This thesis represents part of my research efforts aiming at the generation of new knowledge on the functionalization of carbon nanodiscs as well as the intercalation of graphene oxide and clays using a simple diamondoid derivative or polyhedral oligomeric silsesquioxanes (POSS). The thesis also contains a study on fabrication of new complex materials by the Langmuir-Schaefer method based on metal decorated POSS. The target of this work was the design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications

Potsi, Georgia

University of Groningen

   University of GroningenDesign and development of novel layered nanostructured hybrid materials for environmental,medical, energy and catalytic applicationsPotsi, GeorgiaIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2016Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Potsi, G. (2016). Design and development of novel layered nanostructured hybrid materials forenvironmental, medical, energy and catalytic applications. [Groningen]: University of Groningen.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 12-11-2019	169		List	of	Publications		1. Spyrou	K.*,	Potsi	G.*,	Diamanti	E.K.*,	Ke	X.,	Serestatidou	E.,	Verginadis	I.,	 et	 al.	 Towards	 Novel	 Multifunctional	 Pillared	 Nanostructures:	Effective	 Intercalation	 of	 Adamantylamine	 in	 Graphene	 Oxide	 and	Smectite	Clays.	Adv	Funct	Mater	[Internet].	2014;	24	(37):5841–50.		2. Zygouri	 P.,	Potsi	G.,	Mouzourakis	 E.,	 Spyrou	K.,	Gournis	D.,	 Rudolf	 P..	Non-covalent	 interactions	 of	 graphene	 with	 polycyclic	 aromatic	hydrocarbons.	Curr	Org	Chem.	2015;	19	(18).		3. Potsi	 G.,	 Rossos	 A.,	 Kouloumpis	 A.,	 Antoniou	 M.K.,	 Spyrou	 K.,	Karakassides	M.A.,	et	al.	Carbon	Nanostructures	Containing	Polyhedral	Oligomeric	 Silsesquioxanes	 (POSS)	 [Internet].	 Vol.	 20,	 Current	Organic	Chemistry.	2016.	p.	662–73.		4. Simari	 C.,	Potsi	 G.,	 Policicchio	 A.,	 Perrotta	 I.,	 Nicotera	 I.	 Clay–Carbon	Nanotubes	 Hybrid	 Materials	 for	 Nanocomposite	 Membranes:	Advantages	 of	 Branched	 Structure	 for	 Proton	 Transport	 under	 Low	Humidity	Conditions	in	PEMFCs.	J	Phys	Chem	C	[Internet].	2016	Feb	11;	120	(5):2574–84.		5. Terzopoulou	 Z.,	 Bikiaris	 D.N.,	 Triantafyllidis	 K.S.,	 Potsi	 G.,	 Gournis	 D.,	Papageorgiou	 G.Z.,	 et	 al.	 Mechanical,	 thermal	 and	 decomposition	behavior	of	 poly(ε-caprolactone)	nanocomposites	with	 clay-supported	carbon	nanotube	hybrids.	Thermochim	Acta.	2016;	642.		6. Madhushankar	B.	N., Kaverzin	A.,	Giousis	T.,	Potsi	G.,	Gournis	D.,	Rudolf	P.,	Blake	G.R.,Van	Der	Wal	C.H,	Van	Wees	B.J.	Electronic	properties	of	germanane	field-effect	transistors	(submitted)	7. Potsi	 G.,	 Ladavos	 A.K,	 Petrakis	 D.,	 Douvalis	 A.P,	 Sanakis	 Y.,	 Katsiotis	M.S.,	 Alhassan	 S.,	 Gournis	 D.,	 Rudolf	 P.,	 Iron-substituted	 cubic	silsesquioxane	 pillared	 clays:	 Synthesis,	 characterization	 and	 catalytic	applications	(to	be	submitted)	8. Zygouri	P.,	Tsoufis	T.,	Kouloumpis	A.,	Patila	M.,	Potsi	G.,	 Sideratou	Z.,	Katsaros	F.,	Charalambopoulou	G.,	Stamatis	H,	Rudolf	P.,	Steriotis	T.A.,	Gournis	 D.,	 Hydrophilic	 oxidized	 carbon	 nanodiscs:	 A	 promising	multifunctional	nanocarbon	for	bioapplication	(to	be	submitted)		*Equal	contribution		 		170			

Design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications

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University of Groningen Research Database

  
 University of Groningen
Design and development of novel layered nanostructured hybrid materials for environmental,
medical, energy and catalytic applications
Potsi, Georgia
IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from
it. Please check the document version below.
Document Version
Publisher's PDF, also known as Version of record
Publication date:
2016
Link to publication in University of Groningen/UMCG research database
Citation for published version (APA):
Potsi, G. (2016). Design and development of novel layered nanostructured hybrid materials for
environmental, medical, energy and catalytic applications [Groningen]: University of Groningen
Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the
author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).
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If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
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Download date: 11-02-2018
Design and development of novel layered 
nanostructured hybrid materials for environmental, 
medical, energy and catalytic applications 
	
	
	
	
	
	
This	PhD	thesis	is	the	result	of	an	effort	that	started	4	years	ago	at	the	Ceramics	and	
Composites	 Laboratory	 in	University	 of	 Ioannina	 and	was	 continued	 at	 the	 Zernike	
Institute	for	Advanced	Materials	in	University	of	Groningen.	
	
