Rational Design of Nonprecious Metal Oxide Catalysts by Means of Advanced Synthetic and Promotional Routes

306 Pages·2023·18.553 MB·English

by  Konsolakis M., Stathopoulos V. (ed.)

Rational Design of
Non-precious Metal
Oxide Catalysts by
Means of Advanced
Synthetic and
Promotional Routes
Edited by
Michalis Konsolakis and Vassilis Stathopoulos
Printed Edition of the Special Issue Published in Catalysts
www.mdpi.com/journal/catalysts
Rational Design of Non-precious
Metal Oxide Catalysts by Means of
Advanced Synthetic and Promotional
Routes
Rational Design of Non-precious
Metal Oxide Catalysts by Means of
Advanced Synthetic and Promotional
Routes
Editors
Michalis Konsolakis
Vassilis Stathopoulos
MDPI‚Basel‚Beijing‚Wuhan‚Barcelona‚Belgrade‚Manchester‚Tokyo‚Cluj‚Tianjin
Editors
MichalisKonsolakis VassilisStathopoulos
SchoolofProduction DepartmentofAgricultural
Engineeringand Development,Agrofoodand
Management ManagementofNatural
TechnicalUniversityofCrete Resources
Chania,Crete NationalandKapodistrian
Greece UniversityofAthens
Psachna,Evia
Greece
EditorialOffice
MDPI
St. Alban-Anlage66
4052Basel,Switzerland
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Contents
AbouttheEditors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
MichalisKonsolakisandVassilisN.Stathopoulos
RationalDesignofNon-PreciousMetalOxideCatalystsbyMeansofAdvancedSyntheticand
PromotionalRoutes
Reprintedfrom: Catalysts2021,11,895,doi:10.3390/catal11080895 . . . . . . . . . . . . . . . . . . 1
MichalisKonsolakisandMariaLykaki
Recent Advances on the Rational Design of Non-Precious Metal Oxide Catalysts Exemplified
by CuO /CeO Binary System: Implications of Size, Shape and Electronic Effects on Intrinsic
x 2
ReactivityandMetal-SupportInteractions
Reprintedfrom: Catalysts2020,10,160,doi:10.3390/catal10020160 . . . . . . . . . . . . . . . . . . 7
MariaLykaki,SofiaStefa,SniaA.C.Carabineiro,PavlosK.Pandis,VassilisN.Stathopoulos
andMichalisKonsolakis
Facet-Dependent Reactivity of Fe O /CeO Nanocomposites: Effect of Ceria Morphology on
2 3 2
COOxidation
Reprintedfrom: Catalysts2019,9,371,doi:10.3390/catal9040371 . . . . . . . . . . . . . . . . . . . 61
Maria Lykaki, Eleni Papista, Nikolaos Kaklidis, Snia A. C. Carabineiro and Michalis
Konsolakis
Ceria Nanoparticles’ Morphological Effects on the N O Decomposition Performance of
2
Co O /CeO MixedOxides
3 4 2
Reprintedfrom: Catalysts2019,9,233,doi:10.3390/catal9030233 . . . . . . . . . . . . . . . . . . . 83
KveˇtaJira´tova´,KaterˇinaPacultova´,JanaBalaba´nova´,KaterˇinaKara´skova´,AnnaKlegova´and
TerezaB´ılkova´ etal.
PrecipitatedK-PromotedCo–Mn–AlMixedOxidesforDirectNODecomposition: Preparation
andProperties
Reprintedfrom: Catalysts2019,9,592,doi:10.3390/catal9070592 . . . . . . . . . . . . . . . . . . . 103
KaterˇinaPacultova´,TerezaB´ılkova´,AnnaKlegova,KaterˇinaKara´skova´,DagmarFridrichova´
andKveˇtaJira´tova´ etal.
