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In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
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In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
1132
ACS SYMPOSIUM SERIES
Novel Materials for Catalysis and
Fuels Processing
Juan J. Bravo-Suáŕ́ ez, Editor
The University of Kansas
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1 Michelle K. Kidder, Editor
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AmericanChemicalSociety,Washington,DC
DistributedinprintbyOxfordUniversityPress
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
LibraryofCongressCataloging-in-PublicationData
Novelmaterialsforcatalysisandfuelsprocessing/JuanJ.Bravo-Suárez,editor,MichelleK.
1 Kidder,editor,VivianeSchwartz,editor;sponsoredbytheACSDivisionofEnergyand
0
0 Fuels.
w
2.f pagescm.-- (ACSsymposiumseries;1132)
13 Includesbibliographicalreferencesandindex.
1
3- ISBN978-0-8412-2811-5(alkalinepaper) 1. Catalysis--Research.2. Catalysts--
01 Research.3. Fuel--Research. I.Bravo-Suárez,JuanJ.II.Kidder,MichelleK.III.Schwartz,
2
k- Viviane.IV.AmericanChemicalSociety.DivisionofEnergyandFuels.
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0 660'.2995--dc23
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g 10. 2013016859
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4, We
June 1Date ( Copyright©2013AmericanChemicalSociety
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PRINTEDINTHEUNITEDSTATESOFAMERICA
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Foreword
The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of
the series is to publish timely, comprehensive books developed from the ACS
sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare
developed from symposia sponsored by other organizations when the topic is of
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13 Beforeagreeingtopublishabook,theproposedtableofcontentsisreviewed
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3- forappropriateandcomprehensivecoverageandforinteresttotheaudience. Some
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2 papersmaybeexcludedtobetterfocusthebook;othersmaybeaddedtoprovide
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b comprehensiveness. When appropriate, overview or introductory chapters are
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02 added. Draftsofchaptersarepeer-reviewedpriortofinalacceptanceorrejection,
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In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Preface
Catalysis drives the majority of industrial chemical processes and is
an essential element for the current fossil fuel based economy. Continual
improvement and innovation in catalysis plays a key role in the development of
more efficient and effective fuel processing technologies. To achieve this goal,
novel catalysts need to be designed for chemical conversions running at much
1
0
0 higher yields and with better selectivity, which can improve the economics and
pr
2. sustainability of these processes by reducing the consumption of raw materials,
3
11 energy,andemissionstotheenvironment.
3-
1 This book is based on contributions to the symposium “Novel Materials
0
2
k- for Catalysis and Fuels Processing” that took place at the 243rd ACS National
b
1/ Meeting in San Diego, California on March, 2012. Many topics concerning the
2
10 growing area of materials for catalysis and fuel processing were presented in
0.
s.org doi: 1 tthheisorseytmicaplosaiunmd,eaxnpdertihmeyenctaolnsatidtuvtaenctehse minaintheconatreenatsooffthcisatbaloyoskt, siynncltuhdesinisg,
p://pubs.ac11, 2013 | cfauhneadlracpcartroebdroiuzncasttiieooqnnu,,eesatmnraditsiskoiinonneatncidcosntrtfaroonrls,froesrnemleewacttaiiobvnlee.rfeedeudcsttiovceksancdonovxeidrsaitoivne, aplrtoercneastsievse,
013 | httb): June organTihziesdbionofikvecosnetcatiinosns1:4(Ip)egeer-nreervaileowveedrvcihewapt(eCrhs.apTtehre1s)e,(cIhIa)pctoemrsphuatevre-abideeedn
2e
4, W design (Chapters 2 and 3), (III) spectroscopic characterization (Chapter 4),
ne 1ate ( (IV) kinetics-aided design (Chapter 5), and (V) applications of novel catalysts
uD
V on Jation (ChaPpatertrsI6ctoon1si4s)t.s of an introductory chapter (Chapter 1) by Bravo-Suárez,
UNIPublic Cinhasyundthhaersi,isa,ncdhSaurabcrtaemriaznatiiaomn,,wanhdichkipnreotvicidseassantooovlserfvoirewdeosfigthneinrgecceanttalpyrsotgsrefossr
targeted applications. The remaining chapters feature a unique overview of
syntheticmethods,advancedcharacterizationtechniques,andcomputationaland
kinetic tools to assist in the understanding and development of new catalytic
materials as well as compelling applications in fuels and chemicals processing.
