Academic literature on the topic 'Gold/silicon catalysis'

Utilizing porous silicon as a reducing agent and a substrate, gold complex ions [AuCl4]- were reduced from aqueous solution to produce nanoparticles of gold upon the surface of porous silicon. Scanning electron microscopy (SEM) was utilized to study the morphology of the porous silicon layers and the deposits of gold nanoparticles. It is found that preparation conditions have a profound effect on the morphology of the deposits, especially on porous silicon prepared from a p-type wafer. The gold nanoparticles, varying from micrometric aggregates of clusters of the order of 10 nm, to a distribution of nearly spherical clusters of the order of 10 nm, to strings of ~10 nm were observed and compared to bulk gold metal using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). These techniques confirm and complement the SEM findings. The potential for this reductive deposition technique is noted.Key words: gold nanostructures, reductive deposition, porous silicon, morphology, X-ray spectroscopy.

Different arylgold(i), one alkynylgold(i), and one vinylgold(i) triphenylphosphane complexes were subjected to electrophilic halogenation reagents. With N-chlorosuccinimid, N-bromosuccinimid, and N-iodosuccinimid as well as the Barluenga reagent, selectively halogenated compounds were obtained. Trifluoroacetic acid, as a source of protons, leads to a clean protodeauration. With N-fluorobenzenesulfonimide or Selectfluor, exclusively a homocoupling was observed. For the precursor of the vinylgold(i) complex, a similar oxidative coupling could be induced by gold(iii) chloride. Reactions with silicon or tin electrophiles failed.

X-ray photoelectron spectroscopy (XPS) is used to determine the oxidation state of gold deposited from an aqueous solution of AuCl4- on to various oxidized surfaces of silicon. Although the observed Au4f signal decreased with the thickness of the oxide layer, the oxidation state of Au was determined as 0 for all the samples analyzed. From the angular dependence of the Si2p and Au4f signals it was determined that Au is deposited on top of the oxidized surfaces of metallic silicon. It is postulated that from an aqueous solution of AuCl4-, gold would deposit in its zerovalent form on to any surface due to its large and positive electrochemical reduction potential (ε°red(Au3+ /Au) = +1.50 V) and the substrate plays a role only in providing active deposition sites. To further support the proposal, it is shown that the same process takes place even in inert and hydrophobic polypropylene substrates. Similarly, it is also shown that more gold deposits if the surface of the polypropylene is made less hydrophobic (but probably more active) via the industrially used corona discharge treatment.Key words: XPS, gold, electroless deposition, oxidized silicon surface.

We report the chemical synthesis and structural studies of thiol-capped Au nanoparticles (NPs) using extended X-ray absorption fine structures (EXAFS) and high-resolution transmission electron microscopy (HRTEM). Synthesis of Au NPs was conducted in one case in a toluene/water two-phase system using alkanethiols with varied hydrocarbon chain length (C6, C12, and C18), resulting in NPs of sizes ranging from 1.6 nm to 5.4 nm. Au L3-edge EXAFS reveals a systematical trend of the local structure of Au in the NPs when the Au/S ratio and chain-length of thiols are varied. In another synthesis, thiol-capped Au NPs were prepared on the surface of silicon nanowires, which act as both substrates and reducing agents. HRTEM reveals that not only spherical particles but also very small quasi-1D nanostructures of Au were formed. The formation and structure of these Au NPs was discussed in terms of ligand and template effect associated with the silicon nanowire substrates.Key words: thiol-capped Au nanoparticles, EXAFS, silicon nanowires, electroless deposition, quasi-1D Au nanostructures.

A knowledge of the structure of small metal particles is fundamental to understanding their role in heterogeneous catalysis. It is therefore of much topical interest that structural rearrangements have been found to take place as a result of intense electron irradiation within the electron microscope. Initial observations were of gold particles on supports of carbon and silica-covered silicon, but further studies confirmed that qualitatively similar behaviour also took place for particles of Pt, Ru and Rh. Some of the factors which influence the motion have been noted, including the particle size, the nature of the substrate and, obviously, the current density of the electron beam. Considerable debate has been generated by these observations. It has been suggested, for example, that the structural fluctuations should be dampened by an electrically conducting substrate which would prevent the particles from becoming charged. It was also proposed that the “quasimelting” of gold particles was triggered by Auger decay, in effect heating the particles electronically rather than thermally. The energetics of these fluctuations have also been considered.In this paper, we report our initial efforts to quantify some of the experimental factors involved in this quasimelting process. Three sets of samples were prepared: one was a normal holey carbon support film, the second was a holey silicon support film, and the third was a carbon film upon which graphitised carbon had been deposited.

Porous gold films presented in this paper are formed by combining gold electroless deposition and polystyrene beads templating methods. This original approach allows the formation of conductive films (2 × 106 (Ω·cm)−1) with tailored and interconnected porosity. The porous gold film was deposited up to 1.2 μm on the silicon substrate without delamination. An original zirconia gel matrix containing gold nanoparticles deposited on the substrate acts both as an adhesion layer through the creation of covalent bonds and as a seed layer for the metallic gold film growth. Dip-coating parameters and gold electroless deposition kinetics have been optimized in order to create a three-dimensional network of 20 nm wide pores separated by 20 nm thick continuous gold layers. The resulting porous gold films were characterized by GIXRD, SEM, krypton adsorption-desorption, and 4-point probes method. The process is adaptable to different pore sizes and based on wet-chemistry. Consequently, the porous gold films presented in this paper can be used in a wide range of applications such as sensing, catalysis, optics, or electronics.

We report a novel process to selectively pattern nanomaterials, specifically gold nanoparticles, onto a silicon surface through “click” chemistry, to consistently and efficiently join together small units through a quick and simple reaction. We employed the UV-initiated thiol-ene reaction, which is used in tandem with microcontact printing. Dithiol-capped nanoparticles were used as a printing ink and were grafted onto ene-terminated Si(100) wafers by pressing a nanoparticle-impregnated poly(dimethylsiloxane) stamp, while irradiating with ultraviolet light to activate a radical initiator. The resulting structures were characterized using scanning electron microscopy and atomic force microscopy.

The creation of nanostructures with precise chemistries on material surfaces is of importance in a wide variety of areas such as lithography, superhydrophobicity, and cell adhesion. We describe a platform for surface functionalization that involves the fabrication of cylindrical micellar brushes on a silicon wafer through seeded growth of crystallizable block copolymers at the termini of immobilized, surface-confined crystallite seeds. The density, length, and coronal chemistry of the micellar brushes can be precisely tuned, and post-growth decoration with nanoparticles enables applications in catalysis and antibacterial surface modification. The micellar brushes can also be grown on ultrathin two-dimensional materials such as graphene oxide nanosheets and further assembled into a membrane for the separation of oil-in-water emulsions and gold nanoparticles.

