Scientific Bases for the Preparation of Heterogeneous Catalysts

Proceedings of the 10th International Symposium, Louvain-la-Neuve, Belgium, July 11-15, 2010

E. Gaigneaux, M Devillers, S. Hermans, P.A. Jacobs, J. Martens, P. Ruiz

• Publisher: Elsevier
• Year: 2010
• Print ISBN:
  9780444536013
• eBook ISBN:
  9780444536020
• Topic: Technology & Engineering
• Subtopic: Industrial & Technical Chemistry
• Index: Technology & Engineering

These meetings, held every four years, bring together researchers from academia and industry and offer a forum for discussions on the chemistry involved in the preparation of industrial heterogeneous catalysts. Contributions focus on the aspects of catalyst preparation. Reports on physico-chemical characteristics of catalysts and catalytic performances are limited to correlations with the preparation parameters. - Contains a collection of the papers presented at the workshop

Effect of the carbon nanotube basicity in Pd/N-CNT catalysts on the synthesis of R-1-phenyl ethyl acetate

Serap Sahin^a; Päivi Mäki-Arvela^a; Jean-Philippe Tessonnier^b; Alberto Villa^b; Lidong Shao^b; Dang Sheng Su^b; Robert Schlögl^b; Tapio Salmi^a; Dmitry Yu. Murzin^{a a} Process Chemistry Centre, Åbo Akademi University, Turku, FI-20500, Finland
^b Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradagweg 4–6, 14195 Berlin, Germany

Abstract

Catalytic activities of palladium catalysts supported on activated carbon and carbon nanotubes were investigated in the one-pot synthesis of R-1-phenylethyl acetate in combination with an immobilized lipase in toluene. Palladium catalysts on carbon nanotubes with nitrogen-containing surface groups were prepared by incipient wetness impregnation. The basic N-CNT support was synthesized by post-treating oxidized CNTs in gaseous NH₃ at high temperature, prior to Pd addition. The basic character of the support was adjusted by controlling the temperature of the post-treatment step. The results showed that the desired product yield was enhanced over palladium catalysts with the lowest basicity.

Keywords

one-pot cascades

carbon nanotubes

immobilized lipase

acetophenone

1 Introduction

Cascade methodology, implying several reactions in one reactor pot, has gained interest recently due to the savings in equipment and separation costs in particular for production of fine chemicals. One of the ways to utilize cascades efficiently is to combine biological and chemical (i.e. heterogeneous and homogeneous) catalysis [1]. Synthesis of the R-1-phenylethyl acetate, which is an important building block for the production of biologically active pharmaceuticals, was studied over a heterogeneous palladium (Pd) catalysts supported on carbon nanotubes (or activated carbon) in combination with an immobilized lipase in one-pot under mild reaction conditions.

Pd supported catalysts on activated carbon (AC) have been widely studied as catalysts for hydrogenation, dehydrogenation and oxidation reactions for the production of fine chemicals [2]. Activated carbons as catalyst supports present several advantages being relatively inexpensive and inert materials [3]. However, they also exhibit a major drawback as their surface properties can vary from batch to batch. Furthermore, typically Pd/AC catalysts exhibit acidic surface groups, such as carbonyl, carboxylic, phenolic hydroxyl, lactone and quinone groups [4]. It was recently reported that Brønsted acid sites enhance the hydrogenolysis of secondary alcohols, such as 1-phenylethanol, in the model reaction [5].

Carbon nanotubes (CNTs), thanks to their unique properties such as high surface area, electrical properties, high mechanical stability, and adjustable surface properties [2]. Pd has been deposited on CNTs with various methods such as incipient wetness impregnation [6], homogeneous deposition precipitation [6, 7], ion exchange [6, 8] and organometallic grafting [6, 9]. Typically, the dispersion of the metal can be improved by pre-treating the carbon nanotubes in order to introduce functional groups (e.g. oxygencontaining surface groups) to the surface to enhance interactions between the support and the catalyst precursor [10, 11].

In the present work, the catalytic activity of palladium catalysts either on activated carbon or carbon nanotubes was studied in the one-pot synthesis of R-1-phenylethyl acetate. The influence of the acid-base properties of the support on the catalytic activity has been investigated by treating oxidized CNTs with NH₃ at different temperatures in order to introduce various amounts of basic N-containing groups on the surface [12].