Topicsthataddresscurrentenergyandenvironmentalneedsarecovered,suchas
deoxygenationofalternativefuels,productionofhigheralcoholsasfueladditives,
hydrocarbon production, hydrodesulfurization, materials for carbon dioxide
adsorption,andemissioncontrolcatalystsfordieselengines. Additionally,topics
aimed at a fundamental understanding of catalytic processes such as probing
surface interactions via advanced spectroscopic techniques and computational
simulationsarealsodiscussed.
xi
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Current advances in computational power and theoretical methods have
tremendously contributed to the understanding of structure–activity and
structure–property relationships of catalysts and materials, which can be used
to guide the design of novel structures. These topics are covered in Part II of
this book. In Chapter 2, Cheng and Curtiss present a review of the theoretical
studies covering the nature of supported vanadia clusters for propane oxidative
dehydrogenation via Density Functional Theory (DFT) calculations and their
implications for the design of improved catalysts. In Chapter 3, Houndonougbo
describes important structural factors required for the design of novel Zeolitic
ImidazolateFrameworks(ZIFs)forCO adsorption. Thesefactorsareestablished
2
frommolecularsimulationsofCO adsorptionathighpressuresonZIFsascarried
2
outbyacombinationofGrandCanonicalMonteCarlo(GCMC)andforcefields
methods.
01 The utilization of spectroscopic techniques for the characterization of
0
pr catalystsisessentialfortheunderstandingofthenatureofactivesites,adsorbed
2.
13 species, and ultimately the reaction mechanism. This fundamental knowledge
1
3- of the catalyst structure and the catalytic cycle is necessary for the development
1
20 of improved and new catalysts. This topic is the focus of Part III. In Chapter
k-
b 4, Formo, Wu, Mahurin, and Dai describe recent developments in the use of
1/
02 Surface Enhanced Raman spectroscopy (SERS) for studying catalyst structure
1
0. and interface interactions with molecular probes. As detailed in the chapter,
s.org doi: 1 the application of SERS for catalyst characterization in various environments
p://pubs.ac11, 2013 | wsauthbeiscltehrvaitanetset,durnntaemcmaepnleyar,casttuialrvseesarsinusapnmpooawrdtierfeopsroccsaostiaabtlelyedstbwcyihtahthraaectpgereroinzteearctaitotiivnoensltauoydfeierrsoo.bfusatluSmEiRnaS,
httne Part IV focuses on the use of modern kinetic tools for catalyst and reactor
013 | b): Ju design. Inthissection, Sharma, Suib, andMhadeshwar(Chapter5)describethe
2e challengesassociatedwiththedesignofsulfur-resistantdieseloxidationcatalysts
4, W
une 1Date ( (eDngOinCess).,aInnipmaprtoicrtualnatr,csoumlfpuornsepnetcoiefsthienteexrhacatuisotnesmwisitshioPnt–coPndt/rAollusmysitneam, aintydpieicsaell
UNIV on JPublication lDaintOedrCact,oumarerperueitvnaitveieowsn.taigFlausttteuuddreivedsiairoeafcttmihoeincsrreofaokcritniteohtneicdmeaesnciaghlnaynsoiifssmssuulapfsuprdoreretresivdisetdbaynftreomxmapteearriicmarliestnifctoaarll
efficientandeconomicalDOCsarealsodiscussed.
