Table Of ContentMaterials Science in Photocatalysis
Materials Science
in Photocatalysis
Edited by
Elisa I. Garcı´a-Lo´pez
Professor, Department of Biological Chemical and Pharmaceutical Sciences and Technologies
(STEBICEF), University of Palermo, Palermo, Italy
Leonardo Palmisano
“Schiavello-Grillone” Photocatalysis Group, Department of Engineering, University of Palermo,
Palermo, Italy
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Contributors
Numbers in parentheses indicate the pages on which the authors’ University,CenterforMembraneTechnology,Aalborg,
contributionsbegin. Denmark
ZahraAbbasi(235),DepartmentofChemistry,Facultyof VlastaBrezova´ (125),InstituteofPhysicalChemistryand
Science,ShahidChamranUniversityofAhvaz,Ahvaz, ChemicalPhysics,FacultyofChemicalandFoodTech-
Iran nology,SlovakUniversityofTechnologyinBratislava,
Bratislava, Slovak Republic
Sambandam Anandan (283), Department of Chemistry,
National Instituteof Technology,Trichy,India Adele Brunetti(523),InstituteonMembraneTechnology
(ITM-CNR), National Research Council c/o The
MasakazuAnpo(171),DepartmentofAppliedChemistry,
University ofCalabria, Rende CS, Italy
GraduateSchoolofEngineering,OsakaPrefectureUni-
versity, Sakai, Osaka, Japan V.Capucci(649),IrisCeramicaGroup,FioranoM.se,Italy
K Aswani Raj (505), Department of Chemistry, IIT Erik Cerrato (221), Department of Chemistry and NIS
Dharwad, Dharwad,Karnataka, India Centre,University ofTorino, Torino, Italy
Ana Bahamonde (83), Environmental Catalystis Engi- G. Cerrato (649), Department of Chemistry, Universita`
neering Group, Institute of Catalysis and Petrochem- degliStudi diTorino, Torino, Italy
istry, Madrid, Spain
FedericoCesano(385),ChemistryDepartment;NISInter-
F. Baldassarre (603), Biological and Environmental departmental Centre, Torino University,Torino,Italy
SciencesDepartment&UdRINSTMofLecce,University
G. Ciccarella (603), Biological and Environmental
of Salento; Institute of Nanotechnology, CNR
Sciences Department & UdR INSTM of Lecce,
NANOTEC,NationalResearchCouncil,Lecce,Italy
University of Salento; Institute of Nanotechnology,
Giuseppe Barbieri (523), Department of Environmental CNR NANOTEC, National Research Council, Lecce,
andChemicalEngineering,TheUniversityofCalabria, Italy
Rende CS, Italy
Juan C. Colmenares (575), Institute of Physical Chem-
Zuzana Barbierikova´ (125), Institute of Physical Chem- istry, Polish Academy of Sciences,Warsaw, Poland
istry and Chemical Physics, Faculty of Chemical and
JoseC.Conesa(267),InstituteofCatalysisandPetrochem-
Food Technology, Slovak University of Technology
istry, CSIC, Madrid,Spain
inBratislava, Bratislava, Slovak Republic
JuanM.Coronado(139),InstituteofCatalysisandPetro-
E. Bernardini (357), Chemistry Department, Torino
chemistry, CSIC,Madrid,Spain
University,Torino, Italy
M.Covei(371),CenterforRenewableEnergySystemand
C.L. Bianchi (649), Department of Chemistry, Universita` Recycling, Transilvania University of Brasov, Bra¸sov,
degli Studi di Milano, Milano, Italy
Romania
Vittorio Boffa (385), Aalborg University, Center for
F. Deganello (357), Institute for the Study of Nanostruc-
Membrane Technology,Aalborg, Denmark
tured Materials (ISMN)—Italian National Research
C.Bogatu(371),CenterforRenewableEnergySystemand Council(CNR), Palermo,Italy
Recycling, Transilvania University of Brasov, Bra¸sov,
Francesco Di Franco (115), Dipartimento di Ingegneria,
Romania
Universita` degli Studi di Palermo, Palermo,Italy
Fabr´ıcio Eduardo Bortot Coelho (385), Chemistry
R. Djellabi (649), Department of Chemistry, Universita`
Department, Torino University, Torino, Italy; Aalborg
degliStudi diMilano, Milano, Italy
xv
xvi Contributors
A. Duta (371), Center for Renewable Energy System and Cd. Universitaria, San Nicola´s de los Garza, NL,
Recycling, Transilvania University of Brasov, Bra¸sov, Mexico
