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Catalytic Methods
in Flow Chemistry
Edited by
Christophe Len and Renzo Luisi
Printed Edition of the Special Issue Published in Catalysts
www.mdpi.com/journal/catalysts
Catalytic Methods in Flow Chemistry
Catalytic Methods in Flow Chemistry
SpecialIssueEditors
ChristopheLen
RenzoLuisi
MDPI•Basel•Beijing•Wuhan•Barcelona•Belgrade
SpecialIssueEditors
ChristopheLen RenzoLuisi
ChimieParisTech—CNRS, DepartmentofPharmacy—Drug
InstituteofChem.For Sciences,Universityof
Life&HealthSciences Bari“A.Moro”
France Italy
EditorialOffice
MDPI
St.Alban-Anlage66
4052Basel,Switzerland
ThisisareprintofarticlesfromtheSpecialIssuepublishedonlineintheopenaccessjournalCatalysts
(ISSN2073-4344)from2018to2019(availableat:https://www.mdpi.com/journal/catalysts/special
issues/catalflow).
Forcitationpurposes,citeeacharticleindependentlyasindicatedonthearticlepageonlineandas
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ISBN978-3-03928-732-1(Pbk)
ISBN978-3-03928-733-8(PDF)
(cid:2)c 2020bytheauthors. ArticlesinthisbookareOpenAccessanddistributedundertheCreative
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disseminationandawiderimpactofourpublications.
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licenseCCBY-NC-ND.
Contents
AbouttheSpecialIssueEditors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
ChristopheLenandRenzoLuisi
CatalyticMethodsinFlowChemistry
Reprintedfrom:Catalysts2019,9,663,doi:10.3390/catal9080663 . . . . . . . . . . . . . . . . . . . 1
LauraDaviot,ThomasLen,CarolSzeKiLinandChristopheLen
Microwave-AssistedHomogeneousAcidCatalysisandChemoenzymaticSynthesisofDialkyl
SuccinateinaFlowReactor
Reprintedfrom:Catalysts2019,9,272,doi:10.3390/catal9030272 . . . . . . . . . . . . . . . . . . . 4
NoeliaLa´zaro,AnaFranco,WeiyiOuyang,AlinaM.Balu,AntonioA.Romero,RafaelLuque
andAntonioPineda
Continuous-Flow Hydrogenation of Methyl Levulinate Promoted by Zr-Based
MesoporousMaterials
Reprintedfrom:Catalysts2019,9,142,doi:10.3390/catal9020142 . . . . . . . . . . . . . . . . . . . 14
Michael Burkholder, Stanley E. Gilliland III, Adam Luxon, Christina Tang and B. Frank
Gupton
Improving Productivity of Multiphase Flow Aerobic Oxidation Using a Tube-in-Tube
MembraneContactor
Reprintedfrom:Catalysts2019,9,95,doi:10.3390/catal9010095 . . . . . . . . . . . . . . . . . . . . 27
JunXiongandYingMa
Catalytic Hydrodechlorination of Chlorophenols in a Continuous Flow Pd/CNT-Ni Foam
MicroReactorUsingFormicAcidasaHydrogenSource
Reprintedfrom:Catalysts2019,9,77,doi:10.3390/catal9010077 . . . . . . . . . . . . . . . . . . . . 36
VirginieLiautard,Me´lodieBirepinte,CamilleBettoliandMathieuPucheault
Mg-Catalyzed OPPenauer Oxidation—Application to the Flow Synthesis of a
NaturalPheromone
Reprintedfrom:Catalysts2018,8,529,doi:10.3390/catal8110529 . . . . . . . . . . . . . . . . . . . 47
XiaojiaWang,BaoshengJin,HaoLiu,BoZhangandYongZhang
Prediction of In-Situ Gasification Chemical Looping Combustion Effects of
OperatingConditions
Reprintedfrom:Catalysts2018,8,526,doi:10.3390/catal8110526 . . . . . . . . . . . . . . . . . . . 58
YunshanDong,ZongliangQiao,FengqiSi,BoZhang,CongYuandXiaomingJiang
ANovelMethodforthePredictionofErosionEvolutionProcessBasedonDynamicMeshand
ItsApplications
Reprintedfrom:Catalysts2018,8,432,doi:10.3390/catal8100432 . . . . . . . . . . . . . . . . . . . 80
AlexandraGimbernat,MarieGuehl,NicolasLopesFerreira,EgonHeuson,PascalDhulster,
MickaelCapron,FranckDumeignil,DamienDelcroix,Jean-Se´bastienGirardonandRe´nato
Froidevaux
FromaSequentialChemo-EnzymaticApproachtoaContinuousProcessforHMFProduction
fromGlucose
Reprintedfrom:Catalysts2018,8,335,doi:10.3390/catal8080335 . . . . . . . . . . . . . . . . . . . 96
v
Katarzyna Maresz, Agnieszka Ciemięga and Julita Mrowiec-Białoń
Selective Reduction of Ketones and Aldehydes Microreactor—Kinetic in Continuous-Flow
Studies
Reprintedfrom:Catalysts2018,8,221,doi:10.3390/catal8050221 . . . . . . . . . . . . . . . . . . . 116
ClaudiaCarlucci,LeonardoDegennaroandRenzoLuisi
TitaniumDioxideasaCatalystinBiodieselProduction
Reprintedfrom:Catalysts2019,9,75,doi:10.3390/catal9010075 . . . . . . . . . . . . . . . . . . . . 124
vi