Co-Mn-Al Mixed Oxides Promoted by K for Direct NO Decomposition: Effect of
PreparationParameters
Reprintedfrom: Catalysts2019,9,593,doi:10.3390/catal9070593 . . . . . . . . . . . . . . . . . . . 123
ConstantinosM.Damaskinos,MichalisA.Vasiliades,VassilisN.StathopoulosandAngelos
M.Efstathiou
The Effect of CeO Preparation Method on the Carbon Pathways in the Dry Reforming of
2
MethaneonNi/CeO StudiedbyTransientTechniques
2
Reprintedfrom: Catalysts2019,9,621,doi:10.3390/catal9070621 . . . . . . . . . . . . . . . . . . . 149
AndoniChoya,BeatrizdeRivas,JoseIgnacioGutie´rrez-OrtizandRube´nLo´pez-Fonseca
ComparativeStudyofStrategiesforEnhancingthePerformanceofCo O /Al O Catalystsfor
3 4 2 3
LeanMethaneCombustion
Reprintedfrom: Catalysts2020,10,757,doi:10.3390/catal10070757 . . . . . . . . . . . . . . . . . . 173
XiaoliLi,JunfengZhang,MinZhang,WeiZhang,MengZhangandHongjuanXieetal.
The Support Effects on the Direct Conversion of Syngas to Higher Alcohol Synthesis over
Copper-BasedCatalysts
Reprintedfrom: Catalysts2019,9,199,doi:10.3390/catal9020199 . . . . . . . . . . . . . . . . . . . 191
v
YuyaoMa,YuxiaMa,MinLiu,YangChen,XunHuandZhengmaoYeetal.
StudyonNanofibrousCatalystsPreparedbyElectrospinningforMethanePartialOxidation
Reprintedfrom: Catalysts2019,9,479,doi:10.3390/catal9050479 . . . . . . . . . . . . . . . . . . . 209
LitingXu,QileiYang,LihuaHu,DongWang,YuePengandZheruShaoetal.
Insights over Titanium Modified FeMgO Catalysts for Selective Catalytic Reduction of NO
x x
withNH : InfluenceofPrecursorsandCrystallineStructures
3
Reprintedfrom: Catalysts2019,9,560,doi:10.3390/catal9060560 . . . . . . . . . . . . . . . . . . . 223
Cong Wang, Xinyu Mao, Jennifer D. Lee, Tzia Ming Onn, Yu-Hao Yeh and Christopher B.
Murrayetal.
ACharacterizationStudyofReactiveSitesinALD-SynthesizedWO /ZrO Catalysts
x 2
Reprintedfrom: Catalysts2018,8,292,doi:10.3390/catal8070292 . . . . . . . . . . . . . . . . . . . 239
RubyPhul, MohammadPerwez, Jahangeer Ahmed, MeryamSardar, SaadM.Alshehriand
NorahAlhokbanyetal.
Efficient Multifunctional Catalytic and Sensing Properties of Synthesized Ruthenium
OxideNanoparticles
Reprintedfrom: Catalysts2020,10,780,doi:10.3390/catal10070780 . . . . . . . . . . . . . . . . . . 255
EuaggeliaSkliri,IoannisVamvasakis,IoannisT.Papadas,SteliosA.ChoulisandGerasimos
S.Armatas
MesoporousCompositeNetworksofLinkedMnFe O andZnFe O NanoparticlesasEfficient
2 4 2 4
PhotocatalystsfortheReductionofCr(VI)
Reprintedfrom: Catalysts2021,11,199,doi:10.3390/catal11020199 . . . . . . . . . . . . . . . . . . 267
Baburajeev Chumadathil Pookunoth, Shilpa Eshwar Rao, Suresha Nayakanahundi
Deveshegowda,PrashantKashinathMetri,KashifaFazl-Ur-RahmanandGangaPeriyasamy
etal.