Romania
Sam Hseien-Y. Hsu (575), School of Energy and
Dana Dvoranova´ (125), Institute of Physical Chemistry Environment, Hong Kong, China
and Chemical Physics, Faculty of Chemical and Food
Shin-Ting Hwang (283), Department of Environmental
Technology, Slovak University of Technology in
Engineering and Science, Feng Chia University,
Bratislava, Bratislava, Slovak Republic
Taichung, Taiwan
Gabriela Dyrda (183), Institute of Chemistry, University
Ana Iglesias-Juez (139), Institute of Catalysis and Petro-
ofOpole,Opole, Poland
chemistry,CSIC, Madrid, Spain
MayaEndo-Kimura(421),InstituteforCatalysis(ICAT),
Lakshmanan Karuppasamy (283), Department of Envi-
Hokkaido University,Sapporo, Japan
ronmental Engineering and Science, Feng Chia
D. Fabbri (357), Chemistry Department, Torino University,Taichung,Taiwan
University,Torino, Italy
MarcinKobielusz(95),FacultyofChemistry,Jagiellonian
IrinaM.Factori(341),HumanandNaturalSciencesCenter, University,Krako´w, Poland
FederalUniversity ofABC—UFABC, Santo Andr(cid:1)e,SP,
Ewa Kowalska (421), Institute for Catalysis (ICAT);
Brazil
Graduate School of Environmental Science, Hokkaido
Marisol Faraldos (83), Environmental Catalystis Engi- University,Sapporo, Japan
neering Group, Institute of Catalysis and Petrochem-
Anna Kubacka (409), Institute of Catalysis and Petro-
istry, Madrid,Spain
chemistry,CSIC, Madrid, Spain
Junting Feng (485), State Key Laboratory of Chemical
Joanna Kuncewicz (95), Faculty of Chemistry, Jagiel-
ResourceEngineering, Beijing University ofChemical
lonian University,Krako´w,Poland
Technology,Beijing, China
Maria Kuznetsova (341), Human and Natural Sciences
Pablo S. Ferna´ndez (341), Chemistry Institute, State
Center, Federal University of ABC—UFABC, Santo
University of Campinas—UNICAMP, Campinas, SP, Andr(cid:1)e, SP, Brazil
Brazil
Xianjun Lang (561), Sauvage Center for Molecular Sci-
Marcos Ferna´ndez-Garc´ıa (409), Institute of Catalysis
ences, College of Chemistry and Molecular Sciences,
and Petrochemistry, CSIC, Madrid, Spain
Wuhan University, Wuhan,China
Bel(cid:1)en Ferrer (543), Chemistry Department, Universitat
Enzo Laurenti (589), Chemistry Department, Torino
Polite`cnica deVale`ncia, Valencia, Spain
University,Torino,Italy
Paolo Fornasiero (485), Chemistry Department, INSTM
Xia Li (561), Sauvage Center for Molecular Sciences,
and ICCOM-CNR Trieste Research Unit, University
College of Chemistry and Molecular Sciences, Wuhan
ofTrieste, Trieste, Italy
University,Wuhan, China
Fernando Fresno (139), Photoactivated Processes Unit,
Leonarda F. Liotta (13), Institute for the Study of Nano-
InstituteIMDEAEnergy,Madrid,Spain
structured Materials, Palermo,Italy
R.Galli (649), DiSTAS-Department for SustainableFood
WojciechMacyk(95),FacultyofChemistry,Jagiellonian
Process,Universita`CattolicadelSacroCuore,Piacenza,
University,Krako´w, Poland
Italy
GiulianaMagnacca(357,385,589),ChemistryDepartment;
Hermenegildo Garc´ıa (543), Instituto Universitario de
NISInterdepartmentalCentre,TorinoUniversity,Torino,
Tecnolog´ıa Qu´ımica, CSIC-UPV, Universitat Poli-
Italy
te`cnicade Vale`ncia, Valencia,Spain
GiuseppeMarc`ı(13,37,319),DepartmentofEngineering,
Elisa I. Garc´ıa-Lo´pez (3, 13, 37, 235, 319), Department
Universityof Palermo, Palermo, Italy
of Biological, Chemical and Pharmaceutical Sciences
andTechnologies(STEBICEF),UniversityofPalermo, Michele Mazzanti (301), Department of Chemical,
Palermo,Italy Pharmaceutical and Agricultural Sciences, University
ofFerrara, Ferrara,Italy
DimitriosA.Giannakoudakis(575),InstituteofPhysical
Chemistry, Polish Academy of Sciences, Warsaw, Giuseppe Mele (183), Department of Engineering for
Poland Innovation,University ofSalento, Lecce,Italy
D.B.Hernandez-Uresti(211),AutonomousUniversityof AriannaMelillo(543),ChemistryDepartment,Universitat
