Catalysis Volume 24

371 Pages·2012·13.356 MB·English

by  Kiyotaka Asakura, James J Spivey

Specialist Periodical Reports
Edited by J J Spivey and M Gupta
Catalysis
Volume 24
Catalysis
Volume 24

A Specialist Periodical Report
Catalysis
Volume 24
A Review of Recent Literature
Editors
James J.Spivey, Louisiana State University, USA
Mayank Gupta, Louisiana State University, USA
Authors
Kiyotaka Asakura, Hokkaido University, Japan
Perla B.Balbuena, Texas A&M University, College Station, Texas, USA
Alina Mariana Balu, Universidad de Cordoba, Spain
Miguel A. Ban˜ares, Institute of Catalysis and Petrochemistry (ICP) of the Spanish
Councilfor Scientific Research (CSIC), Madrid, Spain
Aurora Caldarelli, Universita`di Bologna, Italy
Rafael Callejas-Tovar, Texas A&M University, College Station, Texas, USA
Vanesa Calvino-Casilda, Institute of Catalysis and Petrochemistry (ICP) of the
Spanish Council for Scientific Research (CSIC), Madrid, Spain
Juan Manuel Campelo, Universidad de Cordoba, Spain
Fabrizio Cavani, Universita`di Bologna, Italy
Carlotta Cortelli, Polynt SpA, Scanzorosciate (BG), Italy
Federico Cruzzolin, Polynt SpA, Scanzorosciate (BG), Italy
Olaf Deutschmann, Karlsruhe Institute of Technology (KIT), Germany
Cristina Freire, Universidade do Porto, Portugal
Maria Dolores Gracia, Universidad de Cordoba, Spain
Gabriela Guillena, Universidad de Alicante, Spain
Wenta Liao, Texas A&M University, College Station, Texas, USA
Elia Losada, Universidad de Cordoba, Spain
Silvia Luciani, Universita`di Bologna, Italy
Rafael Luque, Universidad de Cordoba, Spain
JulibethM.MartinezdelaHoz,TexasA&MUniversity,CollegeStation,Texas,USA
Clara Pereira, Universidade do Porto, Portugal
Antonio Pineda, Universidad de Cordoba, Spain
Diego J.Ramo´n, Universidad de Alicante, Spain
Susana Rebelo, Universidade do Porto, Portugal
Antonio Angel Romero, Universidad de Cordoba, Spain
Juan Carlos Serrano-Ruiz, Universidad de Cordoba, Spain
Miguel Yus, Universidad de Alicante, Spain
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ISBN: 978-1-84973-375-5
DOI: 10.1039/9781849734776
ISSN: 0140-0568
A catalogue record for this book is available from the British Library
& The Royal Society of Chemistry 2012
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Preface
James J. Spivey and Mayank Gupta
DOI: 10.1039/9781849734776-FP005
This volume consists of reviews of topics of current interest to catalysis
researchers, specifically Total Reflection Fluorescence Extended X-ray
Absorption Fine Structure (PTRF-EXAFS), effects of continuously chan-
ging surface during oxidation using DFT and MD simulation methods,
operando Raman spectroscopy, the selective oxidation of o-xylene to
phthalicanhydride,catalyticreformingoflogisticfuelsathigh-temperature,
progressonthedesignandcatalyticactivityofrecyclablehybridcatalysts,
origin of the coverage dependence for atomic adsorbates on late transition
metal surfaces, and catalytic applications of mesoporous silica-based
materials.
In the first chapter, Kiyotaka Asakura (Hokkaido University, Japan)
discusses polarization-dependent Total Reflection Fluorescence Extended
X-ray Absorption Fine Structure (PTRF-EXAFS) and its application to
supported catalysts. PTRF-EXAFS is a powerful characterization techni-
quewhichrevealsthebondingcharacterofthemetal-supportinteractionin
metal species on single crystal oxide supports. In addition, this technique
producesathree-dimensionalstructureofmetalspeciessupportedonoxide
surfaces. Several examples of metal-support interaction and three-dimen-
sional structures of supported species determined by the PTRF-EXAFS
techniquearereviewed.FinallythefutureofPTRF-EXAFSincombination
with the next generation light sources, such as X-ray free electron laser
(XFEL) and energy recovery linac (ERL), is discussed.
InChapter2,RafaelCallejas-Tovar,WentaLiao,JulibethM.Martinezde
la Hoz, and Perla B. Balbuena (Texas A&M University, College Station,
USA) report the effects of continuously changing surface during oxidation
using DFT and MD simulation methods. They modeled the oxidation of
Pt-based alloy surfaces for fuel cell cathode electrocatalysts. They have
found that as the degree of surface oxidation increases, surface atoms
experience different degrees of buckling which is enhanced by the presence
of hydronium and other oxidants such as chloride ions. Buckling is a dis-
tortion of the position of the metal atoms with respect to the crystal
structure.Thedetachmentofbuckledatomsisfavoredbyinteractionswith
the solvent and other non-reacting species. In the case of alloys, large sur-
facemodificationsareobservedduetomigrationofnon-noblemetalsfrom
the core towards the surface. To develop an improved understanding of
theseproblems,theauthorshavedevelopedanewapproachthatusesDFT
todescribeelectronicchargesonsurface,subsurface,andoxygenatomsand
toevaluatethestructureanddynamicsofthecatalystforpurePt(111)and
an alloy: Pt/PtCo/Pt Co under increasing oxidation conditions, using
3
classical MD simulations.