Depuis le début des années 2000, la catalyse à l'or s'est particulièrement développée en chimie organique, offrant de nouvelles méthodes de synthèse très efficaces, généralement dans des conditions très douces. Ces avancées ont également conduit à une utilisation abondante en glycoscience, mais malgré d'importantes percées, l'application de la catalyse à l'or en glycochimie est typiquement limitée aux modes conventionnels d'activation des donneurs de sucres, dans lesquels le complexe d'or reste strictement confiné au rôle d'un acide σ- ou π-Lewis. Les travaux de recherche présentés au travers de ce manuscrit tendent à introduire un nouveau paradigme dans les réactions de glycosylation catalysées par l'or, en développant des réactions d'alcynylations catalytiques dans lesquelles le complexe d'or devrait surmonter les difficultés intrinsèques de ces couplages en contribuant à l'activation simultanée du donneur de sucre et de l'aglycone alcyne, sur la base d'une stratégie originale de catalyse synergique or/silicium. La combinaison idéale de catalyseur à l'or et de contre-ion a été recherchée (L et X) pour atteindre une réactivité catalytique et un contrôle stéréochimique optimums à la fois pour la réaction d’alcynylation de glycosides saturés simple mais aussi pour l’alcynylation de glycals. La découverte d’un impact important d’un contre-ion du complexe d’Au(I) jusque-là encore inexploité en catalyse synergique or/silicium associée à une phosphine fortement désactivante a permis d’étendre le champ d’application de la catalyse synergique or/silicium au-delà de l’alcynylation des glycosides
Since the early 2000s, gold catalysis has developed particularly well in organic chemistry, offering new highly efficient synthetic methods, generally under very mild conditions. These advances have also led to abundant use in glycoscience, but despite important breakthroughs, the application of gold catalysis in glycochemistry is typically limited to conventional modes of sugar donor activation, in which the gold complex remains strictly confined to the role of a σ- or π-Lewis acid. The research work presented through this manuscript tends to introduce a new paradigm in gold-catalysed glycosylation reactions, by developing catalytic alkynylation reactions in which the gold complex should overcome the intrinsic difficulties of these couplings by contributing to the simultaneous activation of the sugar donor and the alkyne aglycone, based on an original gold/silicon synergistic catalysis strategy. The ideal combination of gold catalyst and counterion was sought (L and X) to achieve optimum catalytic reactivity and stereochemical control both for the alkynylation reaction of simple saturated glycosides and for the alkynylation of glycals. The discovery of a major impact of a hitherto unexploited Au(I) complex counterion in synergistic gold/silicon catalysis associated with a strongly deactivating phosphine has made it possible to extend the field of application of synergistic gold/silicon catalysis beyond the alkynylation of glycosides

Yolk-shell nanostructures/yolk-shell nanoparticles are defined as a hybrid structure, a mixture of core/shell and hollow particles, where a core particle is encapsulated inside the hollow shell and may move freely inside the shell. Of the various classifications of yolk-shell nanostructures, a structure with an inorganic core and inorganic shell (inorganic/inorganic) has been studied widely due to their unique optical, magnetic, electrical, mechanical, and catalytic properties. In the work presented here, among the different inorganic/inorganic yolk-shell nanostructures noble metal@silica yolk-shell nanostructures has been chosen as the topic of interest. Silica shell possesses many advantages such as chemical inertness, tunable pore sizes, diverse surface morphologies, increasing suspension stability, no reduction in LSPR properties of noble metal nanoparticles when used as a coating for such particles. Noble metal nanoparticles such as AgNPs and AuNPs, on the other hand, possess unique structural, optical, catalytic, and quantum properties. Hence yolk-shell nanostructures with a combination of Ag or Au core and a silica shell (Ag@SiO2 and Au@SiO2) would open to endless possibilities. In this study, four areas were mainly explored: mechanism of silica shell formation over a given template, the synthetic modifications of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, their application as a potential catalyst, and devising of a flow type catalytic reactor. Despite the growing number of contributions on the topic of yolk-shell nanostructures, particularly Au@SiO2 and Ag@SiO2 yolk-shell nanostructures, a potential for improvement lies in all four aforementioned areas. As an initial study, the effect of different processing conditions as well as the mechanism of silica shell formation over reactive block copolymer templates was investigated. An asymmetric PS-b-P4VP block copolymer was chosen as a structure directing component to deposit silica shell. In order to deposit silica shell, PS-b-P4VP micelles with a collapsed PS core and a swollen P4VP corona was prepared via a solvent exchange method. The growth of silica shell over the PS-b-P4VP micelles (reactive template) was done using in-situ DLS and TEM. The experimental data obtained revealed the 4 distinct stages involved in the silica shell formation over the reactive BCP micellar template starting from the accumulation of silica precursor around the P4VP corona followed by a reactive template mediated hydrolysis-condensation reaction of the silica precursor which eventually lead to the shell densification and shell growth around the micelles. An understanding of the mechanism of silica shell formation over reactive templates provides a direct way to encapsulate various active species such as metal nanoparticles and quantum dots and paves the way for the template mediated synthesis of hybrid nanostructures such as yolk-shell nanoparticles. These studies also serve as a platform to fine-tune the properties of such hybrid nanostructures by varying the reaction parameters during silica shell deposition and reaction time. The next part of the work focused mainly on the synthesis, process optimisation and characterization of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, and their potential use as a nanocatalyst. A well-known soft template mediated synthesis of the yolk-shell nanostructure was adopted for the present work. For this PS-b-P4VP micelle was used as a dual template for both encapsulation of nanoparticle and the deposition of silica shell. The nanoparticles were entrapped selectively to the BCP micellar core and silica deposition was done by reacting the nanoparticle-loaded micelles with an acidic silica sol which lead to the formation of Ag@PS-b-P4VP@SiO2 or Au@PS-b-P4VP@SiO2 particles with respect to the nanoparticle used. In the case of Ag@PS-b-P4VP particles, upon silica deposition, a partial dissolution of AgNPs was observed whereas AuNPs were stable against dissolution. Hence yolk-shell nanostructures with AuNPs were studied further. As-prepared Au@PS-b-P4VP@SiO2 particles were then subjected to pyrolysis to remove the BCP template. The resulting yolk-shell nanostructures comprised of an AuNP core and a hollow mesoporous silica shell. Upon removal of the BCP template, the Au@SiO2 particles fused together and formed large aggregates. The catalytic properties of Au@SiO2 yolk-shell nanoparticles were explored using a model reaction of reduction of 4-nitrophenol and proved to have good catalytic activity and efficient recyclability. It was observed that catalytic efficiency was hindered by the particle aggregates formed after pyrolysis by creating an inhomogeneity in the system and inaccessibility of the catalytic surface for the reactants. Hence synthetic modifications were needed to overcome such drawbacks. Next part of the work deals with the synthetic modification of Au@SiO2 yolk-shell nanoparticles done by embedding them in a porous silica structure (PSS). Such structural morphology was attained by gelating the excess silica precursor while synthesising the Au@PS-b-P4VP@SiO2 particles. The pyrolytic removal of block copolymer results in the formation of Au@SiO2@PSS catalyst and the porous nature of both the shell and the silica structure provides an easy access for the reactants to the nanocatalyst surface located inside. The catalytic properties of Au@SiO2@PSS were studied using a model reaction of catalytic reduction of 4-nitrophenol (4-NP) and reductive degradation of different dyes. Kinetic studies show that Au@SiO2@PSS catalyst possesses enhanced catalytic activity as compared to other analogous systems reported in the literature so far. Furthermore, catalytic experiments on the reductive degradation of different dyes show that Au@SiO2@PSS catalyst can be considered as a very promising candidate for wastewater treatment. Another proposed direction of applying the Au@SiO2 yolk-shells is by devising a continuous flow catalytic system composed of Au@SiO2 yolk-shell nanoparticles for the effective degradation of azo dyes as a promising candidate for wastewater treatment. This was done by infiltrating the Au@PS-b-P4VP@SiO2 particles inside a porous glass substrate (frits) and the subsequent pyrolytic removal of the BCP template resulting in the formation of Au@SiO2 yolk-shell nanostructures sintered inside the frit pores. The flow catalytic reactor was exploited in terms of studying its catalytic activity in the degradation of azo dyes and 4-nitrophenol and proved to have a catalytic efficiency of ca. 99% in terms of reagent conversion and has a long-term stability under flow. Thus, with a few modifications, these flow type systems can open the doors to a very promising continuous flow catalytic reactor in the future.