Nuevo Leo´n, Physical-Mathematical Sciences Faculty, Polite`cnicade Vale`ncia, Valencia, Spain
Contributors xvii
Marco Minella (449), Department of Chemistry and IleniaRossetti(63),ChemicalPlantsandIndustrialChem-
NIS—Nanostructured Interfaces and Surfaces Inte- istryGroup,DepartmentofChemistry,Universita`degli
rdepartmental Centre, University of Turin, Turin, Studi di Milano and INSTM Unit Milano Universita`,
Italy Milan, Italy
Claudio Minero (449), Department of Chemistry and D. Sa´nchez-Mart´ınez (211), Autonomous University of
NIS—Nanostructured Interfaces and Surfaces Interde- NuevoLeo´n,CivilEngineeringFaculty—Ecomaterials
partmental Centre, Universityof Turin, Turin, Italy andEnergyDepartment,Cd.Universitaria,SanNicola´s
de los Garza, NL, Mexico
Alessandra Molinari (301), Department of Chemical,
Pharmaceutical and Agricultural Sciences, University Monica Santamaria (115), Dipartimento di Ingegneria,
ofFerrara, Ferrara, Italy Universita` degli Studi di Palermo, Palermo,Italy
Nikolaos G. Moustakas (255), Leibinz Institute for Patricia V.B. Santiago (341), Chemistry Institute, State
Catalysis (LIKAT),Rostock,Germany University of Campinas—UNICAMP, Campinas, SP,
Brazil
Vaishakh Nair (575), National Institute of Technology
Karnataka, Mangalore,India Rudolf Słota (183), Institute of Chemistry, University of
Opole,Opole, Poland
SergioNavalo´n(543),ChemistryDepartment,Universitat
Polite`cnica de Vale`ncia, Valencia,Spain Fabrizio Sordello (449), Department of Chemistry and
NIS—Nanostructured Interfaces and Surfaces Interde-
Bunsho Ohtani (159), Institute for Catalysis, Hokkaido
partmental Centre, UniversityofTurin, Turin, Italy
University,Sapporo, Japan
Juliana S. Souza (341), Human and Natural Sciences
Sibila A.A. Oliveira (341), Human and Natural Sciences
Center, Federal University of ABC—UFABC, Santo
Center, Federal University of ABC—UFABC, Santo
Andr(cid:1)e,SP, Brazil Andr(cid:1)e,SP, Brazil
G. Spigno (649), DiSTAS-Department for Sustainable
L.Operti(649),DepartmentofChemistry,Universita`degli
Food Process, Universita` Cattolica del Sacro Cuore,
Studi diTorino, Torino,Italy
Piacenza, Italy
MariaCristinaPaganini(221),DepartmentofChemistry
Taymaz Tabari (95), Faculty of Chemistry, Jagiellonian
andNIS Centre,University ofTorino,Torino, Italy
University, Krako´w,Poland
L. Palmisano (3), Engineering Department, University of
Mai Takashima (159), Institute for Catalysis, Hokkaido
Palermo, Palermo,Italy
University, Sapporo,Japan
D. Perniu (371), CenterforRenewableEnergySystemand
Recycling, Transilvania University of Brasov, Bra¸sov, Masato Takeuchi (171), Department of Applied Chem-
istry,GraduateSchoolofEngineering,OsakaPrefecture
Romania
University, Sakai, Osaka, Japan
Albin Pintar (397), Laboratory for Environmental Sci-
MariaLuisaTesta(589),InstitutefortheStudyofNano-
encesandEngineering,DepartmentofInorganicChem-
structuredMaterials,ItalianNationalResearchCouncil,
istry and Technology, National Institute of Chemistry,
Palermo, Italy
Ljubljana, Slovenia
JovanaR.Prekodravac(575),Vin(cid:3)caInstituteofNuclear A´lvaro Tolosana-Moranchel (83), Nanotechnology and
Integrated BioEngineering Centre, School of Engi-
Sciences—National Institute of the Republic of
neering, Ulster University, Belfast, Northern Ireland,
Serbia, University of Belgrade Belgrade, Belgrade,
United Kingdom
Serbia
Alessandra Bianco Prevot (357, 589), Chemistry Mateusz Trochowski (95), Faculty of Chemistry, Jagiel-
Department, Torino University,Torino, Italy lonian University,Krako´w,Poland
Tharishinny Raja-Mogan (421), Institute for Catalysis MariaLauraTummino(357,589),ChemistryDepartment,
(ICAT); Graduate School of Environmental Science, TorinoUniversity,Torino,Italy
HokkaidoUniversity, Sapporo,Japan Kunlei Wang (421), Institute for Catalysis (ICAT),
M Rajeswara Rao (505), Department of Chemistry, IIT HokkaidoUniversity,Sapporo,Japan;NorthwestResearch