The final section of this book, Part V, covers applications of novel catalysts
for various reactions including hydrodesulfurization, epoxidation, syngas
conversion, dehydrogenation, and emerging applications such as renewables
conversion. InChapter6,Soni,Bhaskar,Kumar,Seetha,Rao,andDhardescribe
thedevelopmentofmoreactivehydrodesulfurizationandhydrogenationcatalysts
based on mesostructured silica (SBA-16) supported Mo, Co–Mo, and Ni–Mo.
Detailedandcomplementarycharacterizationsofcatalystmetalcoverageareused
to establish correlations with catalyst reactivity to explain the observed higher
activitiesoftheSBA-16catalystsincomparisonwithrelated2Dandamorphous
silica supported materials. Chapter 7 by Pachamuthu, Ramanathan, Santhi, and
MaheswariandChapter8byRamanathan,Maheswari,Thapa,andSubramaniam
investigate novel Cu–TUD-1 and Ce–MCM-48 catalysts, respectively, for the
epoxidation of alkenes. These catalysts consist of highly dispersed isolated
xii
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
species of CuO and oligomeric CuO in a 3D amorphous silica matrix and Ce4+
partially incorporated in the MCM-48 framework, whose presence is shown to
improve activity and selectivity towards the corresponding epoxide products.
In Chapter 9, Chai, Howe, Kidder, Wang, Schwartz, Overbury, Dai, and Jiang
report small Rh nanoparticles supported on an ordered mesostructured carbon
(OMC)fortheconversionofsyngastoethanol. Thepresenceofacarbonsupport,
rhodium, and promoters (Mn, Li, Fe) in the catalyst is shown to be responsible
for the increased alcohol selectivities in comparison with similar conventional
SiO supportedcatalysts. InChapter10,Schwartz,Overbury,andLiangdescribe
2
theuseofcarbonasanalternativematerialtoconventionalmetal-basedcatalysts
for the oxidative dehydrogenation of alkanes. Challenges and future directions
associatedwiththedevelopmentofmoreactiveandselectivecarboncatalystsare
alsodiscussedinthischapter.
01 Thesustainableproductionoffuelsandchemicalsfromplant-basedbiomass
0
pr isatopicofcurrentandintenseresearchworldwide. Chapters11to14focuson
2.
13 the catalytic conversion of renewable feedstocks including bioderived ethanol,
1
3- sugars (e.g., xylitol, sorbitol), and bio-oil components. In Chapter 11, Kandel,
1
20 Althaus, Pruski, and Slowing report the synthesis of a novel bifunctional
k-
b enzyme–alkylamine–mesostructuredSiO catalystforC–Ccouplingreactionsof
1/ 2
02 alcohols. Thecatalystisabletocarryoutthecondensationofethanolwithhigh
1
0. selectivityviaatwo-step,singlepot,lowtemperatureprocess. InChapter12,Jin,
s.org doi: 1 Subramaniam, and Chaudhari report the hydrogenolysis of xylitol and sorbitol
p://pubs.ac11, 2013 | tctohawetaalryredsastcstCiao2nnadnnsdeotClwid3olbrikqausfeiodprprboroamsdeou-tcpetrrsso.omnToahtdeisdmwihxoytrudkrreopsgroeonvfoicdlayerssbiomsneascnuhdpapnthoiserttieccdoirnnroseibsgplheotnmsdienitntaogl
httne effects on activity and selectivity of liquid products. Chapters 13 and 14 cover
013 | b): Ju theupgradingofbio-oilmodelcompoundssuchasphenolsandcarboxylicacids,
2e respectively. In Chapter 13, Whiffen and Smith report the application of a Ni P
4, W 2
une 1Date ( cpaotsatl-yssytntfhoersitshtehehrymdaroldtreeoaxtmygeenntsatoionnth(eHcDaOta)lyostfpmhyesthicyolcphheemnoicl.alpTrhoepeerftifeesctanodf
UNIV on JPublication rcaeacqttaiuvliyirtetyidcinfdoetrhotexhyHegdDeenOsaigtrienoanocftoiiofmncpairsrobdvoiexsdcyulcisacsteaadlcy.isdItsns.CinThchaleupdtaeiunrtg1h4oth,rseHfpeorcaeunsesdnoWcneatonhfgemrpeervtoaipelwesritttieheses,
acidsites,andsupportoxygenvacancies. Currentchallengesinthefundamental
studyofthedeoxygenationofacidspresentinbio-oilarealsodiscussed.