La séparation magnétique a reçu beaucoup d'attention en tant que technologie de séparation de catalyseurs solides, très efficace et rapide. De nombreuses études ont porté sur l'immobilisation de systèmes catalytiques actifs sur un support magnétique afin de les séparer par la simple application d'un aimant. Cependant, le développement de supports magnétiques s'avère limité à des nanoparticules (NPs) magnétiques encapsulées dans une silice, un polymère ou du carbone. La conception de nanocomposites magnétiques incorporant d'autres oxydes est donc intéressante afin d'élargir l'application de cette technologie de séparation dans le domaine de la catalyse. Dans ce contexte, des études de stabilité thermique ont été menées sur magnétite revêtue de silice (Fe3O4@SiO2) pour évaluer la possibilité de la calciner sans perdre les propriétés magnétiques du support. La calcination permettrait le dépôt de différents oxydes sur la surface de la silice, tels que l'oxyde de cérium et l'oxyde de titane. Il a été observé que le matériau Fe3O4@SiO2 calciné a conservé sa morphologie core-shell et ses propriétés magnétiques, tandis que sa surface spécifique at a augmenté de 6 odres de grandeur. Un processus a pu être développé pour le dépôt d'oxyde de cérium et d'oxyde de titane sur Fe3O4@SiO2. Des nanocatalyseurs aisément récupérables par séparation magnétique à base de Rh, Pd et Ru ont pu être préparés en utilisant ces supports de silice modifiés par dépôt de CeO2 et TiO2. Ces nanocatalyseurs obtenus ont été évalués en catalyse d'hydrogénation du cyclohexène, du benzène ou du phénol. L'étude de l'influence de chaque support sur l'activité catalytique des nanocatalyseurs a consitué l'objectif principal de cette thèse. Le dépôt des nanoparticules métalliques sur les supports pour l'obtention des catalyseurs actifs a été réalisé par deux approches différentes: l'imprégnation et l'immobilisation de sols contenant des NP métalliques préformées. Quant aux NPs métalliques colloïdales, elles ont été préparées par réduction de sels métalliques et par la décomposition de complexes organométalliques précurseurs. Des catalyseurs de rhodium préparés par imprégnation de rhodium (III) chlorure et réduction avec H2 ont montré des problèmes de reproductibilité qui ont été contournés en utilisant NaBH4 ou l'hydrazine comme agents réducteurs. La préparation des catalyseurs par l'immobilisation des NP colloïdales s'est avérée une alternative intéressante pour obtenir des catalyseurs très actifs de façon reproductible. Des nanoparticules de Pd, Rh et Ru ont été préparées par l'approche organométallique et immobilisées sur les supports Fe3O4@SiO2 calciné, Fe3O4@SiO2CeO2 et Fe3O4@SiO2TiO2. L'élimination de l'agent stabilisant pour les NPs de Rh déposées sur Fe3O4@SiO2CeO2 semble conduire à un état de surface différent comparativement aux autres supports car ce catalyseur s'est montré le plus actif vis-à-vis de l'hydrogénation du cyclohexène (TOF 125 000 h-1). Les catalyseurs à base de Rh, Pd et Ru ont été utilisées pour l'hydrogénation de phénol. Le palladium s'est avéré le catalyseur le plus sélectif envers la cyclohexanone, quel que soit le support utilisé. La formation de cyclohexanol a été renforcée avec le support fonctionnalisé par l'oxyde de titane et la production de cyclohexane par hydrodéoxygénation a eu lieu principalement avec le support de silice
Magnetic separation has received a lot of attention as a robust, highly efficient and rapid catalyst separation technology. Many studies have focused on the immobilization of catalytic active species, but the development of magnetic supports has been limited to silica, polymer or carbon-coated magnetic nanoparticles (NPs). The design of magnetic nanocomposites and the incorporation of other oxides are thus highly welcome to broaden the application of this separation technology in the field of catalysis. In this context, studies of the thermal stability of silica coated magnetite (Fe3O4@SiO2) were performed to evaluate the possibility of calcining it without losing the magnetic properties of the support. The calcination would permit the deposition of different oxides on the silica surface, such as ceria and titania. The calcined Fe3O4@SiO2 material preserved its core-shell morphology and magnetic properties, and increased its surface area six times. A post-coating process was developed for the deposition of ceria and titania on Fe3O4@SiO2. Magnetically recoverable Rh, Pd and Ru nanocatalysts were prepared on the surface of the magnetic supports. The obtained catalysts were employed in hydrogenation of cyclohexene, benzene or phenol and the study of the influence of each support on the catalytic activity was the main objective of this thesis. For the deposition of the metallic nanoparticles on the supports in order to obtain the active catalysts two different approaches were followed: the impregnation and the sol immobilization of pre-formed metal NPs. Concerning the synthesis of the colloidal metal NPs, they were prepared either by reduction of metal salts or by decomposition of organometallic complexes. Rhodium catalysts prepared by impregnation of rhodium(III) chloride and reduction with H2 showed some reproducibility issues that were surpassed by using NaBH4 or hydrazine as reducing agents. The preparation of catalysts by the immobilization of colloidal NPs is an interesting alternative to obtain reproducible and very active catalysts. Nanoparticles of Pd, Rh and Ru were prepared by an organometallic approach and immobilized on calcined Fe3O4@SiO2, Fe3O4@SiO2CeO2 and Fe3O4@SiO2TiO2. The elimination of Rh stabilizing agent over ceria support appears to be different than in other supports and was the most active catalyst in the hydrogenation of cyclohexene (TOF 125,000 h-1). The Rh, Pd and Ru catalysts were employed in the hydrogenation of phenol. Palladium was the most selective catalyst to cyclohexanone, no matter the support used. The formation of cyclohexanol is enhanced in the support with titania and the hydrodeoxygenation to produce cyclohexane occurred mainly in the support with silica