2 Experimental

2.1 Catalyst synthesis

CNTs were first oxidized with concentrated nitric acid at 100 °C for 2h. After washing and drying, the oxidized CNTs were further treated with gaseous ammonia at 200 °C, 400 °C or 600 °C, respectively [12]. 2% (w/w) Pd/N-CNT catalysts were subsequently prepared by incipient impregnation using an aqueous solution of Pd (NO₃)₂.2H₂O. After drying at room temperature for overnight, the samples were calcined in air at 350 °C for 2h and reduced in hydrogen at 400 °C for 2h. Part of the N-containing basic sites was lost during the calcination and reduction. For compariso...

Table of contents

• Cover image
• Title page
• Table of Contents
• Copyright page
• Foreword
• Organizing Committee
• The nanoscale integration of heterostructures in chemo- and bio-catalysis
• How the manufacturing technology of industrial catalysts can influence their mechanical strength
• Coating metallic foams and structured reactors by VOx/TiO2 oxidation catalyst: Application of RPECVD
• Washcoating of metallic monoliths and microchannel reactors
• Monolithic catalysts for the decomposition of energetic compounds
• Glass fiber materials as a new generation of structured catalysts
• A novel electrochemical route for the catalytic coating of metallic supports
• Solution Combustion Synthesis as intriguing technique to quickly produce performing catalysts for specific applications
• Impact of NO on the decomposition of supported metal nitrate catalyst precursors and the final metal oxide dispersion
• A novel approach to synthesize highly selective nickel silicide catalysts for phenylacetylene semihydrogenation
• Preparation of calcium titanate photocatalysts for hydrogen production
• A new procedure to produce carbon-supported metal catalysts
• Use of zeta potential measurements in catalyst preparation
• The superior activity of the CoMo hydrotreating catalysts, prepared using citric acid: what's the reason?
• Elucidation of the surface configuration of the Co(II) and Ni(II) aqua complexes and of the Cr(VI), Mo(VI) and W(VI) monomer and polymer oxo–species deposited on the titania surface during impregnation
• Innovative characterizations and morphology control of γ-AlOOH boehmite nanoparticles: towards advanced tuning of γ-Al2O3 catalyst properties
• Highly active and selective precious metal catalysts by use of the reduction-deposition method
• Investigation of the role of stabilizing agent molecules in the heterogeneous nucleation of rhodium(0) nanoparticles onto Al-SBA-15 supports
• Preparation of the polymer-stabilized and supported nanostructured catalysts
• Carbon nanotube-supported sulfided Rh catalysts for the oxygen reduction reaction
• Synthesis and characterization of highly loaded Pt/carbon xerogel catalysts prepared by the Strong Electrostatic Adsorption method
• Catalytic wet air oxidation of succinic acid over monometallic and bimetallic gold based catalysts: Influence of the preparation method
• Design of hierarchical functional porous mixed oxides from single precursors
• Hierarchical porous catalyst support: shaping, mechanical strength and catalytic performances
• Catalytic property of carbon-supported Pt catalysts covered with organosilica layers on dehydrogenation of organic hydride
• Molecular aspects of solid silica formation
• A novel continuous approach for the synthesis and characterization of pure and mixed metal oxide systems applied in heterogeneous catalysis
• Innovative preparation of Au/C by replication of gold-containing mesoporous silica catalysts
• TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 in aqueous solutions
• Metal complex-assisted polymerization of thermosetting resins: a convenient one-step procedure for the preparation of heterogeneous catalysts
• Synthesis and study of mesoporous WO3-ZrO2-SiO2 solid acid
• Citral hydrogenation over Pt-M/CeO2 catalysts (M= Zn, Zr)
• Foam-supported catalysts tailored for industrial steam reforming processes
• Synthesis of ordered nanostructured CuO-CeO2 catalysts by hard template method
• Fine-tuning of Vanadium Oxide Nanotubes
• Plasma-assisted design of supported cobalt catalysts for Fischer-Tropsch synthesis
• Chemical vapor deposition of Fe(CO)4(SiCl3)2 for the synthesis of hydrogenation catalyst made of highly dispersed iron silicide particles on silica
• Laser electrodispersion method for the preparation of self-assembled metal catalysts
• Nitrogen doped TiO2 photocatalyst prepared by low energy N+ implantation technique