Dharwad, Dharwad,Karnataka, India Institute,Co.Ltd.ofC.R.E.C.,Lanzhou,P.R.China
Ba´rbaraS.Rodrigues(341),HumanandNaturalSciences Qian Wang (485), State Key Laboratory of Chemical
Center, Federal University of ABC—UFABC, Santo Resource Engineering,BeijingUniversityof Chemical
Andr(cid:1)e,SP, Brazil Technology, Beijing, China; Chemistry Department,
xviii Contributors
INSTMandICCOM-CNRTriesteResearchUnit,Uni- Gregor Zˇerjav (397), Laboratory for Environmental Sci-
versity of Trieste, Trieste,Italy encesandEngineering,DepartmentofInorganicChem-
istry and Technology, National Institute of Chemistry,
ZhishunWei(421),SchoolofMaterialsandChemicalEngi-
Ljubljana,Slovenia
neering,HubeiUniversityofTechnology,Wuhan,China
Shuaizhi Zheng (421), Key Laboratory of Low Dimen-
JerryJ.Wu(283),DepartmentofEnvironmentalEngineering
sional Materials and Application Technology of Min-
andScience,FengChiaUniversity,Taichung,Taiwan
istry of Education, School of Materials Science and
Andrea Zaffora (115), Dipartimento di Ingegneria, Uni-
Engineering,Xiangtan University,Xiangtan, China
versita` degli Studi diPalermo,Palermo, Italy
Preface
Materialssciencehasbecomeanextremely broadandmultidisciplinaryfieldofresearchandtheemergingtechnologies
whereitisappliedintherecentyearshavebeenastonishinglyincreasing.Photocatalysis,asabranchofcatalysis,hasbeen
oneofthesetechnologicfields,wherethestudyofthematerialsscienceresultedparticularlyimportant.Thisbookattempts
tocoverthemainaspectsintheverybroadfieldofmaterialsscienceaddressedtomaterialsappliedinheterogeneousphoto-
catalyticprocessofvariousnature.Averywideclassofphotocatalyticmaterialshavebeentreatedhereinanattemptof
coverboththemain basicaspectstoapproachthestudyofphotocatalyticmaterialsandalsoexamplesofsolidphotoca-
talysts, their features and applications, without, of course, being exhaustive due to the plethora of materials and aspects
which would be treated insuch aneffort.
Thisbookreportsinformationonseveraltypesofmaterialsusedinheterogeneousphotocatalysisbothfromatheoretical
andanapplicativepointofview.Wehopethatthe6sectionscomprising37chapterswillprovideafairlybroadoverview
for readers interested in this fascinating field of research. In addition to very popular bare and mixed metal oxides and
sulfidessuchasTiO ,ZnO,WO ,MoS ,othermorecomplexandinnovativematerialsareproposedsuchasmetal-organic
2 3 2
structures,grapheneandgrapheneoxide,magneticmaterials,plasmonicnanoparticles,and2Dmaterialsamongothers.The
readerwillbeabletoevaluatetheadvantagesanddisadvantagesofusingthevariousmaterials,takingintoaccountnotonly
theircostbutalsotheir(photo)stability,toxicity,andeaseofpreparation.Moreover,readerscanfindinthebookdifferent
typesofexamplesofphotocatalyticreactionsofoxidationandreductioncarriedoutinliquid–solidandingas–solidsystems
where the different heterogeneous photocatalysts would be suitable. The various materials presented have been tested,
amongotherreactions,forpollutantsdegradation, chemicaltransformations including CO activation, organic synthesis
2
and applications of biomimetic photocatalytic systems, fungal abatement in photocatalytic surfaces. We would like to
underline that the authors have tried to deal with the topics so that the reader who wishes to deepen them can find the
necessaryliteratureamongthenumerousreferencescitedineachchapter.Webelievethatabookthatsummarizesconcepts
andtopicsfromacertainfieldthatcanthenbefurtherexploredinthescientificliteratureisparticularlyusefulforyoung
researchersandPhDstudents,aswellasforexperiencedresearcherswhoareabouttostartresearchinthatfield.Finally,we
wanttothankallthecolleaguesandfriendswhoenthusiasticallyjoinedusinwritingthebook,andalastbutnotleastthanks
goestoElsevierandthestaffwhoaccompanieduswithgreatprofessionalismandpatienceduringthisrewardingadventure.