Le surplus mondial et le faible prix du lactose ont attiré l’attention de chercheurs et de l’industrie pour développer des procédés novateurs pour la production de dérivés du lactose à valeur ajoutée, tels que l’acide lactobionique (ALB), qui est un produit à haute valeur ajoutée obtenu par l’oxydation du lactose, avec d’excellentes propriétés pour des applications dans les industries alimentaire et pharmaceutique. Des recherches sur la production d’ALB via l’oxydation catalytique du lactose avec des catalyseurs à base de palladium et de palladium-bismuth, ont montré des bonnes conversions et sélectivités envers l’ALB. Cependant, le principal problème de ces catalyseurs est leur instabilité par lixiviation et désactivation par suroxydation au cours de la réaction. Les catalyseurs à base d’or ont montré une meilleure performance que les catalyseurs de bismuth-palladium pour l’oxydation de glucides. Cependant, trouver un catalyseur robuste pour l’oxydation du lactose est encore un grand défi. Dans cette dissertation, des nouveaux catalyseurs à base d’or supportés sur des matériaux mésostructurés de silicium (Au/MSM) ont été synthétisés par deux méthodes différentes, et évalués comme catalyseurs pour l’oxydation du lactose. Les catalyseurs ont été caractérisés à l’aide de la physisorption de l’azote, DRX, FTIR, TEM et XPS. Les effets des conditions d’opération, telles que la température, le pH, la charge d’or et le ratio catalyseur/lactose, sur la conversion du lactose ont été étudiés. Finalement, le procédé de déminéralisation de la solution de lactobionate de sodium à la sortie du réacteur a été étudié à l’aide de deux approches: l’électrodialyse avec des membranes bipolaires (EDMB) et la technologie d’échange d’ions. Des catalyseurs Au/MSM hautement actifs ont été synthétisés avec succès par la co-condensation d’un mélange de bis [3-(triéthoxysilyl) propyle] tétrasulfide (BTESPTS), tétra-éthyle ortho-silicate (TEOS) et le précurseur d’or (HAuCl4) en milieu acide, avec le tribloc co-polymère EO20PO70EO20 utilisé comme agent structurant. Il a été trouvé que l’augmentation du ratio molaire BTESPTS/TEOS provoque un changement dans la structure des matériaux, laquelle passe d’une structure 2D-hexagonal très ordonnée à une structure mixte de type hexagonal-vésicule et mousse cellulaire. Dans les conditions opératoires optimales (charge d’or = 0.7% en poids, T = 65ºC, catalyseur/lactose ratio = 0.2, pH = 8-9, débit d’air = 40 mL·min-1), le lactose a été complètement converti en ALB après 80-100 min de réaction, lorsqu’on a utilisé les catalyseurs synthétisés à partir des mélanges contenant une concentration molaire de BTESPTS entre 6-10%. Ces catalyseurs ont été caractérisés par une structure de type « wormhole-like », favorable pour l’accessibilité des réactifs aux nanoparticules d’or (AuNPs) d’environ 8 nm intercalées dans les murs de la silice. AuNPs d’environ 5-6 nm ont été aussi chargées avec succès sur les matériaux mésoporeux SBA-15 et SBA-15-CeO2, par l’adsorption du complexe [Au(en)2]3+ (en=éthylènediamine) en milieu alcalin. Ces catalyseurs ont conservé la structure hexagonale 2D très ordonnée typique de la SBA-15, et ils ont présenté une grande activité pour l’oxydation du lactose. Après 60 min de réaction, les catalyseurs Au/SBA-15-CeO2 (ratio molaire Ce/Si = 0.2) ont présenté l’activité catalytique la plus élevée (100% conversion du lactose) et 100% de sélectivité envers l’ALB, lorsqu’ils ont été utilisés dans les conditions optimales décrites ci-dessus. Ces résultats suggèrent que l’oxyde de cérium joue un rôle dans l’augmentation de l’activité catalytique, où la coordination et les états d’agglomération des atomes du Ce pourraient avoir un effet important. En général, les résultats des analyses XPS sur les états d’oxydation de l’or à la surface des Au/MSM, ont montré la coexistence d’espèces d’or métalliques et oxydées, avec une abondance relative suivant l’ordre Au0 >>>Au+1 > Au+3. Dans le cas des catalyseurs Au/SBA-15-CeO2, la présence des deux états d’oxydation Ce3+ et Ce4+ a été aussi observée. Les expériences de recyclage des catalyseurs ont montré que l’activité des échantillons Au/SBA-15 et Au/SBA-15-CeO2 a été significativement réduite (40-65%) après des cycles de réaction d’oxydation consécutifs, lorsque le lavage avec de l’eau a été utilisé comme procédé de régénération. Par contre, les catalyseurs ont conservé leur activité catalytique, en utilisant la calcination comme méthode de régénération, ce qui indique qu’une des causes de désactivation des catalyseurs Au/MSM pourrait être due à une forte adsorption d’espèces organiques sur la surface des catalyseurs. De plus des quantités significatives d’or ont été trouvées dans la solution après des cycles de réaction consécutifs, ce qui démontre la désactivation est aussi due à la lixiviation de la phase active dans la solution de réaction. Les données expérimentales ont révélé que tant l’EDMB que la technologie d’échange d’ions pourraient être utilisées pour produire l’ALB à partir de son sel de sodium. Cependant, en tenant compte du fait que l’EDMB a été utilisée pour la première fois pour cette application, ce procédé a donc besoin d’une amélioration pour des applications industrielles. En effet, une déminéralisation de 50% a été atteinte après l’application d’une différence de potentiel de 5.0-5.5 V pendant 100-180 min aux bornes d’une cellule d’électrodialyse à trois compartiments, tandis que la solution de lactobionate de sodium a été complètement dépourvue de sodium après 10-30 min, lorsqu’on a utilisé une résine échangeuse de cations commerciale fortement acide (AmberliteTM FPC23 H).
The worldwide surplus and low cost of lactose have drawn the attention of researchers and industry to develop innovative processes for the production of value-added lactose derivatives, such as lactobionic acid (LBA), which is a high value-added product obtained from lactose oxidation, with excellent properties for applications in the food and pharmaceutical industries. Investigations on LBA production by means of catalytic oxidation of lactose over palladium and bismuth-palladium supported catalysts have shown good conversion rates and selectivities towards LBA, but the main problem of these catalysts is their instability by leaching and deactivation by over-oxidation during the reaction. Supported gold catalysts have shown to outperform palladium and bismuth-palladium catalysts for the oxidation of carbohydrates. However, there is still a big challenge in finding a robust catalyst for the lactose oxidation. In this dissertation, new gold catalysts supported on mesoporous silica materials (Au/MSM) have been synthesized by two different methods, and evaluated as catalysts in the oxidation of lactose. The catalytic materials were characterized by nitrogen physisorption, XRD, FTIR, TEM and XPS. The effects of the operating conditions such as temperature, pH, gold loading and catalyst/lactose ratio on the lactose conversion were investigated. Finally, the demineralization process of the sodium lactobionate solution obtained at the reactor outlet has been studied using two approaches: bipolar membrane electrodialysis (BMED) and ion-exchange technology. Highly active Au/MSM were successfully formulated by the co-condensation of a mixture of bis [3-(triethoxysilyl) propyl] tetrasulfide (BTESPTS), tetraethyl orthosilicate (TEOS) and the gold precursor (HAuCl4) in acidic media, using the triblock co-polymer EO20PO70EO20 as template. It was found that by increasing the BTESPTS/TEOS molar ratio, the structure of the synthesized materials changed from a highly ordered 2D hexagonal structure to a mixed hexagonal-vesicle and cellular foam structure. Under the optimal operating conditions (gold loading = 0.7%wt, T = 65ºC, catalyst/lactose ratio = 0.2, pH = 8-9, air flow = 40 mL·min-1), the lactose was completely converted into LBA after 80-100 min reaction, when using the catalysts synthesized from mixtures containing 6-10% molar concentration of BTESPTS. These catalytic materials were characterized by the predominance of a wormhole-like structure, favorable for the reagent accessibility to the gold nanoparticles (AuNPs) of about 8 nm intercalated in the silica walls. AuNPs of about 5-6 nm were also successfully loaded of mesoporous SBA-15 and SBA-15-CeO2 materials, by the wet adsorption of the gold cationic complex [Au(en)2]3+ (en=ethylenediamine) in alkaline media. These catalysts retained the well-ordered 2D hexagonal structure typical of SBA-15, and showed high activity to lactose oxidation. After 60 min of reaction, the Au/SBA-15-CeO2 catalysts (Ce/Si = 0.2) showed the highest catalytic activity (100% lactose conversion) and 100% selectivity towards LBA, when used at the optimal operating reaction conditions described above. These results suggest that ceria plays a role in the enhancement of the catalytic activity, where the coordination and agglomeration states of Ce atoms could have an important effect. In general, the XPS study on the oxidation states of gold on the Au/MSM surfaces revealed the coexistence of metallic and oxidized Au species, whose relative abundance followed the order Au0 >>>Au+1 > Au+3. In the case of Au/SBA-15-CeO2 catalysts, the presence of both Ce3+ and Ce4+ oxidation states was also observed. Catalysts’ recycling experiments showed that the activity of Au/SBA-15 and Au/SBA-15-CeO2 was significantly reduced (40-65%) after consecutive oxidation reaction cycles, when washing with water was used as regeneration process. On the contrary, these catalytic samples conserved their catalytic activity when calcination was used as regeneration method, indicating that one of the causes of deactivation of Au/MSM might be the strong adsorption of organic species on the catalyst surface. Moreover, significant amounts of Au were found in the solution after consecutive reaction cycles, demonstrating that the leaching of the active phase into the reaction solution is another important cause of the catalyst’ deactivation. Experimental data showed that both BMED and ion exchange technology might be used for producing LBA from its sodium salt. However, taking into account that it is the first time that BMED is used for this application, this process still needs further improvement for industrial applications, since a demineralization rate of 50% was achieved after applying a voltage difference of 5.0-5.5 V during 100-180 min to a three-compartment electrodialysis stack, while a complete sodium removal was achieved after 10-30 min when using a commercial strong cation exchange resin (AmberliteTM FPC23 H).