• Preparation and characterization of shape-selective ZSM-5 catalyst for para-methyl ethylbenzene production with toluene and ethylene
• Microwave-assisted preparation of Mo2C/CNTs nanocomposites as an efficient support for electrocatalysts toward oxygen reduction reaction
• Laser-induced photocatalytic inactivation of coliform bacteria from water using pd-loaded nano-WO3
• Effect of the carbon nanotube basicity in Pd/N-CNT catalysts on the synthesis of R-1-phenyl ethyl acetate
• Metal-carbon nanocomposite systems as stable and active catalysts for chlorobenzene transformations
• Development and design of Pd-containing supported catalysts for hydrodechlorination
• Role of deposition technique and support nature on the catalytic activity of supported gold clusters: experimental and theoretical study
• Nanosized nickel ferrite catalysts for CO2 reforming of methane at low temperature: effect of preparation method and acid-base properties
• Hierarchical porous Ce-Zr materials for oxidation of diesel soot particulate
• The role of organic additives in the synthesis of mesoporous aluminas and Ni/mesoporous alumina catalysts
• Inverse replica of porous glass as catalyst support
• The use of small volume TOC analysis as complementary, indispensable tool in the evaluation of photocatalysts at lab-scale
• Enzymatic oxidation of phenols by immobilized oxidoreductases
• A coordinative saturated vanadium containing metal organic framework that shows a remarkable catalytic activity
• Influence of preparation conditions on properties of gold loaded on the supports containing group five elements
• High loaded Ni/SiO2 catalyst for producing ultra-pure inert gas
• The effect of 3d-cation modification on the properties of cordierite-like catalysts
• Large-scale synthesis of porous magnetic composites for catalytic applications
• Preparation of gallium oxide photocatalysts for reduction of carbon dioxide
• Catalytic combustion of methane on ferrites
• Polymer-based nanocatalysts for phenol CWAO
• A new sulphonic acid functionalized periodic mesoporous organosilica as a suitable catalyst
• Effect of the preparation procedure on the structural peculiarities and catalytic properties of Pt/(CeO2–TiO2) catalyst in CO oxidation
• Study of the sorption of Cu (II) species on the “TiO2/KNO3” interface
• Hydrogenation/Hydrogenolysis of benzaldehyde over CaTiO3 based catalysts
• VSbOx phases formed on MCM-41 supports
• Influence of the preparation conditions of Ca doped Ni/olivine catalysts on the improvement of gas quality produced by biomass gasification
• Effect of ethylenediamine as chelating agent of cobalt species upon the cobalt-support interactions: application to the VOC catalytic removal
• Influence of support on the ammoxidation activity of VPO catalysts
• Rationalization of the aqueous impregnation of molybdenum heteropolyanions on γ-alumina support
• Mesoporous SBA-15 silica modified with cerium oxide: Effect of ceria loading on support modification
• Synthesis and characterization of catalysts obtained by trifluoromethanesulfonic acid immobilization on zirconia
• Influence of precursor on the particle size and stability of colloidal gold nanoparticles
• V-Mo-Nb-W-containing hydrotalcite-like materials as precursors of catalysts for oxidative dehydrogenation of hydrocarbons and alcohols
• Synthesis of high-surface area CeO2 through silica xerogel template: influence of cerium salt precursor
• Iron based catalyst for hydrocarbons catalytic reforming: A metal-support interaction study to interpret reactivity data
• Ecofriendly catalysts based on mixed xerogels for liquid phase oxidations by hydrogen peroxide
• Preparation of MgF2-MgO supports with specified acid-base properties, and their influence on nickel catalyst activity in toluene hydrogenation
• Pd supported catalysts: Evolution of the support during Pd deposition and K doping
• Investigation of carbon and alumina supported Pd catalysts during catalyst preparation
• Advanced photocatalytic activity using TiO2/ceramic fiber-based honeycomb
• Incorporation of group five elements into the faujasite structure
• Glycerol conversion into H2 by steam reforming over Ni and PtNi catalysts supported on MgO modified γ-Al2O3
• Butyraldehyde production by butanol oxidation over Ru and Cu catalysts supported on ZrO2, TiO2 and CeO2
• Preparation of Au nanoparticles on Ce-Ti-O supports
• Preparation, active component and catalytic properties of supported vanadium catalysts in the reaction of formaldehyde oxidation to formic acid
• Investigation of different preparation methods of PtIr, PtIrSn and PtIrGe catalysts