Development of a New Arylamination Reaction Catalyzed by Polymer Bound
1,3-(Bisbenzimidazolyl) Benzene Co(II) Complex and Generation of Bioactive
AdamanateAmines
Reprintedfrom: Catalysts2020,10,1315,doi:10.3390/catal10111315 . . . . . . . . . . . . . . . . . 283
vi
About the Editors
MichalisKonsolakis
Dr. KonsolakisMichalisisaFullProfessorof“HeterogeneousCatalysis&SurfaceScience”atthe
School of Production Engineering & Management of the Technical University of Crete, Greece. His
research activities are mainly focused in the areas of heterogeneous catalysis and surface science,
with particular emphasis on structure–property relationships. Recently, he has focused on the
rational design and nano-engineering of metal oxide catalysts by means of advanced synthetic
and promotional routes. His published work includes >100 articles in international peer-reviewed
journalsand>150articlesinconferenceproceedings.HeisamemberoftheEditorialBoardofseveral
internationaljournalsinthefieldsofmaterialsandsurfacescience,alsoservingasaregularreviewer
for>100scientificjournalsandresearchfundingagencies.
VassilisStathopoulos
Dr. Stathopoulos Vassilis is a Full Professor of “Ceramic, Porous and Catalytic Materials”at
the Department of Agricultural Development, Agrofood and Management of Natural Resources,
National and Kapodistrial University of Athens. His research activities mainly focus in the areas
ofheterogeneouscatalysis, porousmaterialsandsurfaceengineering. Hispublishedworkincludes
>95articlesininternationalpeer-reviewedjournals.HeisamemberofseveralEditorialBoardsinthe
fieldofmaterialsandsurfacescience,alsoservingasaregularreviewerforseveralscientificjournals
andresearchfundingagencies.
vii
catalysts
Editorial
Rational Design of Non-Precious Metal Oxide Catalysts by
Means of Advanced Synthetic and Promotional Routes
MichalisKonsolakis1,* andVassilisN.Stathopoulos2
1 SchoolofProductionEngineeringandManagement,TechnicalUniversityofCrete,73100Chania,Greece
2 GeneralDepartment,NationalandKapodistrianUniversityofAthens,PsachnaCampusEvia,
34100Psachna,Greece;[email protected]
* Correspondence:[email protected];Tel.:[phone]
1. Background
Catalysisisanindispensablepartofoursociety,involvedinnumerousenergyand
environmentalapplications,suchastheproductionofvalue-addedchemicals/fuels,hy-
drocarbonsprocessing,fuelcellsapplications,abatementofhazardouspollutants,among
others. Although,noblemetals(NMs)-basedcatalystsaretraditionallyemployedinvari-
ousprocesses,duetotheirpeculiarcharacteristicsandenhancedreactivity,theirscarcity
andconsequentlyhighcostrendersthemdisincentiveforpracticalapplications. Inthis
perspective,therationaldesignanddevelopmentofearth-abundantNMs-freemetaloxides
ofadequateactivity,selectivityanddurabilityconstitutesoneofthemainresearchpillars
inheterogeneouscatalysis[1–6]. Towardsthisdirection, however, onecrucialquestion
must beanswered: Isit possible tofine-tune the localsurface chemistry/structure of a
single,binaryormulticomponentmetaloxideinordertobehighlyefficient-likeNMs-in
aspecificprocess? Thankstothehugeresearchprogresssofarachievedinthefieldsof
Citation: Konsolakis,M.; (nano)materialssynthesis,catalysttailoring/promotionandsurfacescience,theanswerto
Stathopoulos,V.N.RationalDesignof theaforementionedquestioniscertainlyyes.
Non-PreciousMetalOxideCatalysts Inspecific,thecatalyticperformanceofmetaloxides,suchastransitionmetals(TMs)-
byMeansofAdvancedSyntheticand based mixed metal oxides, spinels, perovskites, hexaaluminates and hydrotalcites can
PromotionalRoutes.Catalysts2021, beconsiderablyimprovedbytailoringthelocalsurfacechemistry/structure(e.g.,work
11,895. https://doi.org/10.3390/ function, reducibility, oxygen vacancies) and interfacial interactions. The latter can be
catal11080895 accomplished by the employment of state-of-the-art nano-synthesis routes towards en-
gineeringparticle’ssizeandshape(e.g.,nanocubes,nanorods)inconjunctiontotheuse
Received:22July2021
ofappropriatemodifiers(e.g.,alkali,grapheneoxide)andspecialpretreatmentprotocols.