ElisaI. Garc´ıa-Lo´pez and Leonardo Palmisano
Every greatadvanceinscience has issuedfrom a new audacity of imagination
JohnDewey, 1929
xix
Chapter 1
Fundamentals of photocatalysis: The role
of the photocatalysts in heterogeneous
photo-assisted reactions
Elisa I.Garcı´a-Lo´pezaand L.Palmisanob
aDepartmentofBiological,ChemicalandPharmaceuticalSciencesandTechnologies(STEBICEF),UniversityofPalermo,Palermo,Italy,bEngineering
Department,UniversityofPalermo,Palermo,Italy
1 Introduction
The contemporary world is facing energy shortages and environmental problems, which hinder the evolution of human
civilizationgivingrisetovarioustypesofcrises.Thehugeconsumptionofenergyandenvironmentalpollutionfromtra-
ditional industrial processes, along with the increasing need for synthetic chemicals to satisfy current requirements, are
urgent issues tobe addressed for the development of new foundationsfor a sustainable future. These criticalchallenges
need solutions that require an important upgrade in energy sources and the conception of new generation processes and
manufacturingtechnologies. Researchers, over the past few decades, have been studyingseveral methods to understand
howtoovercometheseproblems.Inthiscontext,heterogeneousphotocatalysisappearsasoneoftheusefultechnologies
to help these urgent efforts, and it can contribute to managing the conversion of solar energy into chemical energy in a
sustainableway.
Thisintroductorychapterdiscussessomeessentialcharacteristicsofheterogeneousphotocatalysisbymakingconnec-
tionswiththermalcatalysis.Wehopethattheiranalysistogetherwiththeexplanationofsomekeyconceptsleadstobetter
understandingthecontentsofthechaptersinthisbook.Inparticular,thechapterhighlightstheimportanceofthefeatures
andparameters ofsolid photocatalysts.
2 Basic principles of photocatalysis
Whenthetermphotocatalysisfirstappearedinscientificliterature,photochemistsfocusedontheaspectsrelatedtospecific
processesacceleratedbylight.Fortheirpart,researchersactiveincatalysishighlightedthecatalyticaspects,focusingtheir
attentiononthecharacterizationtechniquestypicalofthermalcatalysisandonthereactionprocessesandmechanismsthat
canoccuronthesurfaceofsolidparticles,minimizingtheimportanceoflightfortriggeringandcontinuingthereaction.
Bothapproachesshouldbecombinedtofullyunderstandthephotochemicalandcatalyticaspectsofaheterogeneousphoto-
catalyticreaction.Therehasalwaysbeencompleteagreementinthescientificcommunityregardingtheconceptsanddef-
initionsofcatalysis[1],whereasagreementonthesesameaspectsofphotocatalysishasbeenreachedonlyinthelastyears
[2–4].Thetermphotocatalysisfirstappearedinliteratureasearlyas1911[5],butonlyBalyetal.,forthefirsttimein1921,
studiedthephenomenoninwhichlightacceleratedacatalyticreaction[6].Thepioneeringpapersinwhichphotocatalysis
was defined as the process in which the combination of light and a solid catalyst was able to influence a reaction were
publishedin1964byDoerfflerandHauffe[7,8].Fromthenon,sporadicexamplesofphotocatalyticreactionshavebeen
reportedupuntiltheworkofHondaetal.onthephotoelectrolysisofwaterandthephotoelectrocatalyticreductionofcarbon
dioxide usingtitanium dioxide (TiO ) [9].
2
Anaccelerationofresearchonheterogeneousphoto-assistedcatalysisoccurredfrom1972,whenFujishimaandHonda
publishedaworkonUVlight-inducedwatersplittingusingaTiO photoanode,althoughinprinciplethisworkfitsbetterin
2
thefieldofphoto-electrocatalysis [10]. Since then, considerable efforts have been madenotonly tounderstand the fun-
damentalsofheterogeneousphotocatalysis,butalsotoapplythistechnologytosolvingseveralenvironmentalproblems,
usingbothartificialenergyandsunlight.Theremovalofvirusesandbacteria,theeliminationofpollutingsubstances,the
MaterialsScienceinPhotocatalysis.https://doi.org/10.1016/B978-0-12-821859-4.00004-0
Copyright©2021ElsevierInc.Allrightsreserved. 3