About the Special Issue Editors
Christophe Len received his Ph.D. from the University of Picardie-Jules Verne (UPJV) in Amiens
(France)underthesupervisionofProfessorP.Villainthefieldofcarbohydratechemistry. In1996,
he joined Doctor G. Mackenzie’s group at the University of Hull (UK) as a post-doctoral fellow
toworkonthesynthesisofnucleosideanalogues. In1997,C.L.becameAssistantProfessoratthe
LaboratoiredesGlucidesofUPJVandworkedonthechemistryofantiviralnucleosideanalogues
specializing in those with novel glycone systems. In 2003, C.L. received his habilitation and
was promoted to full Professor in 2004 at the University of Poitiers (France), where he was the
supervisoroftheBiomolecules: SynthesisandMolecularOrganizationtem. For2008,C.L.recieved
a secondment to the University of Technology of Compie`gne—UTC (France) where he created
a new scientific team called Organic Chemistry and Alternative Technologies with the aim of
researching green chemistry and sustainable development. In 2010, C.L. became full Professor at
theUniversityofCompie`gne—UTC(France). SinceNovember2017,CLhasdevelopedhisresearch
at Chimie ParisTech (France) in the group Catalysis, Synthesis of Biomolecules and Sustainable
Development. C.L .is a member of the French Research Network GDR2053 CNRS Continuous
FlowChemistry.Len’sprincipalresearchinterestisorganicsynthesis,including: (i)thereactivityof
biomass-derivedmolecules(glycerol,fattyacids,lignin,cellulose)fortheformationofnewchemical
bonds; (ii) carbon–carbon cross coupling reactions (Suzuki–Miyaura, Tsuji–Trost reactions, etc.)
catalyzedbypalladiumcomplexesinaqueousmediawithorwithoutligands; (iii)homogeneous,
heterogeneous, and micellar catalysis using either commercial surfactants or new bio-based ones;
(iv) the use of unconventional media (water, critical fluids, ionic liquids); and (v) the use of
alternativemethodssuchasmicrowaveirradiation, ultra-sounds, photochemistry, andcontinuous
flow. His scientific work has been published in ca. 200 original international publications and
reviewarticles, 9chapters, and10patentsincludingpublicationsinhighprofilejournals. Among
recentawardsandrecognitionofhisscientificcareer,C.L.is: FellowofRoyalSocietyofChemistry
(FRSC, 2015); Fellow of Association of Carbohydrate Chemists and Technologists (ACCTI, 2015);
HonoraryLifeFellowofIndianSocietyofChemistsandBiologists(ISCB,2014);HonoraryProfessor
of the University of Hull, England (2012–2018); and received the ACI/NBB Glycerine Innovation
ResearchAward(2017).C.L.ismemberoftheEditorialBoardofMolecules,Catalysts,CurrentGreen
Chemistry,Sustainability,andScientificReports-Nature.
Renzo Luisi received a Ph.D. in Chemical Sciences at the University of Bari in 2000 under the
supervisionofProf. SaverioFlorio. In2001,hewasappointedresearchassistantattheUniversity
ofBariandin2005,AssociateProfessorofOrganicChemistryatthesameuniversity. After15years
in this role, in 2020, he was appointed full professor of Organic Chemistry at the Department
of Pharmacy—Drug Sciences of the University of Bari “A. Moro”. In 1999, R.L. was a Visiting
ScholartotheRogerAdamsLaboratoryattheUniversityofIllinoisatUrbana-Champaign,working
in the group of Prof. Peter Beak; in 2012, as visiting professor at the University of Manchester
workinginthegroupofProf. JonathanClayden. Duringhiscareer, hehasbeenvisitingscientist
in several academic institutions and industries. R.L.’s main research interests revolve around
organolithium-mediated stereoselective syntheses, the chemistry of heterosubstituted carbanions
and mecanistic investigations using advanced spectroscopic techniques. In 2014, R.L. created
the Flow Chemistry and Microreactor Technology Lab (FLAME-Lab) at the University of Bari,
vii
andstartedresearchprojectsinthefieldofsustainablechemistryusingenablingtechnology. RLis
funderofanacademicspin-off,memberofItalinaChemicalSocietyandFellowoftheRoyalSociety
ofChemistry. In2014,R.L.wasrecipientoftheCIMPISAwardonInnovationinChemistryforhis
contributiontothefieldofflowchemistrybasedonhighlyreactiveintermediates. Inrecentyears,
R.L.hascontributedtothefieldofnitrene-basedchemistrydevelopingsyntheticstrategiesforthe
synthesisofnitrogenatedmolecules.