Accepted:23July2021
Thisholisticapproachcanexertaprofoundinfluencenotonlytothesurfacereactivityof
Published:24July2021
metalsitesinitsownright,butalsotometal-supportinterfacialactivity,offeringhighly
activeandstablematerialsforreal-lifeenergyandenvironmentalapplications,suchas
Publisher’sNote:MDPIstaysneutral
theCOoxidation[7–12],N Odecomposition[13–15],CO hydrogenationtovalue-added
2 2
withregardtojurisdictionalclaimsin
products[16–20],degradationoforganiccontaminants[21–33],etc.
publishedmapsandinstitutionalaffil-
iations.
2. ThisSpecialIssue
Inlightoftheaboveaspects,thepresentSpecialIssueismainlyfocusedonthefabri-
cationandfine-tuningofNMs-freemetaloxidecatalystsbymeansofadvancedsynthetic
and/orpromotionalroutes. Itconsistsoffourteenhighqualitypapers,involving: acom-
Copyright: © 2021 by the authors.
prehensivereviewarticleontherecentadvancesontherationaldesignandfine-tuningof
Licensee MDPI, Basel, Switzerland.
ceria-basedmetaloxidecatalysts[5];twoarticlesontheceriananoparticlesmorphological
This article is an open access article
effectsonN Odecomposition[14]andCOoxidation[10]overceria-basedbinaryoxides;
2
distributed under the terms and
twoarticlesonNOdecompositionoverK-promotedCo-Mn-Almixedoxides[34,35];one
conditionsoftheCreativeCommons
articleontheeffectofceriasynthesismethodsonthecarbonpathwaysindryreformingof
Attribution(CCBY)license(https://
methane(DRM)overNi/CeO catalysts[36];onearticleontheimpactofsynthesisproce-
creativecommons.org/licenses/by/ 2
dureandaliovalentdopinginCo-Alspinel-typeoxidesforleanmethanecombustion[37];
4.0/).
1
Catalysts2021,11,895
one article on the support effect on the direct conversion of syngas to higher alcohols
overcopper-basedoxides[38];onearticleonnanofibrousNi/Al O catalystspreparedby
2 3
electrospinningformethanepartialoxidation[39];onearticleontheinfluenceofprecur-
sorcompoundsontheselectivecatalyticreduction(SCR)ofNO byNH overFeMgO
x 3 x
oxides[40];onearticleonthesynthesisandactivesitesdeterminationofZrO -supported
2
WO solidacidcatalysts[41];onearticleonthesynthesisandelectrocatalyticperformance
x
ofRuO nanoparticles[42];onearticleonthefabricationandphotocatalyticperformanceof
2
mesoporousframeworksofZnFe O (ZFO)andMnFe O (MFO)nanoparticles[43];and
2 4 2 4
onearticleonthesynthesisofpolymersupportedcatalystsforarylaminationreaction[44].
ContributionHighlights
ThecomprehensivereviewofM.KonsolakisandM.Lykaki[5]addressesthelatest
experimentalandtheoreticaladvancesinthefieldoftherationaldesignofmetaloxidecat-
alystsexemplifiedbyCuO /CeO binarysystem. Inparticular,itsummarizesthegeneral
x 2
optimizationframeworkthatcouldbefollowedtofine-tunemetaloxidesitesandtheirsur-
roundingenvironmentbymeansofappropriatesyntheticandpromotional/modification
routes. Itwasclearlyrevealedthatthemodulationofsize,shapeandelectronicstateat
nanoscalecanexertaprofoundinfluencenotonlytothereactivityofmetalsitesinitsown
right,butalsotometal-supportinterfacialactivity,offeringcost-effectiveandhighlyactive
materialsforreal-lifeenergyandenvironmentalapplications.