• Perovskite-type catalysts for the water-gas-shift reaction
• Evaluation of different methods to prepare the Fe2O3/MoO3 catalyst used for selective oxidation of methanol to formaldehyde
• Formation of active component of MoVTeNb oxide catalyst for selective oxidation and ammoxidation of propane and ethane
• Functionalization of carbon nanofibers coated on cordierite monoliths by oxidative treatment
• Synthesis of mesoporous silicas functionalized with trans (1R,2R)-diaminocyclohexane by sol-gel method
• Physico-chemical and catalytic properties of effective nanostructured MnCeOx systems for environmental applications
• Novel method for doping of nano TiO2 photocatalysts by chemical vapor deposition
• Study on the preparation of active support and multi-porous supported catalyst
• The influence of preparation procedure on structural and surface properties of magnesium fluoride support and on the activity of ruthenium catalysts for selective hydrogenation of chloronitrobenzene
• Bimetallic Co-Mo-complexes with optimal localization on the support surface: A way for highly active hydrodesulfurization catalysts preparation for different petroleum distillates
• Mn, Mn-Cu and Mn-Co mixed oxides as catalysts synthesized from hydrotalcite type precursors for the total oxidation of ethanol
• Mesoporous manganese oxide catalysts for formaldehyde removal: influence of the cerium incorporation
• Nickel nanoparticles with controlled morphologies application in selective hydrogenation catalysis
• Behavior of NiMo(W)/Zr-SBA-15 deep hydrodesulfurization catalysts in presence of aromatic and nitrogen-containing compounds
• Effect of citrate addition in NiMo/SBA-15 catalysts on selectivity of DBT hydrodesulfurization
• Investigation of the microwave heating techniques for the synthesis of LaMnO3+δ
• The novel route of preparation of the supported gold catalysts by deposition-precipitation
• A new approach for the dispersion of VOPO4.2H2O through exfoliation and its catalytic activity for the selective oxidation of cyclohexane
• Mesoporous CuO-Fe2O3 composite catalysts for complete n-hexane oxidation
• Preparation of PtRu/C electrocatalysts by hydrothermal carbonization using different carbon sources
• Preparation of PtSn/C electrocatalysts using electron beam irradiation
• Preparation of PtSn/C skeletal-type electrocatalyst for ethanol oxidation
• Preparation of binary M/Mn (M = Co, Cu, Zn) oxide catalysts by thermal degradation of heterobimetallic complexes
• Preparation of highly active gas oil HDS catalyst by modification of conventional oxidic precursor with 1,5-pentanediol
• Hierarchical meso-/macroporous phosphated and phosphonated titania nanocomposite materials with high photocatalytic activity
• Gold and CuO nanocatalysts supported on hierarchical structured Ce-doped titanias for low temperature CO oxidation
• Facile preparation of MoO3/SiO2-Al2O3 olefin metathesis catalysts by thermal spreading
• Mesoporous TiO2-SBA15 composites used as supports for molybdenum-based hydrotreating catalysts
• p-Hydroxybenzoic acid degradation by Fe/Pd-HNT catalysts with in situ generated hydrogen peroxide
• Synthesis of ionic liquid templated zeolite like structures
• New class of acid catalysts for methanol dehydration
• One-Pot deposition of palladium on hybrid TiO2 nanoparticles: Application for the hydrogenation of cinnamaldehyde
• Catalytic activity of nanostructured Pd catalysts supported on hydrogenotitanate nanotubes
• Temperature – dependent evolution of molecular configurations of oxomolybdenum species on MoO3/TiO2 catalysts monitored by in situ Raman spectroscopy
• Preparation of nanosized bimetallic Ni-Sn and Ni-Au/SiO2 catalysts by SOMC/M. Correlation between structure and catalytic properties in styrene hydrogenation
• Microwave-assisted synthesis of Au, Ag and Au-Ag nanoparticles and their catalytic activities for the reduction of nitrophenol
• A new composite micro/meso porous material used as the support of catalyst for polyaromatic compound hydrogenation
• Photodeposition of Au and Pt on ZnO and TiO2
• Cellulose-templated materials for partial oxidation of methane: effect of template and calcination parameters on catalytic performance
• Highly porous hydrotalcite-like film growth on anodised aluminium monoliths
• The influence of impregnation temperature on the pzc of titania and the loading of Ni upon preparation of Ni/TiO2 catalysts
• Immobilization of homogeneous catalysts in nanostructured carbon xerogels
• Coating method for Ni/MgAl2O4 deposition on metallic foams