Magnetic separation has received a lot of attention as a robust, highly efficient and rapid catalyst separation technology. Many studies have focused on developing methodologies for the immobilization of catalytic active species, but the development of magnetic supports has been mainly limited to silica, polymer or carbon-coated magnetic nanoparticles (NPs). The design of magnetic nanocomposites and the incorporation of other oxides are highly welcome to broaden the application of this separation technology in the field of catalysis. In this context, studies of the thermal stability of silica-coated magnetite (Fe3O4@SiO2) were performed to evaluate the possibility of calcining it without losing the magnetic properties of the support. The calcination would permit the deposition of different oxides on the silica surface, such as ceria and titania. The calcined Fe3O4@SiO2 material preserved the core-shell morphology and magnetic properties, but increased its surface area six times. New magnetic supports were developed by using post-coating process for the deposition of ceria and titania onto silica-coated magnetite. Magnetically recoverable Rh, Pd and Ru nanocatalysts were prepared. The catalysts were employed in hydrogenation of cyclohexene, benzene or phenol and the study of the influence of each support on the catalytic activity was a main objective of this thesis. The catalysts were prepared by two different approaches: the impregnation and the sol-immobilization of pre-formed metal NPs. The colloidal metal NPs were prepared by reduction of metal salts and also by decomposition of organometallic complexes. Rhodium catalysts prepared by impregnation of rhodium(III) chloride and reduction with H2 showed some reproducibility issues that were surpassed by using NaBH4 or hydrazine as reducing agents. The preparation of catalysts by the immobilization of colloidal NPs is an interesting alternative to obtain reproducible and very active catalysts. Nanoparticles of Pd, Rh and Ru were prepared by an organometallic approach and immobilized on calcined Fe3O4@SiO2, Fe3O4@SiO2CeO2 and Fe3O4@SiO2TiO2. The elimination of the stabilizing agent leads to more active catalysts upon recycling. Rhodium catalysts supported on ceria support was the most active catalyst in the hydrogenation of cyclohexene (TOF 125,000 h-1). Palladium catalysts were the most selective catalyst for the hydrogenation of phenol to cyclohexanone, no matter the support used. The formation of cyclohexanol is enhanced with titania and the hydrodeoxygenation to produce cyclohexane occurred mainly with silica.
A separação magnética tem recebido muita atenção como uma tecnologia robusta, altamente eficiente e rápida para recuperar catalisadores sólidos após uso em reações em fase líquida. Muitos estudos têm focado nas metodologias para a imobilização de espécies cataliticamente ativas, mas o desenvolvimento de suportes magnéticos tem se limitado a nanopartículas magnéticas revestidas com sílica, polímeros ou carbono. O desenvolvimento de nanocompósitos magnéticos com a incorporação de outros óxidos é muito desejável para ampliar a aplicação dessa tecnologia de separação em catálise. Nesse contexto, estudos da estabilidade térmica de magnetita revestida com sílica (Fe3O4@SiO2) foram realizados para avaliar a possibilidade de calcina-la sem perder as propriedades magnéticas do suporte. Uma etapa de calcinação é necessária para a deposição de diferentes óxidos na superfície da sílica, tais como céria e titânia. O Fe3O4@SiO2 calcinado preservou a morfologia \"core-shell\" e as propriedades magnéticas, porém apresentou um aumentou de seis vezes na área superficial. Novos suportes magnéticos foram desenvolvidos pela deposição de céria e titânia sobre magnetita previamente revestida com sílica. Nanocatalisadores magneticamente recuperáveis de Rh, Pd e Ru foram preparados. Os catalisadores foram utilizados na hidrogenação de ciclo-hexano, benzeno ou fenol e o principal objetivo dessa tese foi o estudo da influência de cada suporte na atividade catalítica. Os catalisadores foram preparados de duas formas diferentes: impregnação-redução e imobilização de nanopartículas (NPs) metálicas pré-formadas. As NPs coloidais foram preparadas pela redução de sais metálicos e, também, pela decomposição de complexos organometálicos. Catalisadores de ródio preparados pela impregnação de cloreto de ródio(III) e redução com H2 mostraram alguns problemas de reprodutibilidade, que foram superados utilizando NaBH4 ou hidrazina como agentes redutores. A preparação de catalisadores pela imobilização de NPs coloidais é uma alternativa interessante para obter catalisadores reprodutíveis e muito ativos. Nanopartículas de Pd, Rh e Ru foram preparadas a partir de organometálicos e imobilizadas em Fe3O4@SiO2 calcinada, Fe3O4@SiO2CeO2 e Fe3O4@SiO2TiO2. A eliminação do agente estabilizante torna os catalisadores mais ativos durante os reusos. O catalisador de Rh sobre o suporte de céria foi o catalisador mais ativo na hidrogenação de ciclohexeno (TOF 125000 h-1). O catalisador de Pd foi o catalisador mais seletivo para a hidrogenação de fenol em ciclo-hexanona, independente do suporte usado. A formação de ciclo-hexanol é favorecida pelo suporte de titânia e a hidrodesoxigenação para produzir ciclo-hexano ocorreu principalmente no suporte de sílica.

Les nanofils de silicium et de germanium présentent un fort potentiel technologique, d'autant plus important que leur position et leur taille sont contrôlées. Dans le cadre de cette thèse, la croissance de ces nano-objets a été réalisée par dépôt chimique en phase vapeur sous ultravide à l'aide d'un catalyseur d'or via le mécanisme vapeur-liquide-solide.Dans un premier temps, différentes techniques, le démouillage d'un film mince, l'évaporation par faisceau d'électrons et l'épitaxie par jet moléculaire, ont été mises en œuvre pour l'obtention du catalyseur métallique pour la croissance des nanofils.Dans un deuxième temps, la cinétique de croissance des nanofils de silicium a été étudiée en fonction de la pression, de la température de croissance et du diamètre des gouttes. Le gaz précurseur qui a été utilisé est le silane. Cette étude a permis de déterminer un diamètre critique de changement de direction de croissance, au-dessus duquel les nanofils sont épitaxiés sans défauts cristallins et préférentiellement selon la direction <111>. Le diamètre critique a été estimé à 80 nm. La cinétique de croissance en fonction de la pression a pu être interprétée de façon satisfaisante par la relation de Gibbs-Thomson. Ceci a permis la détermination du coefficient de collage des molécules de silane sur la surface de l'or et la pression de vapeur saturante du silicium P∞. Le changement morphologique de la section du nanofil et la distribution de nanoclusters d'or sur les parois ont été aussi détaillé à l'aide d'analyses par microscopie électronique en transmission.L'intégration des nanofils dans un dispositif nécessite de pouvoir les connecter. Pour les localiser et les orienter, un procédé basé sur le procédé d'oxydation localisée du silicium est proposé, pour former des ouvertures Si(111), à partir d'un substrat Si(001). Les gouttes d'or sont alors localisées dans ces ouvertures et vont servir à la croissance de nanofils orientés suivant une seule des directions [111]. Enfin, la cinétique de croissance de nanofils de germanium a été étudié. La limitation de l'utilisation du germane dilué à 10% dans l'hydrogène dans notre système d'épitaxie UHV-CVD a été démontrée. Compte tenu de notre dispositif expérimental, le gaz précurseur a été changé pour du digermane dilué à 10% dans de l'hydrogène afin de favoriser une croissance verticale de nanofils de Ge. Ceci nous a permis d'élaborer des nanofils de Ge avec des vitesses de croissance pouvant atteindre 100 nm/min. Des analyses structurales montrent l'existence d'un évasement des nanofils. Ceci est engendré par la présence d'une croissance latérale qui augmente avec la température. Comme dans le cas des nanofils de Si, nous observons la présence de l'or sur les parois latérales des nanofils. Cependant la présence de l'or est limitée à la partie supérieure des nanofils. Cette diffusion des nanoclusters d'or sur les parois peut être diminuée en augmentant la pression de croissance. En outre, l'étude de la vitesse de croissance des nanofils de Ge en fonction du rayon des gouttes d'or a permis de déterminer un rayon critique de 6 nm en dessous duquel la croissance de nanofil ne peut avoir lieu. Ce résultat a été interprété à l'aide d'un modèle basé sur l'effet Gibbs-Thomson et prenant comme hypothèse que l'étape limitante dans la croissance vapeur-liquide-solide est l'adsorption et l'évaporation du germanium.