In view of above aspects, the impact of ceria morphology (nanorods, nanocubes,
nanopolyhedra)onthephysicochemicalpropertiesandthecatalyticperformanceofceria-
basedtransitionmetalcatalystswasexploredbyM.Konsolakisandco-workers[10,14]. It
wasshownthatCo O /CeO ofrod-likemorphologyexhibitedtheoptimumN Odecom-
3 4 2 2
positionperformanceascomparedtootherdistinctmorphologies,duetoitsabundance
inCo2+ activesitesandCe3+ speciesinconjunctiontoitsimprovedreducibility,oxygen
kineticsandsurfacearea[14]. SimilarconclusionswerederivedforFe O /CeO catalysts
2 3 2
for CO oxidation [10]; the rod-shaped sample exhibited the optimum catalytic perfor-
mance,duetoitsimprovedreducibilityandabundanceinFe2+species[10]. Thesefindings
unambiguouslyrevealedthekeyroleofsupportmorphologytowardsdeterminingthe
redoxpropertiesandinturnthecatalyticperformanceofreactionsfollowingaredox-type
mechanism[5,10,14].
LucieObalováandco-workers[34,35]systematicallyexploredtheimpactofprepa-
ration parameters and alkali doping on the direct NO decomposition of K-promoted
Co-Mn-Al mixed oxides. It was shown that preparation procedure notably affects the
physicochemicalpropertiesandalkalidistribution/stabilitywithgreatconsequencesin
NOdecomposition. Specifically,itwasrevealedthatthepresenceofpotassiumpromoter
notably improves the basicity and reducibility of the catalysts, positively affecting the
catalyticactivity. However,thecalcinationtime/temperaturenotablyaffectsthetextural
characteristicsandalkalimetalvalorizationprocess. Thebestcatalyticperformancewas
achievedforapotassiumloadingofca. 1.0wt.%atacalcinationtemperatureof700–800 C.
◦
Theseresultsclearlyrevealedtheimportanceofpretreatmentconditionsinconjunctionto
surfacepromotiontowardsthedevelopmentofhighlyactivemetaloxides.
A.M. Efstathiou and co-workers [36] elegantly designed and conducted transient
andisotopicstudiestogaininsightintotheimpactofCeO preparationmethodonthe
2
carbonpathwaysinthedryreformingofmethane(DRM)ofNi/CeO catalysts.Amongthe
2
differentpreparationmethodsexplored,precipitationledtothelowestamountofcarbon
deposition. Bymeansofvarioustransientandisotopicstudies,itwasshownthatalarge
poolofoxygenoverprecipitatedcatalystscontributedtothegasificationofcarbonformed
inDRMtowardstheformationofCO,thusofferinganimportantpathforcarbonremoval.
Theimpactofdifferentsynthetic/modificationroutestowardsenhancingthelean
methanecombustionofCo O /Al O spinel-typeoxideswasinvestigatedbyRubénLópez-
3 4 2 3
Fonsecaandco-workers[37]. Threedifferentstrategiesforenhancingtheperformanceof
alumina-supportedcatalystswereexamined: (i)surfaceprotectionofthealuminawith
2
Catalysts2021,11,895
magnesiapriortothedepositionofthecobaltprecursor,(ii)coprecipitationofcobaltalong
withnickeland(iii)surfaceprotectionofaluminawithceria. Theoptimumperformance
wasobtainedbytheadditionofceriatoaluminapriortothedepositionofcobalt,which
wasattributedtotheabundanceofCo3+speciesandoxygenvacanciesduetotheinsertion
ofCe4+ionsintothespinellattice.
X. Li et al. [38] reported on the impact of support nature (SiO , Al O ) and alkali
2 2 3
promotion(K)onthesynthesisofhigheralcoholsfromCOhydrogenationoverCu-based
catalysts. SignificantdifferencesonCOconversionandproduct’sselectivitywererevealed,
attributedtosupport-andalkali-inducedeffectsonredoxandelectronicproperties.