Thebookwillappealtobothbasicandappliedresearchersinacademiaand
industry who would like a comprehensive overview of the most recent studies
targeting the development of the next generation of catalysts. The selection of
topics presented here touches upon current progress and development of novel
materialsandcatalystsforfuelsandchemicalsprocessing. Theeditorshopethat
thereaderwillappreciatethechallengesfacedinthedesignanddevelopmentof
catalystsandcatalytictechnologiesandbeinspiredtocontributetotheirsolution
totackletheincreasinglycomplexenvironmentalandsustainableenergyproblems
ofthe21stcentury.
xiii
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Acknowledgments
Wewishtothankanumberofpeoplewithoutwhomthisbookwouldnothave
beenpossible. Specialthanksaregiventoeachoftheauthorswhoparticipatedin
the symposium and contributed chapters to this book and to the reviewers who
helpedtoprovidecriticalcommentsandsuggestions,whichimprovedthequality
ofthechapters. WethankNikkiLazenby,ArleneFurman,andTimMarneyfrom
theACSBooksDivisionfortheirkindandefficientsupporttocompletethisbook.
WealsowouldliketoacknowledgethegenerousfinancialsupportfromtheACS
Division of Energy & Fuels for the symposium and the colored graphics in the
book.
J.J.B.-S. acknowledges the support by the University of Kansas–Center for
EnvironmentallyandBeneficialCatalysis(CEBC)aswellastheencouragement
1 ofProfessorsBalaSubramaniamandR.V.ChaudhariatCEBCduringthisproject.
0
pr0 J.J.B.-S. would like to thank his wife, Samantha, and son, Ian, for their love,
32. support, andpatience.
1
3-1 M.K.K.acknowledgesthesupportofOakRidgeNationalLaboratoryandthe
1
0 Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic
2
k- Energy Sciences, U.S. Department of Energy. M.K.K. would like to thank her
b
21/ husband, Mark, and sons, Justin and Nathan, for their unwavering support and
0
0.1 affection.
p://pubs.acs.org 11, 2013 | doi: 1 SUEcnsieeerrnVgcFy.Se.as.c,Vilaw.iScthik.einwcsohoDwuisillvedsidpslgiiookennses,ottoOrheetfdhfiaacsnutekpOophafoekrBrtRafasiodmifcgietlEhyNn,eeharteCgiroyenhnaSutelscrbLieaafnnbocdore,rsaSN,tpoUaern.yroSop.bsh,yDaatesnhepdearnSMtecmawieteennbrttioiafiorlncsf
httne son,Marcus,fortheirsupportandinspiration.
013 | b): Ju
4, 2We JuanJ.Bravo-Suárez
ne 1ate ( CenterforEnvironmentallyBeneficialCatalysis
uD TheUniversityofKansas
V on Jation 1501WakarusaDr.,LSRLB133D
UNIPublic Lawrence, KS66047
MichelleK.Kidder
ChemicalSciencesDivision
OakRidgeNationalLaboratory
Bldg. 4100,MS6197
1BethelValleyRoad
OakRidge, TN37381
VivianeSchwartz
CenterforNanophaseMaterialsScience
OakRidgeNationalLaboratory
Bldg. 8610,MS6493
1BethelValleyRoad
OakRidge, TN37831
xiv
In Novel Materials for Catalysis and Fuels Processing; Bravo-Suárez, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