R.L.’s research achievements are collected in more than 130 publications in international research
journals,1book,severalbookchapters,andreviewarticles.R.L.holdsseveralinternationalscientific
collaborationwithpharmacompaniesandeditorialactivities.Findmoreat:www.renzoluisi-lab.com.
viii
catalysts
Editorial
Catalytic Methods in Flow Chemistry
ChristopheLen1,*andRenzoLuisi2,*
1 PSLResearchUniversity,CNRSChimieParisTech,11ruePierreetMarieCurie,F-75005Paris,France
2 DepartmentofPharmacy—DrugSciences,UniversityofBari“A.Moro”viaE.Orabona4,70125Bari,Italy
* Correspondence:[email protected](C.L.);[email protected](R.L.)
Received:14June2019;Accepted:21June2019;Published:2August2019
Continuousflowchemistryisradicallychangingthewayofperformingchemicalsynthesis,and
severalchemicalandpharmaceuticalcompaniesarenowinvestinginthisenablingtechnology[1].
Fromthisperspective, thedevelopmentofcatalyticmethodsincontinuousflowhasprovideda
realbreakthroughinmodernorganicsynthesis. InthisSpecialIssueofCatalysts, recentresults
andnoveltrendsarereportedintheareaofcatalyticreactions(homogeneous,heterogeneous,and
enzymatic,aswellastheircombinations)undercontinuousflowconditions. Contributionstothis
SpecialIssueincludeoriginalresearcharticles,aswellasareviewfromexpertsinthefieldofcatalysis
andflowchemistry.
Twonewtechnologiesweredeveloped,andcompared,forthepreparationofdialkylsuccinates[2].
Inparticular,withtheaidofhomogenousacidcatalysis,thetrans-esterificationofdimethylsuccinate
wasachievedbyusingamicrowave-assistedflowreactor.Theuseofenzymaticcatalysis(withlipase
CalB)underflowconditionsallowedforthepreparationofdialkylsuccinatesbytrans-esterification
ofdimethylsuccinate.Theadvantagesofflowreactorscomparedtotraditionalbatchsettingswere
demonstratedinthisesterificationprocess.
Aninnovativecontinuousflowprocessfortheproductionofvaluable5-hydroxymethylfurfural
(HMF)fromglucosewasdeveloped[3].Theprocessproceedsviaenzymaticisomerizationofglucose,
selectivearylboronicacid-mediatedfructosecomplexation/transportation,andachemicaldehydration
toHMF.Interestingly,thenewreactorwasbasedontwoaqueousphasesdynamicallyconnectedvia
anorganicliquidmembrane,whichenabledsubstantialenhancementofglucoseconversionwhile
avoidingintermediateseparationsteps.Theuseofanimmobilizedglucoseisomeraseandanacidic
resinfacilitatedcatalystrecycling.
Zirconium-basedmesoporousmaterialswerepreparedandusedassuitablecatalystsforthe
continuousflowhydrogenationofmethyllevulinate[4].Thecatalystswereaccuratelycharacterized
inordertoascertainthestructure,texture,andacidicproperties. Allthepreparedmaterialswere
successfullyemployed, underflowconditions, forthehydrogenationofmethyllevulinateusing
2-propanolasthehydrogendonor.Betterperformancewasobservedwithcatalystspossessinghigher
dispersionofZrO2particles.
MonolithicflowmicroreactorswereemployedforstudyingthekineticsoftheMeerwein–Ponndorf–
Verleyreductionofcarbonylcompounds[5].Zirconium-functionalizedsilicamonolithsconstituted
thecoreofthereactorandperformedwellinpromotingthereductionofcyclohexanoneandother
ketonesandaldehydesusing2-butanolasthehydrogendonor.Importantkineticparametersanddata
onthereactionrateswerethemainoutputofthisstudy.
In the context of the treatment of wastewater containing chlorinated organic pollutants,
acontinuousflowprocessforhydrodechlorinationofchlorophenolswasreported[6]. Theprocess
reliesontheuseofaPd/carbonnanotube(CNT)-Nifoammicroreactorsystemandformicacidasthe
hydrogensource.Thecatalyticsystemperformedwellindechlorinationreactions,andthecatalyst
couldberegeneratedbyremovingtheabsorbedphenolfromthePdcatalystsurface.
Anoxidativeprocessconductedundercontinuousflowconditions,theMg-catalyzedOppenauer
reactionwasreported[7]. Byusingpivaldehydeorbromaldehydeasoxidants, andinexpensive
Catalysts2019,9,663;doi:10.3390/catal9080663 1 www.mdpi.com/journal/catalysts