Yolk-shell nanostructures/yolk-shell nanoparticles are defined as a hybrid structure, a mixture of core/shell and hollow particles, where a core particle is encapsulated inside the hollow shell and may move freely inside the shell. Of the various classifications of yolk-shell nanostructures, a structure with an inorganic core and inorganic shell (inorganic/inorganic) has been studied widely due to their unique optical, magnetic, electrical, mechanical, and catalytic properties. In the work presented here, among the different inorganic/inorganic yolk-shell nanostructures noble metal@silica yolk-shell nanostructures has been chosen as the topic of interest. Silica shell possesses many advantages such as chemical inertness, tunable pore sizes, diverse surface morphologies, increasing suspension stability, no reduction in LSPR properties of noble metal nanoparticles when used as a coating for such particles. Noble metal nanoparticles such as AgNPs and AuNPs, on the other hand, possess unique structural, optical, catalytic, and quantum properties. Hence yolk-shell nanostructures with a combination of Ag or Au core and a silica shell (Ag@SiO2 and Au@SiO2) would open to endless possibilities. In this study, four areas were mainly explored: mechanism of silica shell formation over a given template, the synthetic modifications of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, their application as a potential catalyst, and devising of a flow type catalytic reactor. Despite the growing number of contributions on the topic of yolk-shell nanostructures, particularly Au@SiO2 and Ag@SiO2 yolk-shell nanostructures, a potential for improvement lies in all four aforementioned areas. As an initial study, the effect of different processing conditions as well as the mechanism of silica shell formation over reactive block copolymer templates was investigated. An asymmetric PS-b-P4VP block copolymer was chosen as a structure directing component to deposit silica shell. In order to deposit silica shell, PS-b-P4VP micelles with a collapsed PS core and a swollen P4VP corona was prepared via a solvent exchange method. The growth of silica shell over the PS-b-P4VP micelles (reactive template) was done using in-situ DLS and TEM. The experimental data obtained revealed the 4 distinct stages involved in the silica shell formation over the reactive BCP micellar template starting from the accumulation of silica precursor around the P4VP corona followed by a reactive template mediated hydrolysis-condensation reaction of the silica precursor which eventually lead to the shell densification and shell growth around the micelles. An understanding of the mechanism of silica shell formation over reactive templates provides a direct way to encapsulate various active species such as metal nanoparticles and quantum dots and paves the way for the template mediated synthesis of hybrid nanostructures such as yolk-shell nanoparticles. These studies also serve as a platform to fine-tune the properties of such hybrid nanostructures by varying the reaction parameters during silica shell deposition and reaction time. The next part of the work focused mainly on the synthesis, process optimisation and characterization of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, and their potential use as a nanocatalyst. A well-known soft template mediated synthesis of the yolk-shell nanostructure was adopted for the present work. For this PS-b-P4VP micelle was used as a dual template for both encapsulation of nanoparticle and the deposition of silica shell. The nanoparticles were entrapped selectively to the BCP micellar core and silica deposition was done by reacting the nanoparticle-loaded micelles with an acidic silica sol which lead to the formation of Ag@PS-b-P4VP@SiO2 or Au@PS-b-P4VP@SiO2 particles with respect to the nanoparticle used. In the case of Ag@PS-b-P4VP particles, upon silica deposition, a partial dissolution of AgNPs was observed whereas AuNPs were stable against dissolution. Hence yolk-shell nanostructures with AuNPs were studied further. As-prepared Au@PS-b-P4VP@SiO2 particles were then subjected to pyrolysis to remove the BCP template. The resulting yolk-shell nanostructures comprised of an AuNP core and a hollow mesoporous silica shell. Upon removal of the BCP template, the Au@SiO2 particles fused together and formed large aggregates. The catalytic properties of Au@SiO2 yolk-shell nanoparticles were explored using a model reaction of reduction of 4-nitrophenol and proved to have good catalytic activity and efficient recyclability. It was observed that catalytic efficiency was hindered by the particle aggregates formed after pyrolysis by creating an inhomogeneity in the system and inaccessibility of the catalytic surface for the reactants. Hence synthetic modifications were needed to overcome such drawbacks. Next part of the work deals with the synthetic modification of Au@SiO2 yolk-shell nanoparticles done by embedding them in a porous silica structure (PSS). Such structural morphology was attained by gelating the excess silica precursor while synthesising the Au@PS-b-P4VP@SiO2 particles. The pyrolytic removal of block copolymer results in the formation of Au@SiO2@PSS catalyst and the porous nature of both the shell and the silica structure provides an easy access for the reactants to the nanocatalyst surface located inside. The catalytic properties of Au@SiO2@PSS were studied using a model reaction of catalytic reduction of 4-nitrophenol (4-NP) and reductive degradation of different dyes. Kinetic studies show that Au@SiO2@PSS catalyst possesses enhanced catalytic activity as compared to other analogous systems reported in the literature so far. Furthermore, catalytic experiments on the reductive degradation of different dyes show that Au@SiO2@PSS catalyst can be considered as a very promising candidate for wastewater treatment. Another proposed direction of applying the Au@SiO2 yolk-shells is by devising a continuous flow catalytic system composed of Au@SiO2 yolk-shell nanoparticles for the effective degradation of azo dyes as a promising candidate for wastewater treatment. This was done by infiltrating the Au@PS-b-P4VP@SiO2 particles inside a porous glass substrate (frits) and the subsequent pyrolytic removal of the BCP template resulting in the formation of Au@SiO2 yolk-shell nanostructures sintered inside the frit pores. The flow catalytic reactor was exploited in terms of studying its catalytic activity in the degradation of azo dyes and 4-nitrophenol and proved to have a catalytic efficiency of ca. 99% in terms of reagent conversion and has a long-term stability under flow. Thus, with a few modifications, these flow type systems can open the doors to a very promising continuous flow catalytic reactor in the future.

碩士
國立臺灣大學
化學研究所
99
In recent years, hollow nanostructures have been reported of their unique properties such as high surface-to-volume ratio and the large fraction of void space in hollow structure. Those materials could be used in various applications including catalysis, drug delivery, hydrogen storage, and rechargeable batteries. In general, the as-synthesized materials are prepared through coating the target materials on the templates. Then, hollow structures are obtained by removal of the templates. However, the synthetic procedures were complicated and involved numerous steps. It was difficult to reduce the particle size to 100 nm. Thus, those methods restricted the development of hollow nanostructure in the biomedical applications. Herein, we synthesized hollow silica nanospheres (HSNs) with tunable sizes from 25 nm to 170 nm by a one-step water in oil reverse microemulsion (W/O) method. The size of HSNs could be adjusted via three approaches: (1) changing the oil phase in the reverse microemulsion, (2) adjusting the volume of co-surfactant, and (3) varying the ratio of surfactant CA-520 to Triton X-100. The compositions and structures were characterized by different characterization techniques, such as transmission electron microscope (TEM), and nitrogen adsorption-desorption isotherms. Furthermore, the functional materials such as metal, metal oxide, drug, and protein could be encapsulated in the hollow silica nanospheres through this novel method. Hollow silica nanospheres have potential applications in catalysis, cell-labeling and drug delivery. Herein, we demonstrate its application in catalysis. The gold nanoparticle encapsulated in hollow silica nanospheres (Au@HSNs) were examined on p-nitrophenol reduction and CO oxidation reaction. The silica shell of hollow silica sphere protected the gold nanoparticle from sintering during calcination and reaction. In p-nitrophenol reduction, the Au@HSNs displayed high catalytic activity and resistance to DMSA (meso-2,3-dimercaptosuccinic acid) poisoning. In CO oxidation reaction, the catalyst performed amazingly at low-temperature CO oxidation even at -20℃, and displayed high stability after many catalytic cycles. Furthermore, the water vapor could not only enhance the catalytic activity but also be a switch to turn on/off the nanoreactor.

