Contemporary Solutions for Advanced Catalytic Materials with a High Impact on Society

170 Pages·2023·8.853 MB·English

by  Coman S.M., Tudorache M., Jacobsen E.E. (ed.)

Contemporary
Solutions for
Advanced Catalytic
Materials with
a High Impact
on Society
Edited by
Simona M. Coman, Madalina Tudorache
and Elisabeth Egholm Jacobsen
Printed Edition of the Special Issue Published in Catalysts
www.mdpi.com/journal/catalysts
Contemporary Solutions for Advanced
Catalytic Materials with a High Impact
on Society
Contemporary Solutions for Advanced
Catalytic Materials with a High Impact
on Society
Editors
Simona M. Coman
Madalina Tudorache
Elisabeth Egholm Jacobsen
MDPI Basel Beijing Wuhan Barcelona Belgrade Manchester Tokyo Cluj Tianjin
Editors
SimonaM.Coman MadalinaTudorache ElisabethEgholmJacobsen
OrganicChemistry, OrganicChemistry DepartmentofChemistry
BiochemistryandCatalysis BiochemistryandCatalysis NorwegianUniversityof
UniversityofBucharest UniversityofBucharest ScienceandTechnology
Bucharest Bucharest Trondheim
Romania Romania Norway
EditorialOffice
MDPI
St. Alban-Anlage66
4052Basel,Switzerland
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Contents
Preface to ”Contemporary Solutions for Advanced Catalytic Materials with a High Impact
onSociety” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Magdi El Fergani, Natalia Candu, Iunia Podolean, Bogdan Cojocaru, Adela Nicolaev and
CristianM.Teodorescuetal.
CatalyticHydrotreatmentofHuminsWasteoverBifunctionalPd-BasedZeoliteCatalysts
Reprintedfrom: Catalysts2022,12,1202,doi:10.3390/catal12101202 . . . . . . . . . . . . . . . . . 1
Sabina G. Ion, Octavian D. Pavel, Nicolae Guzo, Madalina Tudorache, Simona M. Coman
andVasileI.Parvulescuetal.
Use of Photocatalytically Active Supramolecular Organic–Inorganic Magnetic Composites as
EfficientRoutetoRemoveβ-LactamAntibioticsfromWater
Reprintedfrom: Catalysts2022,12,1044,doi:10.3390/catal12091044 . . . . . . . . . . . . . . . . . 19
SusanneHansen Troøyen, LucasBocquin, Anna LifenTennfjord, KristofferKlungsethand
ElisabethEgholmJacobsen
GreenChemo-EnzymaticProtocolsfortheSynthesisofEnantiopureβ-Blockers(S)-Esmololand
(S)-Penbutolol
Reprintedfrom: Catalysts2022,12,980,doi:10.3390/catal12090980 . . . . . . . . . . . . . . . . . . 33
AnnaKozioł,KristoferGunnarPasoandStanisławKuciel
PropertiesandRecyclabilityofAbandonedFishingNet-BasedPlasticDebris
Reprintedfrom: Catalysts2022,12,948,doi:10.3390/catal12090948 . . . . . . . . . . . . . . . . . . 45
Elena E. Toma, Giuseppe Stoian, Bogdan Cojocaru, Vasile I. Parvulescu and Simona M.