The	front	cover	page	designed	by	Antonios	Kouloumpis	represents	an	aluminosilicate	
clay	 structure	 and	 a	 graphene	 sheet.	 The	 photos	 used	 show:	 Pfizer's	 Unisom	
Diphenhydramine	 pills,	 (source	 Flickr,	 licensed	 under	 the	 Creative	 Commons	
Attribution),	 an	 Industrial	 Refinery	 Petroleum	 Plant,	 (source	 https://pixabay.com,	
free	photo),	a	close	shot	of	wind	turbines	at	a	wind	farm	(source:	http://www.public-
domain-image.com/public-domain-images-pictures-free-stock-photos/wallpapers-
public-domain-images-pictures/a-close-shot-of-wind-turbines-wind-farm.jpg,	 public	
domain,	not	copyrighted,	no	rights	reserved,	free	for	any	use).	
	
	
	
Zernike	Institute	PhD	thesis	series	2016-32	
ISSN:	1570-1530		
ISBN:	978-90-367-9340-7	(print)	
ISBN:	978-90-367-9339-1	(digital)	
	
         
 
 
Design and development of novel layered 
nanostructured hybrid materials for environmental, 
medical, energy and catalytic applications 
 
PhD thesis 
 
to obtain the degree of PhD of the 
University of Groningen 
on the authority of the 
Rector Magnificus Prof. E. Sterken 
and in accordance with 
the decision by the College of Deans. 
 
and 
 
to obtain the degree of PhD of 
University of Ioannina  
on the authority of the 
Rector Prof. G. Kapsalis 
and in the accordance with 
the decision of the General Meeting  
of the Department of Materials Science and Engineering 
 
Double PhD degree 
 
This thesis will be defended in public on 
 
Friday 16 December 2016 at 12.45 hours at University of Groningen 
& 
Wednesday 21 December 2016 at 12.00 hours at University of 
Ioannina 
	
	
by 
	
 
Georgia Potsi 
 
born on 11 April 1982 
in Ioannina, Greece 
 
Supervisors 
Prof. Dr. P. Rudolf 
Prof. Dr. D. Gournis 
	
 
		
	
	
Assessment committee for University of Groningen 
Prof. F.Picchioni 
Prof. M. Bonchio 
Prof. A. Paipetis 
Prof. G. Froudakis 
 
Assessment committee for University of Ioannina 
Prof. D. Gournis 
Prof. M. Karakassides 
Prof. A. Bourlinos  
Prof. P. Rudolf 
Prof. A. Douvalis 
Prof. H. Stamatis 
Prof. A. Paipetis 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
	
Keep	Ithaka	always	in	your	mind.	
Arriving	there	is	what	you’re	destined	for.	
But	don’t	hurry	the	journey	at	all.	
Better	if	it	lasts	for	years,	
so	you’re	old	by	the	time	you	reach	the	island,	
wealthy	with	all	you’ve	gained	on	the	way,	
not	expecting	Ithaka	to	make	you	rich.	
	
Ithaka	gave	you	the	marvelous	journey.	
Without	her	you	wouldn't	have	set	out.	
She	has	nothing	left	to	give	you	now.	
	
And	if	you	find	her	poor,	Ithaka	won’t	have	fooled	you.	
Wise	as	you	will	have	become,	so	full	of	experience,	
you’ll	have	understood	by	then	what	these	Ithakas	mean..	
	