碩士
國立中正大學
化學暨生物化學研究所
104
In 1987, Japan scientist M. Haruta was the first person to use gold nanoparticles embedded in transition metal oxide to catalyze the oxidation of carbon monoxide. Haruta pointed out that the catalytic ability was related to the interaction between gold nanoparticles and metallic oxides. Gold nanoparticles could be a catalyst when the sizes of the particles are around 2 nm to 5 nm, according to the literature. Here, we examined the catalytical ability of mesoporous silica-coated gold nanorod (AuNR@SiO2) with diameter from 13 nm to 24 nm and found they could catalyze the oxidation of ethylene glycol (EG) to glycolaldehyde (GA). GA is the reducing agent for the wet chemical synthesis of silver nanocubes. However, GA is unstable and not commercially available. We obtained it only by heating the EG up to 150 ˚C, but the yield was hard to control. We examined if AuNR@SiO2 could be a catalyst for this reaction. We first used AuNRs with dimensions of 70 × 20 nm2 (aspect ratio of 3.5). Then, we coated the surface of AuNRs with a mesoporous silica shell to protect them from aggregation and destruction. The mesoporous pores in the silica shell serve as sieves and channels, allowing only small reagents pass through. We improved the method of 2,4-DNPH spectrophotometry for the detection of GA. We replaced extraction solvent of benzene with toluene and decreased the deterioration rate of products by using ice bath. We found that AuNR@SiO2 can decrease the reaction temperature from 150°C to as low as 60°C. We examined the recycling times of AuNR@SiO2. The preliminary results indicated that AuNR@SiO2 could be used for four times. So, the number of recycling are three. We further investigated the catalytic ability of AuNR@SiO2 with different sizes of AuNRs（length = 44 ~ 70 nm, diameter = 14 ~ 23 nm）. We found that catalytic ability of AuNR@SiO2 was mainly related to the adsorption of reactants to the whole surface of AuNRs, not particularly sensitive to the ends of the nanorods. Finally, we etched AuNRs in AuNR@SiO2 by using HCl and bubbling with O2. Etching made AuNRs shorter and forming a hollow space between AuNR and the silica shell. Then we found they have no catalytic ability. So, we thought that the catalytic ability of AuNR@SiO2 may be attributed to the synergic effect of the AuNRs with the silica shell in contact from the above experimental results. By using absorption spectra, we also found the amount of GA in EG that is heated in 150˚C for 1 hour is about 1/300000 of EG.

The development of cost-effective, efficient and stable materials helps to provide the affordable solutions to get safe and fresh water to increasing population with health guidelines of emerging contaminants. Nanomaterials (NMs)-based techniques involve the design, synthesis, manipulation, characterization and exploitation of materials for adsorption and separation of target species from the contaminated and waste water. NMs show better adsorption capacity and catalytic for number chemical species and microbes because of their small size and large surface area that favors the purification and treatment of waste or contaminated environmental water. Here, we present the chemical properties, adsorption/removal mechanism and applications of advanced NMs such as magnetic nanoparticles (MNPs), carbon nanotubes (CNTs), graphene and graphene oxide (GO), titanium oxide (TiO2), silica (SiO2), silver (Ag), gold (Au) NPs and zeolites in effective and efficient removal of toxic metal ions, organic and inorganic chemical substances and disease-causing microbes from contaminated and wastewater.

Abstract Since their introduction by M. J. O𠄙Donnell in the late 11970s, benzophenone Schiff bases have become increasingly useful as chiral intermediates for the enantioselective synthesis of unnatural amino acids. These sterically hindered Schiff bases (O𠄙Donnell𠄙s Schiff bases) are particularly convenient because of their good thermal stability, enhanced tolerance of moisture, stability during chromatography over silica gel, and their tendency to crystallize. As a protecting group, the benzophenone Schiff base is extremely versatile. The imine bond can be hydrolysed by use of a variety of acidic conditions, hydrogeno lysed at atmospheric pressures with Pd-C as catalyst, or may be reduced with metal hydrides (cf. LiAlH4, NaBH4 or NaH3BCN) to provide N-benzhydryl protected amines. (cf. Fig. 9.11) All these cleavage reactions proceed in excellent yield.

Recent increase in need for a portable power source drives research on micro fuel cell and micro fuel reformer as a key component of micro power generation system. Various concept of reforming system is proposed and has been studied. As an attempt to develop wafer based micro reforming system, preparation, coating, and patterning of Cu-based catalysts for methanol steam reforming for micro fuel reformer are presented. Preliminary step to develop MEMS based micro fuel reformer is carried. As a first step, Cu-based catalysts are prepared by co-precipitation method. The effect of precipitation condition on physical characteristics and catalytic activity of the catalyst such as particle size, conversion rate and quality of coating on substrate are reported. And then coating processes of prepared catalysts on glass and silicon wafer are developed. A uniform and robust catalyst layer is obtained. The amount of coated catalyst on unit area of wafer is measured to be 5∼8 mg/cm2, and the thickness of catalyst layer is about 50μm. By multiple coating processes, catalyst thickness can be controlled and up to 15mg/cm2 is obtained that has good reactivity. After then, patterning of coated catalyst layer is reported. Deposited catalyst layer is patterned by way of lift-off process of PVA (Poly-Vinyl Alcohol), organic sacrificial layer, by heating the substrate instead of etching a sacrificial layer. With the results aforementioned on catalyst preparation, coating, and patterning, a prototype micro catalytic reactor for micro fuel reformer is fabricated with MEMS technology. The fabrication process includes wet anisotropic etching of photosensitive glass wafer, coating/patterning of catalyst and bonding of layers. Next step that is challenging part of development of micro reformer is to find a way to overcome the effect of heat loss that lowers the conversion rate of reforming process and to achieve fast kinetics for reduction of the device scale. We are pursuing further optimization of structural design to improve conversion efficiency and to obtain fast kinetics.

Climate change is one of the biggest global challenges. As a result of human activity, large amounts of greenhouse gases are released into the atmosphere, contributing to global warming. Carbon dioxide (CO2) is a major greenhouse gas, therefore, hydrogenation of CO2 to value-added chemicals and liquid fuels is of great importance for a sustainable future. It is well known that iron-based catalysts can demonstrate good activity in the hydrogenation of CO2. However, catalysts need to be improved to promote the formation of liquid hydrocarbons. In this study, a series of silica supported iron catalysts promoted with potassium were prepared by impregnation method. The samples were characterized by X-ray fluorescence spectroscopy, X-ray diffraction, and N2 adsorption-desorption analysis. Catalytic performance of K-0, K-2, and K-5 was investigated for CO2 hydrogenation in a fixed bed reactor operated at 300 degrees Celsius and 20 bar. The reaction products were analysed by gas chromatography and FT-IR spectroscopy. The results showed that promotion with potassium reduces the selectivity of methane and reduces the amount of gas phase hydrocarbons. At the same time promotion with potassium contributed to the formation of alcohols in the liquid phase products. The highest methanol yield was obtained using the K-2 catalyst, while the K-5 catalyst promoted the formation of both methanol and ethanol in the liquid phase.