Coman
ZnO/CQDsNanocompositesforVisibleLightPhotodegradationofOrganicPollutants
Reprintedfrom: Catalysts2022,12,952,doi:10.3390/catal12090952 . . . . . . . . . . . . . . . . . . 61
ChongChen,YunLiandJilinCao
Methane Hydrate Formation in Hollow ZIF-8 Nanoparticles for Improved Methane Storage
Capacity
Reprintedfrom: Catalysts2022,12,485,doi:10.3390/catal12050485 . . . . . . . . . . . . . . . . . . 79
Serly Jolanda Sekewael, Remi Ayu Pratika, Latifah Hauli, Amalia Kurnia Amin, Maisari
UtamiandKarnaWijaya
Recent Progress on Sulfated Nanozirconia as a Solid Acid Catalyst in the Hydrocracking
Reaction
Reprintedfrom: Catalysts2022,12,191,doi:10.3390/catal12020191 . . . . . . . . . . . . . . . . . . 93
HonghaiWang,WendaYue,ShulingZhang,YuZhang,ChunliLiandWeiyiSu
Modification of Silica Xerogels with Polydopamine for Lipase B from Candida antarctica
Immobilization
Reprintedfrom: Catalysts2021,11,1463,doi:10.3390/catal11121463 . . . . . . . . . . . . . . . . . 117
Giulia Roxana Gheorghita, Victoria Ioana Paun, Simona Neagu, Gabriel-Mihai Maria,
MadalinEnacheandCristinaPurcareaetal.
Cold-Active Lipase-Based Biocatalysts for Silymarin Valorization through Biocatalytic
AcylationofSilybin
Reprintedfrom: Catalysts2021,11,1390,doi:10.3390/catal11111390 . . . . . . . . . . . . . . . . . 133
v
Morten Andre Gundersen, Guro Buaas Austli, Sigrid Sløgedal Løvland, Mari Bergan
Hansen,MariRødsethandElisabethEgholmJacobsen
LipaseCatalyzedSynthesisofEnantiopurePrecursorsandDerivativesfor-BlockersPractolol,
PindololandCarteolol
Reprintedfrom: Catalysts2021,11,503,doi:10.3390/catal11040503 . . . . . . . . . . . . . . . . . . 147
vi
Preface to ”Contemporary Solutions for Advanced
Catalytic Materials with a High Impact on Society”
“Contemporarysolutionforadvancedmaterialswithhighimpactonsociety”isaSpecialIssue
dedicated to a workshop with a similar name (with the acronym CoSolMat) organized on the
11th–15th of October 2021 within the GREENCAM project (project no. 18-COP-0041, October
2019–September 2022, project partners University of Bucharest (UB, Bucharest, Romania), and
NorwegianUniversityofScienceandTechnology(NTNU,Trondheim,Norway)).
The GREENCAM project proposes an alliance between Green Chemistry and Advanced
Materials in response to the contemporary issues related to the environmental pollution and
eco-friendly industry, which emerged from the general concept of environmental preservation. In
thisway,GREENCAMoffersaproperconditionforthedevelopmentofanextensivestudyinthearea
of advanced (e.g. nano-) materials with a critical awareness of the theoretical and practical aspects
related to the modern concepts of green (nano)synthesis. GREENCAM advocates for the extensive
applicationoftheprinciplesofgreenchemistryinchemicalsynthesis,especiallyforthepreparation
oftheseadvancedmaterialsasapromisingperspectiveforaneco-friendlyindustry.
Basedonthecontinuousadvancementsintheareaofadvancedmaterialsand,asaconsequence,
the new challenges to be faced, a focus on this matter is highly desirable. UB, represented by Prof.
SimonaM.ComanandAssoc.Prof.MadalinaTudoracheincollaborationwiththeNTNUrepresented
byAssoc. Prof. ElisabethJacobsenlaunchedtheideaforcollectingvaluablepublicationsdedicated
to contemporary solutions for issues related to the preparation/characterization and applications
of the advanced materials with a high impact on society. The main aim of this Special Issue is to
highlightnoveldevelopedstrategiesdesignedforpromotingGreenAdvancedMaterials(GAM),i.e.,
newconceptsandstrategiesfordesigningGAMstogetherwiththeirmostimportantapplicationfor
improvingthehealthandsecurityofourpresent-daysociety.Teachersandresearchersfromacademic
andindustrialareaswithexpertiseintheGAMsfieldhaveofferedtheircontributions. Furthermore,
youngresearchersarewellrepresented,alsodemonstratingtheirinterestsinthisresearchdirection.
Therefore, this Special Issue has collected original topics, most of which were shared during the
CoSolMatworkshop,providingnewinsightsintotheGAMsfield.