• Use of commercial carbons as template for the preparation of high specific surface area perovskites
• Ethyl acetate combustion catalyzed by oxidized brass micromonoliths
• Preparation of CMI-1 supported H3+xPMo12-xVxO40 for the selective oxidation of propylene
• Direct addition of the precursor salts of Mo, Co or Ni oxides during the sol formation of γ-Al2O3 and ZrO2 - The effect on metal dispersion
• Glycothermal synthesis as a method of obtaining high surface area supports for noble metal catalysts
• Synthesis and characterization of cok-12 ordered mesoporous silica at room temperature under buffered quasi neutral pH
• Spray drying of porous alumina support for Fischer-Tropsch catalysis
• Ni/SiO2 fiber catalyst prepared by electrospinning technique for glycerol reforming to synthesis gas
• Selective preparation of β-MoO3 and silicomolybdic acid(SMA) on MCM-41 from molybdic acid precursor and their partial oxidation performances
• Functionalization of carbon xerogels for the preparation of Pd/C catalysts by grafting of Pd complex
• Preparation of Pd-Bi catalysts by grafting of coordination compounds onto functionalized carbon supports
• Novel dicarboxylate heteroaromatic metal organic frameworks as the catalyst supports for the hydrogenation reaction
• Monitoring of the state of silver in porous oxides during catalyst preparation
• Strong electrostatic adsorption for the preparation of Pt/Co/C and Pd/Co/C bimetallic electrocatalysts
• Preparation of gold catalysts supported on SiO2-TiO2 for the CO PROX reaction
• A method of preparation of active TiO2-SiO2 photocatalysts for water purification
• n-Heptane hydroconversion on bifunctional hierarchical catalyst derived from zeolite MCM-22
• Preparation and characterization of nanocrystallines Mn-Ce-Zr mixed oxide catalysts by sol-gel method: application to the complete oxidation of n-butanol
• SCR activity of conformed CuOX/ZrO2-SO4 catalysts
• Pore design of pelletised VOX/ZrO2-SO4/Sepiolite composite catalysts
• Titanium oxide nanotubes as supports of Au or Pd nano-sized catalysts for total oxidation of VOCs
• Preparation of Alkali-M/ZrO2 (M = Co or Cu) for VOCs oxidation in the presence of NOx or carbonaceous particles
• Design of appropriate surface sites for ruthenium-ceria catalysts supported on graphite by controlled preparation method
• Preparation of monolithic catalysts for space propulsion applications
• Synthesis of mixed zirconium-silver phosphates and formation of active catalyst surface for the ethylene glycol oxidation process
• Characterization of cobalt nanoparticles on different supports for Fischer-Tropsch synthesis
• Enhanced dibenzothiophene desulfurization over NiMo catalysts simultaneously impregnated with saccharose
• Preparation of Pt on NaY zeolite catalysts for conversion of glycerol into 1,2-propanediol
• Alkali metal supported on mesoporous alumina as basic catalysts for fatty acid methyl esters preparation
• Modifications of porous stainless steel previous to the synthesis of Pd membranes
• Design of nano-sized FeOx and Au/FeOx catalysts for total oxidation of VOC and preferential oxidation of CO
• Supported Pd nanoparticles prepared by a modified water-in-oil microemulsion method
• Preparation of silica-coated Pt-Ni alloy nanoparticles using microemulsions and formation of carbon nanofibers by ethylene decomposition
• Sol-gel synthesis combined with solid exchange method, a new alternative process to prepare improved Pd/ZrO2-Al2O3-SiO2 catalysts
• Sol-gel synthesis of micro- and mesoporous silica in strong mineral acid
• Ag-V2O5/TiO2 total oxidation catalyst: autocatalytic removal of the surfactant and synergy between silver and vanadia
• Controlled synthesis of porous heteropolysalts used as catalysts supports
• Influence of the sodium-based precipitants on the properties of aluminum-doped hematite catalysts for ethylbenzene dehydrogenation
• Effect of the preparation method on the properties of hematite-based catalysts with lanthanum for styrene production
• Low-organics method to synthesize silver nanoparticles in an aqueous medium
• Clusters as precursors of nanoparticles supported on carbon nanofibers
• X-ray photoelectron spectroscopy study of nitrided zeolites
• Development of a modified co-precipitation route for thermally resistant, high surface area ceria-zirconia based solid solutions
• Deposition of gold clusters onto porous coordination polymers by solid grinding
• Influence of the preparation methods for Pt/CeO2 and Au/CeO2 catalysts in CO oxidation
• Author Index