的稳定性原因的分析表明选择合适尺寸分子的指示剂与载体配对将可能克服包埋技术中指示剂逸出的缺点。（三）对制备的pH敏感膜及对应的水溶液的pH线性响应范围给出了相应的线性回归方程（R＞98.2）。结果表明这些敏感膜对响应范围内的pH均具有良好的线性响应关系。这些结果与思想不仅丰富了光导pH传感器的试剂相内容，也为后续工作提供了一些有益的借鉴。

PH值、氯离子浓度和监酸浓度对于铁的腐蚀电化学行为的影响

本文研究了Armco铁在盐酸溶液中的腐蚀电化学行为，探讨了ψ~-离子和PH值对铁的阳极溶解过程的影响，并进而讨论了ψ~-离子浓度和PH值对铁的腐蚀电化学行为的影响之间是否存在交互效应。在本工作中，作者提出了两个新的研究方法：(a) 从单支弱极化曲线测定腐蚀电流和阴、阳极反应的Tafep斜率；(b)根据交流方波电流扰动的响应函数方程测定极化电阻Rp和界面电容C。设I_c、I_(2c)、I_(3c)及I_(4c)分别为对应于弱极化区内极化电位为ΔE、2ΔE、3ΔE和4ΔE的极化电流，且令a = I_(2c)/I_c, b = I_(3c)/I_c, c = I_(4c)/I_(2c), 而(4b-3a~2)~(1/2)、(3c-2b)~(1/2)、(2c-a~2)~(1/2)则以S_j表示之，则可得到：I_(corr) = I_c/S_j b_c = ΔE/lg((a+s_j)/2) b_a = -ΔE/lg((a-s_j)/2)为了方便，准确地求出动力学参数，可选用一系列的ΔE值，得出相应的极化电流I_λ，求出S_λ，应用统计方法处理数据，可得：I_(corr) = ∑ from i=1 to n I_λ/∑ from i=1 ton S_λ b_c = ∑ form λ to n ΔE_λ/∑ form i=1 to n lg ((a_λ+S_λ)/2) b_a = ∑ form i=1 ton ΔE_λ/∑ form i=1 to n lg ((a_λ-S_λ)/2)在线性极化区间内向腐蚀金属电极体系施加一交流方波电流扰动讯号时，通过Laplace变换分析，得到相应的响应函数方程为：E_1(t) = λ_o(R_s+R_p) - 2λ_oR_p (e~(-(τ-λ)/RpC))/(1+e~(λ/RpC)) (o<τ<λ) E_2(t) = -λ_o(R_s+R_p) + 2λ_oR_p (e~(-(τ-λ)/RpC))/(1+e~(λ/RpC)) (λ<τ<2λ)由此方程可知，它们在E～λ坐标系统中的轨迹为对称兴致勃勃原点的两条直线。由此方程可进一步得到:ΔE = 2λ_oR_p (e~(λ/RpC)-1)/(e~(λ/RpC)+1) = 2λ_oR_p t_(anh)(λ/(2RpC)) Δh = 2λ_o Rs式中ΔE为单支响应直线的长度，Δh则为两条直线最高点之间的距离。上述公式可进一步简化为：Rp =(ΔE)/(2λ_o) λ>>RpC (λ_o)/(ΔE) = C/λ + 1/(2Rp) λ<partial deriv) ψ_(corr))/((partial deriv) PH)]_([ψ~-]) = -55 毫伏 [((partial deriv) ψ_(corr))/((partial deriv) lg[ψ~-])]_(PH) = -15 毫伏 [((partial deriv) lg I_(corr))/((partial deriv) PH)]_([ψ~-]) = -0.4 [((partial deriv) lg I_(corr))/((partial deriv) lg[ψ~-])]_(PH) = 0.13 αψ_(corr)/α lg[Hψ] = -44 毫伏 α lg I_(corr)/α lg[Hψ] = 0.45 b_a = 40 毫伏，b_c = 120 毫伏，为了与弱极化区内得到的数据相比较，又观察了强极化区内的研究结果。由强极化区内Tafel线段的数据分析而得到的离子反应级数和Tafel斜率值与弱极化区得到的结果是一致的。由此，讨论了铁的阳极溶解过程，提出了反应机理，由此机理推论而得出的有关的电化学参数的理论值与实验值符合得很好。最后，对PH值和ψ~-离子浓度对铁的腐蚀电化学行为的影响之间是否存在交互效应进行了探讨。由实验数据的分析得到，PH值和ψ~-离子浓度的效应之间不存在交互效应，或者交互效应不大。

Low-temperature oxidation of methane to form formaldehyde: role of Fe and Mo on Fe-Mo/SiO2 catalysts, and their synergistic effects

The partial oxidation of methane with molecular oxygen was performed on Fe-Mo/SiO2 catalysts. Iron was loaded on the Mo/SiO2 catalyst by chemical vapor deposition of Fe-3(CO)(12). The catalyst showed good low-temperature activities at 723-823 K. Formaldehyde was a major condensable liquid product on the prepared catalyst. There were synergistic effects between iron and molybdenum in Fe-Mo/SiO2 catalysts for the production of formaldehyde from the methane partial oxidation. The activation energy of Mo/SiO2 decreased with the addition of iron and approached that of the Fe/SiO2. The concentration of isolated molybdenum species (the peak at 1148 K in TPR experiments) decreased as the ion concentration increased and had a linear relationship with the selectivity of methane to formaldehyde. The role of Fe and Mo in the Fe-Mo/SiO2 catalyst was proposed: Fe is the center for the C-H activation to generate reaction intermediates, and Mo is the one for the transformation of intermediates into formaldehyde. Those phenomena were predominant below 775 K.