We conclude by hoping that this Special Issue will act in the future as a manifesto for the
mandatoryimplementationofGAMsandGreenChemistryinordertoensurethe industrialpractices
requiredforahealthyandsecuresociety.
Disclaimer: This publication was realized with the financial support of the EEA Financial
Mechanism 2014-2021. Its content (text and photos) does not reflect the official opinion of
the Programme Operator, the National Contact Point, or the Financial Mechanism Office. The
responsibilityfortheinformationandviewsexpressedthereinliesentirelywiththeauthor(s).
SimonaM.Coman,MadalinaTudorache,andElisabethEgholmJacobsen
Editors
vii
catalysts
Article
Catalytic Hydrotreatment of Humins Waste over Bifunctional
Pd-Based Zeolite Catalysts
MagdiElFergani1 ,NataliaCandu1,IuniaPodolean1,BogdanCojocaru1 ,AdelaNicolaev2,
CristianM.Teodorescu2,MadalinaTudorache1 ,VasileI.Parvulescu1andSimonaM.Coman1,*
1 DepartmentofOrganicChemistry,BiochemistryandCatalysis,FacultyofChemistry,UniversityofBucharest,
BdulReginaElisabeta4-12,030016Bucharest,Romania
2 NationalInstituteofMaterialsPhysics,Atomistilor405b,077125Magurele-Ilfov,Romania
* Correspondence:[email protected]
Abstract:Thecatalytichydrotreatmentofhumins,thesolidbyproductproducedfromtheconversion
ofC6sugars(glucose,fructose)to5-hydroxymethylfurfural(HMF),usingsupportedPd@zeolite
(Beta,Y,andUSY)catalystswithdifferentamountsofPd(i.e.,0.5,1.0and1.5wt%)wasinvestigated
undermolecularhydrogenpressure. Thehighestconversionofhumins(52.0%)wasobtainedon
1.5Pd@USYcatalystwhilethehighestamountofhuminsoil(27.3%)wasobtainedinthepresence
◦
of the 1Pd@Beta zeolite sample, at P = 30 bars and T = 250 C. The major compounds in the
H2
huminsoilevidencedbyGC-MSarealcohols,organicacids,ethers,andalkyl-phenolics.However,
althoughalltheseclassesofcompoundsareobtainedregardlessofthenatureofthecatalystused,
thecompositionofthemixturediffersfromonecatalysttoanother. Furaniccompoundswerenot
identifiedinthereactionproducts. Apossibleexplanationmayberelatedtotheirhighreactivity
underthereactionconditions,inthepresenceofthePd-basedcatalyststhesecompoundsleadto
Citation:ElFergani,M.;Candu,N.; alkylphenolics,importantintermediatesinthepetrochemicalindustry.
Podolean,I.;Cojocaru,B.;
Nicolaev,A.;Teodorescu,C.M.; Keywords:palladium;zeolites;bifunctionalcatalysts;humins;hydrotreatment;biobasedcompounds
Tudorache,M.;Parvulescu,V.I.;
Coman,S.M.Catalytic
HydrotreatmentofHuminsWaste
overBifunctionalPd-BasedZeolite
1. Introduction
Catalysts.Catalysts2022,12,1202.
Inthelastnumberofdecades,significantattentionhasbeenpaidtotheutilizationof
https://doi.org/10.3390/
renewablebiomassplatformmoleculesaspromisingcarbonresourcesthatmightpartlybe
catal12101202
usedasasubstituteforfossilfuels. Furan-derivativecompounds,forinstance,areusedin
AcademicEditor:RomanBulánek
theproductionofawiderangeofchemicals,including2,5-dimethylfuran,furanedioicacid,
Received:31July2022 pentanoicacidesters,levulinicacid(LA)anditsesters,andγ-valerolactone[1,2]. However,
Accepted:1October2022 duetotheirhighreactivity,thefuran-derivativecompoundsalsotendtopolymerizeinthe
Published:9October2022 acid-catalyzedreactions,resultinginlargeamountsofundesirablepolyfuranicpolymer
by-products (i.e., humins) which severely limit an efficient utilization of the renewable
Publisher’sNote:MDPIstaysneutral
biomass[3,4]. Toovercomethisinconvenience,theformationofhuminsshouldbesup-
withregardtojurisdictionalclaimsin
pressedbydevelopingefficientcatalyticsystemsabletoconvertthebiomassinaselective
publishedmapsandinstitutionalaffil-
waytothetargetedproducts. However,suchanobjectiveisdifficulttoachievesincethe
iations.