D.Dongandco-workers[39]investigatednanofibrousNi/Al O catalystspreparedby
2 3
electrospinningformethanepartialoxidation.Theimpactofdifferentsynthesisparameters,
suchasmetalprecursor,metalcontentandcalcinationtemperaturewereexplored. Itwas
shownthatbyappropriatelyadjustingtheaforementionedparametershighlyactiveand
stablecatalystscanbeobtained.
Inasimilarmanner,L.Xuetal.[40]exploredtheinfluenceofprecursorcompounds
on the selective catalytic reduction (SCR) of NO with NH over Ti-modified FeMgO
x 3 x
oxides. The key role of precursors towards determining the surface acidity and redox
propertiesandinturnthecatalyticperformance,wasclearlydemonstrated. Thecatalysts
derivedfromFeSO andMg(NO ) precursorsexhibitedenhancedcatalyticactivityinthe
4 3 2
temperaturerangeofca. 200–400 C,offeringcompleteNO conversion.
◦ x
R.J.Gorteandco-workers[41]exploredthoroughlythereactivesitesinWO /ZrO
x 2
catalystspreparedbyatomiclayerdeposition(ALD).ByacomparisonwithaWO /ZrO
x 2
catalystpreparedviaconventionalimpregnationandbyemployingsurfaceandmicroscopy
techniquesthreetypesofcatalyticsiteswereidentified,withtheirconcentrationvaried
withthenumberofALDcycles. DehydrogenationsitesareassociatedwithZrO ,Brønsted-
2
acidsiteswithmonolayerWO clusters,whileoxidationsitesareassociatedwiththeWO
x x
coverage. Such surface chemistry differentiation with the preparation process notably
affectsacidcatalyzedreactions,suchas2-propanolcatalyticdehydration.
R. Phul et al. [42] reported on a simple wet chemical route to synthesize ultrafine
RuO nanoparticles at controlled temperature as electrocatalysts for oxygen evolution
2
reaction(OER)andoxygenreductionreaction(ORR).TheseRuO nanoparticlesexhibited
2
enhanced bifunctional electrocatalytic performance under different conditions (air, N
2
and O atmosphere), showing excellent potential for electrocatalytic applications. In
2
addition,RuO nanoparticlesshowedefficientsensingpropertiesrenderingthemasactive
2
nonenzymaticelectrochemicalsensorsfortheselectivedetectionofH O .
2 2
ThegroupofG.S.Armatas[43]reportedonthepreparationofhigh-surface-areadual
componentmesoporousframeworksofspinelferriteZnFe O (ZFO)andMnFe O (MFO)
2 4 2 4
nanoparticleswithimprovedphotochemicalactivity. Thesemesoporousnanomaterials
weresynthesizedviaapolymer-assistedmethodthatallowedtheefficientco-assemblyof
thespinelferritecolloidalnanoparticlesandamphiphilicblock-copolymeraggregates. The
MFO-ZFOcompositematerialsexhibitexcellentperformanceforphotocatalyticreduction
ofCr(VI)inaqueoussolutionswithcoexistingorganicpollutants(suchasphenol,citric
acidandEDTA),underUV-vislightirradiation. Theenhancedphotocatalyticactivityof
dualcomponentMFO-ZFOmesoporousnetworksisoriginatedfromthecombinedeffect
ofaccessibleporestructure,whichpermitsfacilediffusionofreactantsandproductsand
suitableelectronicbandstructure,whichefficientlyseparatesandtransportsthecharge
carriersthroughtheZFO/MFOinterface.
B. Chumadathil Pookunoth et al. [44] reported on the immobilization of a
1,3-bis(benzimidazolyl)benzeneCo(II)complexondivinylbenzenecross-linkedchloromethy-
latedpolystyrene,asaninexpensivepolymermatrix. Thisparticularsystemwastested
on the arylamination reaction and showed robustness in the preparation of bioactive
adamantanyl-tethered-biphenylamines. Suchtransitionmetal-catalyzedcross-coupling
reactionsbetweenarylhalidesandprimary/secondaryaminestoobtainaminatedaryl
3