Silicon is an excellent transparent material for building IR micro-optical elements such as holographic and blazed gratings, and curvilinear micro-lenses. Shaping this material in 3D with mirror quality finish and single-digit microscale resolution is challenging due to its brittleness and high-melting point. To achieve these patterning characteristics, electron-beam grayscale lithography is typically selected to pattern a 2.5D feature onto a resist thin-film. Subsequently, the film features are transferred into the underlying silicon substrate by deep-reactive ion etching (DRIE) [1]. Small variations in the resist thickness lead to large shape distortions and reduced patterning repeatability. Further, the direct-write nature of e-beam lithography provides for slow throughput. Developing an alternative, parallel and scalable method to nanopatterning silicon with 2.5D geometrical control may impact emerging areas such as the design of sub-wavelength photonic and micro-optic elements for silicon photonics applications. Micro and nanoscale patterning of inorganic semiconductors (e.g. Silicon) requires traditional micromachining processes such as plasma-assisted etching (e.g. DRIE) and wet-etching (e.g. KOH etching). Neither of the aforementioned processes offer the capability to control the geometry in 3D with resolution in the nanoscale range. Thus, it is desirable to develop a low-temperature, low-stress and ambient approach to nanostructuring silicon in 3D. Wet etching approaches are good candidates for achieving such goal because they bypass the need for high-temperature processing and stressing materials beyond the elastic limit. Yet, they still rely on lithographical steps and offer limited sidewall control, restricting the scope of features it can produce. In recent literature, catalyst-based wet etching processes such as metal-assisted chemical etching (MACE) have been shown to pattern high-aspect ratio structures in semiconductors [2–3]. Some researchers have achieved control over the etch profile and etching direction, generating a limited set of interesting 3D objects [4–6]. The degrees of freedom in MACE patterning are still highly constrained due to limited control of the catalyst motion. Additionally, thin-film based MACE relies on intermediate 2D masking steps to pattern the catalyst which are often lithographical. Thus, this indirect approach to patterning silicon increases lead time and processing costs. In this paper, Mac-imprint, a direct imprint configuration of MACE, is introduced to overcome these fundamental barriers. It relies on the use of a catalytic stamp immersed in the etchant and brought against a silicon chip to selectively dissolve it at contact points. Stamps can be reused multiple times to pattern substrates with lifetimes that are dependent solely on its chemical and mechanical degradation. This process is inherently non-lithographic and occurs at room temperature. As a demonstration of its high-resolution capabilities, silicon wafers were patterned with a sinusoidal wave whose pitch and amplitude were 1 μm and 250 nm, respectively. The patterned surface RMS error from the ideal surface was measured to be 13 nm. The key drawback of this approach is the generation of porous defects near the vicinity of the contact interface between stamp and substrate. Its spatial distribution is qualitatively discussed in the context of the diffusion model of MACE [7].

The transformation of para-aminothiophenol (PATP) to dimercaptoazobenzene (DMAB) is widely believed to be due to the emission of hot electrons from the plasmonic nanostructures,1 which are generated during the decay of the surface plasmons (LSPPs). Our aim here is to separate the catalytic activity of plasmonic nanostructures from their SERS activity by using a 5 nm thick silicon dioxide (SiO2) layer. This layer blocks hot electrons from reaching the PATP molecules but lets the electromagnetic field penetrate, allowing us to measure the SERS of the monomer without triggering a chemical reaction. The SERS measurement was performed at 633 nm on two-dimensional gold nanoparticle (2D AuNP) arrays covered with/without thin SiO2.

Abstract As part of circular model for E&P, production sand waste from oil production process will be converted to new high value-added product, called "Nanosilica", and "Hierarchical Zeolites". This is beneficial in terms of lower amount of production sand waste disposal to landfill. There are three main steps for sand conversion to nanosilica and hierarchical zeolites which compose of1) Sand Pre-treatment, 2) Nanosilica Extraction, and 3) Hierarchical Zeolite Synthesis. In the first step of Sand Pre-treatment process, production sand was pretreated by using water and acid washing 3M HCl, follow by calcination. Secondly, pretreated sand will be extracted to obtain nanosilica by boiling pretreated sand with 3M NaOH solution to get sodium silicate, and finally adding HCl to precipitate nanosilica. Finally, the extracted nanosilica will be further reacted with Structure Directing Agent (SDA); zeolite template, under hydrothermal treatment process for crystallization of Hierarchical Zeolites. Nanosilica extracted from production sand contain high specific surface area around 200 – 600 m2/g, with small particle size less than 50 nm. Nanosilica can be applied in many applications such as Gas separation, Adsorption, Catalysis, Ion-exchange, and Detergent. Hierarchical Zeolites with nanosheets morphology obtain many niche characteristics to overcome the limitation of conventional zeolites in terms of, 1) good mass transportation through active sites due to their microporous structure improvement, 2) high surface area, and 3) longer catalyst lifetime. Hierarchical Zeolites is popularly used in wide range of applications such as separation, ion-exchange to catalysis. Two most popular Hierarchical Zeolites nanosheet ZSM-5, and Faujasite (FAU) topologies have been developed in this work. The physicochemical properties were compared with the one synthesized using the commercial chemical grade of silica sources. The results show that the nanosilica from production sand can be achievable for Hierarchical Zeolites synthesis, by comparing the physicochemical properties such as surface area, porosity, topology, and textural properties with the one obtained using the commercial silica sources. Hierarchical zeolites from production sand waste are initiated in PTTEP as part of Circular Model for E&P. The synthesized hierarchical zeolites from this project will be further possibly applied in-house in PTTEP as the moisture adsorbent in instrument air, or moisture in condensate. This would help company for reduce OPEX cost. From these preliminary findings, all information will be further applied to the process design of in prototype, and scale-up phase.

We present laser-assisted direct synthesis of nanowires with site-, composition-, and shape-selectivity on a single substrate by employing a spatially confined laser heat source. Laser-assisted nanowire growth based on vapor-liquid-solid mechanism is conveniently studied with multiple growth parameters such as temperature, time, and illumination direction. On-demand direct integration of silicon and germanium nanowires are demonstrated in a hetero-array configuration by simply switching the reactant gases as the growth of nanowires is limited within the heat-affected zone induced by the laser. Since laser-induced local temperature field is able to drive the individual growth, each germanium nanowire is successfully synthesized with distinctively different geometric features from cylindrical to hexagonal pyramid shape. By regularly patterning gold catalysts prepared by electron beam lithography on Si(111), especially, we accomplished site- and shape-selective direct integration of germanium nanowires on a single substrate in vertical architecture. Considering that blanket furnace heating only produce nanowires with uniform size and shape, therefore, our work shows a route toward the facile fabrication of multifunctional nanowire based devices.

We demonstrate the possibility of making conductive and dry adhesive interfaces between multiwalled carbon nano-tube (MWNT) and nanofiber (MWNF) arrays grown by chemical vapor deposition with transition-metal as catalyst on silicon substrates. The maximum observed adhesion force between MWNT and MWNF surfaces is 3.5 mN for an apparent contact area of 2 mm by 4 mm. The minimum contact resistance measured at the same time is ∼20 Ω. Contact resistances of MWNT-MWNT and MWNT-gold interfaces were also measured as pressure forces around several milli-Newton were applied at the interface. The resulting minimum contact resistances are on the same order but with considerable variation from sample to sample. For MWNT-MWNT contacts, a minimum contact resistance of ∼ 1 Ω is observed for a contact area of 2 mm by 1 mm. The relatively high contact resistances, considering the area density of the nanotubes, might be explained by the high cross-tube resistances at the contact interfaces and limited inter-penetration of the nanotube arrays.