formationofhuminsisfavoredfromthethermodynamicpointofview. Alternatively,the
huminsformedduringsuchprocessesshouldbevalorizedandseveralreportsindicatetheir
potentialinthefabricationofmaterialssuchascomposites[5],catalysts[6],orfunctional
Copyright: © 2022 by the authors. carbonmaterials[7].
Licensee MDPI, Basel, Switzerland. Thechemicalstructureofhuminsalsorecommendsthemasanimportantsourcefor
This article is an open access article theproductionofchemicals. Thus,severalreportsalreadysuggestedhuminsasaproper
distributed under the terms and feedstock for the production of important compounds such as hydrogen and synthesis
conditionsoftheCreativeCommons gas[8],alkylphenolicsandoligomers(followingadepolymerizationandhydrodeoxygena-
Attribution(CCBY)license(https:// tiontandem)[9],easilytransportablefuelswithahighenergydensityorlowmolecular
creativecommons.org/licenses/by/ weightcompounds(suchasintermediatesfortheproductionofhighaddedvaluebulk
4.0/).
1
Catalysts2022,12,1202
chemicals like acetic and formic acids) [10]. In most of these approaches, the catalytic
alternativeprovidesimportantadvantages[11–13].
However,inspiteofitssocio-economicimportance,thevalorizationofhuminsvia
depolymerizationandsubsequenthydrodeoxygenationtoliquidhydrocarbonsisstillin
theinfancystage. Inthiscontext,Ru/C[9]andPt/C[14]werereportedashighlyefficient
◦
catalystsfortheliquefactionofhumins,affordingconversionsof60–70%at400 C,inthe
presenceofisopropanol(IPA)asahydrogendonor. Otherstudiescarriedoutatthesame
temperatureinvestigatedthehydrodeoxygenationoffructose-derivedhuminsinmethanol,
underH (30bars),takingRu/C,Rh/C,Pt/C,andPd/Cascatalysts. Amongthese,the
2
conversionreached75%onRh/C[15]. ThereplacementofCwithsupportssuchasTiO ,
2
ZrO ,andCeO ledonlytoasmallincreaseinconversion(around80%)[16]. Veryrecent
2 2
reportsalsoindicatedthehighefficiencyofamorecomplexRu/W-P-Si-Obifunctional
catalystintheselectiveproductionofcyclicandaromatichydrocarbonsfromhuminsunder
mildreactionconditions[17].
Inspired by this state of the art, the aim of this work was to develop an efficient
catalyticsystemforthehuminshydrodeoxygenationtofunctionalizedlowmolecularmass
organicmolecules(suchasalcohols,ketones,andphenolics)thatmayserveasasourcefor
valuablebio-basedchemicals. Withthisscope,theinvestigationsfocusedonhierarchical
tailoredbifunctionalPd@zeolites(Beta,Y,andUSY)withenhancedcatalyticperformances.
2. ResultsandDiscussion
The structure of humins is still incompletely understood. However, for humins
prepared from C6 sugars, the characterization studies indicated a core-shell morphol-
ogywithafuran-richstructurecontainingetherand(hemi)acetallinkages[18–21]. The
physico-chemicalcharacterizationofthesynthesizedhumins[19]followingahydrothermal
treatmentofglucoseindicatedachemicalstructurewithamorphologyinlinewiththese
literaturestudies[18,20,21]. Itcorrespondedtosphericalshell-coreinterconnectedparticles
with a structure consisting of a furan-rich polymeric network linked by functionalized
aliphaticchainswithaldehydeandbeta-hydroxyacids[19,21](Figure1).