Vanesa Calvino-Casilda and Miguel A. Ban˜ares (Instituto de Catalisis y
Petroleoquı´mica, CSIC, Spain) review recent advances in imaging and
monitoring of heterogeneous catalysts with Raman spectroscopy.
Catalysis, 2012, 24, v–viii | v
(cid:2)c TheRoyalSocietyofChemistry2012
Specifically,thischapterpresentstheprogress,challengesandopportunities
of operando Raman spectroscopy during reaction and temperature-
programmed treatments for heterogeneous catalysts (solid-gas and solid-
liquid). Its combination with complementary techniques such as EXAFS
andXANESisalsodiscussed.ThisreviewoutlinestheversatilityofRaman
spectroscopy for real-time analyses, in situ variable-programmed investi-
gations and reaction studies. The authors also discuss developments for
Raman imaging of profiles during catalyst synthesis and reaction.
Fabrizio Cavani, Aurora Caldarelli, Silvia Luciani (Alma Mater
Studiorum, Universita` di Bologna, Italy) and Carlotta Cortelli, Federico
Cruzzolin (Polynt SpA, Italy) report the selective oxidation of o-xylene to
phthalicanhydride.Specifically,theyexaminesomeaspectswhichmayoffer
ideasforthedevelopmentofmoreinnovativereactortechnologies,catalyst
(V/Ti/O catalysts)formulations,and some peculiarities of this process that
have been overlooked in the past. They review the role of gas-phase pro-
moters which has been overlooked in literature and report on the role of
alkali dopants in the complex reaction network. In the former case, they
examinedtheroleofco-fedsteamandS-containingcompounds,theformer
sometimes used for the rejuvenation of spent catalysts and the latter
extensively usedin thepast asa gas-phasepromoterof activity. Thesegas-
phase components had different effects on the chemical-physical features
andcatalyticbehaviorofV/Ti/Ocatalysts,eitherfosteringthespreadofthe
vanadium oxide to generate active dispersed V sites, or allowing the
development of an average, more reduced (and more selective) oxidation
state for vanadium during reaction.
OlafDeutschmann(KarlsruherInstitutfu¨rTechnologie(KIT),Germany)
reviews recent studies of catalytic reforming of logistic fuels at high-
temperature. Reforming and partial oxidation of natural gas, gasoline,
diesel, and ethanol-containing fuels are discussed. Methane and iso-octane
as fuel surrogates are used as examples to explain the behavior of the
reformers in particular focusing on the interaction of heterogeneous and
homogeneous chemical reactions and mass and heat transport. Mainly
rhodium-basedsystemsarediscussed,alongwithalternativessuchasnickel-
based catalysts. The deactivation of the catalyst and of downstream pipes
and devices (e.g. fuel cells) due to coking is also covered. Modeling and
simulation of the interaction of mass and heat transfer with heterogeneous
and homogeneous chemical reactions in the reformer are also presented.
Cristina Freire, Clara Pereira, and Susana Rebelo (Universidade do
Porto, Portugal) review the progress on the design and catalytic activity of
recyclable hybrid catalysts based on metallosalen, metal acetylacetonate
andmetalloporphyrincomplexesforoxidationreactions.Awidevarietyof
catalysts iscovered such as metal complexes supported onto bulk supports
such as carbon materials, mesoporous silicas, clay based materials and
metal-organic frameworks and nanosupports such as carbon nanotubes,
nanosilicas,magneticironoxidenanoparticlesandcolloidalgold.Although
transition metal complexes are efficient homogeneous catalysts for a num-
ber of liquid-phase reactions, their low stability, high cost and difficult
recoveryfromthereactionmediumlimittheirimplementationinindustrial
processes. Their immobilization onto solid supports is a potential strategy
vi | Catalysis, 2012, 24, v–viii
to overcome these issues, giving rise to recyclable hybrid catalysts which
have received attention as ‘‘green catalysts’’. An overview of the general
methodologies developed for metal complex immobilization onto solid
supports is presented as a function of the type of interaction between the
complexandthesupport–covalentbonding,non-covalentinteractionsand
encapsulation.Specialemphasisisgiventoliteratureexamplesinwhichthe
immobilization strategy and catalytic performance of the hybrid catalysts,
including activity and reusability, were analyzed; the influence of the sup-
port dimensions on the performance of the hybrid catalysts is also
addressed.