Figure1. ThemorphologyandmolecularstructureofhuminsobtainedfromC6sugars(Adapted
withpermissionfromRef[19,21],Elsevier,2022).
2.1. Physico-ChemicalCharacterizationofPd@zeoliteCatalysts
Zeolite-supported metal species are usually prepared via a simple impregnation
approach [22,23]. However, the resulting catalysts are complex and this complexity is
influencedbyseveralfactors,suchasthezeoliteframework,SiO /Al O ratio,thetypeof
2 2 3
exchangedcation,andthestrengthoftheacidsites[24]. Thisworkconsideredzeolitesin
theH-formwithdifferentSiO /Al O ratios(i.e.,25.0(H-Beta),5.2(H-Y),and30.0(H-USY),
2 2 3
anddifferenttexturalproperties.
2
Catalysts2022,12,1202
− ◦
N adsorption-desorptionisothermsofliquidnitrogenat 196 Candtheporesize
2
distribution(determinedfromtheBJHmethod)areshowninFigures2and3,whilethe
texturalfeaturesofthepreparedcatalystsandsupports(H-Beta,H-Y,andH-USY)arelisted
inTable1.
(cid:12) (cid:12)
(cid:51) m
(cid:55) n
(cid:15)(cid:3)(cid:54) 3m/g.
(cid:74) c
(cid:22)(cid:18) (cid:72)(cid:3)(cid:11)
(cid:80) (cid:80)
(cid:11)(cid:70) (cid:82)(cid:79)(cid:88)
(cid:3) (cid:57)
(cid:80)(cid:72) (cid:72)(cid:3)
(cid:85)
(cid:82)
(cid:88) (cid:51)
(cid:79)
(cid:82) (cid:19) (cid:21)(cid:19) (cid:23)(cid:19) (cid:25)(cid:19) (cid:27)(cid:19) (cid:20)(cid:19)(cid:19)
(cid:57) (cid:51)(cid:82)(cid:85)(cid:72)(cid:3)(cid:39)(cid:76)(cid:68)(cid:80)(cid:72)(cid:87)(cid:72)(cid:85)(cid:3)(cid:11)nm(cid:12)
(cid:3)
(cid:71)
(cid:72)
(cid:69)
(cid:85) (cid:20)(cid:17)(cid:24)(cid:51)(cid:71)(cid:35)(cid:37)(cid:72)(cid:87)(cid:68)
(cid:82)
(cid:86) (cid:3)(cid:20)(cid:51)(cid:71)(cid:35)(cid:37)(cid:72)(cid:87)(cid:68)
(cid:71)
(cid:36) (cid:19)(cid:17)(cid:24)(cid:51)(cid:71)(cid:35)(cid:37)(cid:72)(cid:87)(cid:68)
(cid:3)(cid:3)(cid:3)(cid:3)(cid:43)(cid:16)(cid:37)(cid:72)(cid:87)(cid:68)
(cid:19)(cid:17)(cid:19) (cid:19)(cid:17)(cid:21) (cid:19)(cid:17)(cid:23) (cid:19)(cid:17)(cid:25) (cid:19)(cid:17)(cid:27) (cid:20)(cid:17)(cid:19)
(cid:3)(cid:53)(cid:72)(cid:79)(cid:68)(cid:87)(cid:76)(cid:89)(cid:72)(cid:3)(cid:51)(cid:85)(cid:72)(cid:86)(cid:86)(cid:88)(cid:85)(cid:72)(cid:3)(cid:11)P/P (cid:12)
o
Figure2.N adsorption-desorptionisothermsoftheH-Beta,0.5Pd@Beta,1Pd@Beta,and1.5Pd@Beta.
2
Theporesizedistributionisgivenintheinset.
Figure3.N adsorption-desorptionisothermsofthe1Pd@[email protected]
2
distributionisgivenintheinset.
3