Spencer Miller, Carmeline Dsilva, and John R. Kitchin (Carnegie Mellon
University, USA) discussthe originof thecoverage dependence foratomic
adsorbatesonlatetransitionmetalsurfaces,anditsramificationsinthefield
of heterogeneous catalysis. Oxygen is utilized as the model atom for
demonstration of the d-band mediated mechanism that underlies atomic
adsorption, although its application to other atomic adsorbates and the
ramificationsofthemodel withregards toother adsorption systems isalso
considered. The shared underlying d-band mediated bonding mechanism
leadstorelationshipsintheadsorptionenergiesfordifferentadsorbateson
the same surface, or the same adsorbate across multiple surfaces. The
modificationofthed-bandinthepresenceofadsorbatescanbeunderstood
through the Solid State Table formalism, which utilizes the intrinsic prop-
ertiesoftheelectronicorbitalsofthemetalatomd-bands,andtheadsorbate
s,pbandstodeterminechangesinthed-bandwidthsandd-bandcentersof
thesurfacemetalatoms,whichresultsinchangesinsurfacereactivityoften
observed as changes in adsorption energies.
RafaelLuque,AlinaMarianaBalu,JuanManuelCampelo,MariaDolores
Gracia, Elia Losada, Antonio Pineda, Antonio Angel Romero, and Juan
CarlosSerrano-Ruiz(UniversidaddeCordoba,Spain)provideanoverview
ofthecatalyticapplicationsofmesoporoussilica-basedmaterialsinhetero-
geneous catalysis, with special emphasis on acid and redox catalysed
processes. In this chapter, the authors report some of the most interesting
recent applications of a range of mesoporous materials in heterogeneous
catalysedprocesses.Theseincludeacidcatalysedreactions(e.g.alkylations,
acylations, esterifications, etc.) as well as redoxchemistries (e.g. oxidations
andhydrogenations)fortheproductionofhighaddedvaluechemicals,fuels
andothercompoundsfrombiomass.Thechapterincludeskeyexamplesof
the different heterogeneously catalysed processes that utilize functionalised
mesoporous materials as catalysts.
Gabriela Guillena, Diego J. Ramo´n, and Miguel Yus (Universidad de
Alicante, Spain) report the asymmetric organocatalyzed Morita-Baylis-
Hillman Reactions (MBH reactions). The MBH reaction is an important
and useful carbon-carbon bond-forming process. It is a reaction between
the a-position of an electron-deficient alkene (e.g. acrolein, acrylic esters,
acrylonitriles, vinyl ketones, vinyl sulfones, vinyl sulfonates, vinyl phos-
phates,nitroalkenes)withacarbonelectrophilesuchasanaldehyde,ketone
or a-keto ester promoted by a catalyst, usually a tertiary amine or phos-
phine. Meanwhile when the electrophile used is a N-sulfonyl, N-acyl,
N-phospinoyl or N-alkoxycarbonyl imine the process is commonly known
Catalysis, 2012, 24, v–viii | vii
as the aza-Morita-Baylis-Hillman reaction (aza-MBH). This chapter focu-
sesonthedevelopmentandadvancesaboutthesearchanddesignofchiral
organocatalysts and their application in the enantioselective MBH/aza-
MBHreaction,andtherecentinsightsonthemechanismsinvolvedinsuch
transformations.
Wegreatlyappreciatetheeffortsoftheauthorswhohavecontributedto
thisvolume.WethanktheRoyalSocietyofChemistryfortheirsupportof
this series, especially Dr. Merlin Fox. Comments are welcome.
Gordon A. and Mary Cain
Dept. Chemical Engineering
Louisiana State University
Baton Rouge, LA 70803, USA
E-mail: [email protected]
viii | Catalysis, 2012, 24, v–viii
CONTENTS
Cover
Imageprovidedcourtesyof
computationalsciencecompanyAccelrys
(www.accelrys.com).Anelectrondensity
isosurfacemappedwiththeelectrostatic
potentialforanorganometallicmolecule.
Thisshowsthechargedistributionacross
thesurfaceofthemoleculewiththe
redareashowingthepositivecharge
associatedwiththecentralmetalatom.
ResearchcarriedoutusingAccelrys
MaterialsStudioss.
Preface v
James J. Spivey and Mayank Gupta
Recent advances in imaging and monitoring of heterogeneous catalysts 1
with Raman spectroscopy
Vanesa Calvino-Casilda and Miguel A. Ban˜ares
1 Introduction 1
2 Operando spectroscopy for developing catalysts and 2
catalytic processes
3 Variable-programmed in situ and operando Raman 5
4 In situ and operando Raman spectroscopy and its 16
combination with other techniques
5 Raman mapping and imaging 21
6 Operando Raman Spectroscopy in microreactors 30
7 Raman spectroscopy in electrocatalysis 35
8 Operando Raman spectroscopy in liquid phase 35
9 Conclusions 40
Acknowledgements 41
References 41
Catalytic reforming of logistic fuels at high-temperatures 48
Olaf Deutschmann
1 Introduction 48
2 Fundamentals of high-temperature catalysis 50
Catalysis, 2012, 24, ix–xii | ix
(cid:2)c TheRoyalSocietyofChemistry2012