By	C.	P.	CAVAFY	
Translation	by	E.Keele	
	
Contents	
Introduction	...........................................................................................................	9	
1.1.	Motivation	..............................................................................................................	9	
1.2.	Graphene,	Graphite	oxide	and	carbon	nanodiscs	..................................................	9	
1.2.1.	Graphene	.........................................................................................................	9	
1.2.2.	Graphene	oxide	..............................................................................................	10	
1.2.3.	Carbon	nanodiscs	...........................................................................................	10	
1.3.	Clays	......................................................................................................................	11	
1.3.1.	Pillared	Clays	..................................................................................................	12	
1.4.	Polyhedral	oligosilsesquioxanes	(POSS)	...............................................................	12	
1.5.	Langmuir	Blodgett/Langmuir	Schaefer	techniques	..............................................	13	
1.6.	Outline	of	the	thesis	.............................................................................................	15	
References	...................................................................................................................	16	
Experimental	Techniques	.....................................................................................	21	
2.1.	Preparation	of	host	layered	materials	..................................................................	21	
2.1.1.	Graphene	oxide	(Chapter	3)	...........................................................................	21	
2.1.2.	Natural	and	Synthetic	Clays	(Chapters	3	and	6)	.............................................	21	
2.1.3.	Acid	activation	of	clay	(Chapter	6)	.................................................................	22	
2.1.4.	Carbon	nanodiscs	CNDs	(Chapter	4)	..............................................................	22	
2.1.5.	Preparation	of	Clay/Adamantylamine	hybrid	(Chapter	3)	.............................	22	
2.1.6.	Preparation	of	graphene	oxide/adamantylamine	hybrid	(Chapter	3)	...........	23	
2.1.7.	Oxidation	of	carbon	nanodiscs	(Chapter	4)	....................................................	23	
2.1.8.	Organosilane	solutions	(Chapters	6	and	7)	....................................................	23	
2.2.	Characterization	Techniques	................................................................................	24	
2.2.1.	X-ray	Diffraction	(XRD)	(Chapters	3,	4,	6	and	7)	.............................................	24	
2.2.2.	FTIR	spectroscopy	(Chapters	3,	4	and	6)	........................................................	25	
2.2.3.	Raman	spectroscopy	(Chapters	3	and	4)	........................................................	25	
2.2.4.	Thermal	analysis	(Chapters	3,	4	and	6)	..........................................................	25	
2.2.5.	X-ray	Photoelectron	Spectroscopy	(XPS)	(Chapters	3,	4,	6	and	7)	.................	26	
2.2.6.	Atomic	force	microscopy	(Chapter	4)	............................................................	27	
2.2.7.	Mössbauer	spectra	(Chapter	6)	......................................................................	27	
2.2.8.	High-resolution	transmission	electron	microscopy	(Chapter	3)	....................	27	
2.2.9.	Surface	area	and	porosity	measurements	(Chapter	3	and	6)	........................	27	
2.2.10.	Catalytic	measurements	(Chapter	6)	............................................................	28	
2.2.11.	Study	of	cytotoxicity	in	vitro	(Chapters	3	and	4)	..........................................	29	
2.2.12.	Adsorption	of	chlorophenols	(Chapter	3)	....................................................	30	
References	...................................................................................................................	32	
Towards	novel	multi-functional	pillared	nanostructures:	effective	intercalation	
of	adamantylamine	in	graphene	oxide	and	smectite	clays	................................	35	
3.1.	Introduction	..........................................................................................................	36	
3.2.	Results	and	discussion	..........................................................................................	38	
3.3.	Conclusions	...........................................................................................................	60	
References	...................................................................................................................	62	
Appendix	.....................................................................................................................	68	
Oxidized	carbon	nanodiscs	as	cytotoxic	agents	..................................................	71	
4.1.	Introduction	..........................................................................................................	72	
4.2.	Results	and	discussion	..........................................................................................	74	
4.3.	Conclusions	...........................................................................................................	80	
References	...................................................................................................................	81	
Carbon	Nanostructures	containing	Polyhedral	Oligomeric	Silsesquioxanes	
(POSS)	...................................................................................................................	85	
5.1.	Introduction	..........................................................................................................	86	
5.2.	Fullerene	functionalization	with	POSS	and	their	derivatives	................................	87	
5.3.	Functionalization	of	carbon	nanotubes	with	POSS	and	derived	hybrids	..............	94	
5.4.	POSS	immobilization	on	graphene	and	graphene	oxide	and	resulting	hybrids	..	102	
5.5.	Conclusions	.........................................................................................................	106	
References	.................................................................................................................	107	
Iron-substituted	cubic	silsesquioxane	pillared	clays:	........................................	113	
Synthesis,	characterization	and	catalytic	applications	.....................................	113	
6.1.	Introduction	........................................................................................................	114	
6.2.	Results	and	Discussion	........................................................................................	116	
6.3.	Isopropanol	decomposition.	...............................................................................	125	
6.4.	Conclusions	.........................................................................................................	127	
References	.................................................................................................................	129	
Appendix	...................................................................................................................	134	
Fabrication	of	highly	ordered	Cu2+/Fe3+	substituted	POSS	thin	films,	a	case	study	
of	structure	influenced	by	metal	coordination	.................................................	137	
7.1.	Introduction	........................................................................................................	137	
7.2.	Method	of	preparation	.......................................................................................	139	
7.3.	Results	and	Discussion	........................................................................................	140	
7.3.1.	Characterization	of	the	deposition	of	AA-	Metal	(Cu+2,Fe+3)	POSS	hybrid	films
	...............................................................................................................................	140	
7.3.2.	XRR	Patterns	of	AA-POSS-Metal	hybrid	films	...............................................	142	
7.3.3.	Probing	the	surface	of	AA-Metal	POSS	hybrid	films	by	XPS	.........................	144	
7.4.	Perspectives	........................................................................................................	147	
7.5.	Conclusion	..........................................................................................................	147	
References	.................................................................................................................	149	
Summary	............................................................................................................	153	
Samenvatting	.....................................................................................................	157	
Περίληψη	...........................................................................................................	161	
Acknowledgements	............................................................................................	165	
List	of	Publications	.............................................................................................	169	
	
	


This thesis represents part of my research efforts aiming at the generation of new knowledge on the functionalization of carbon nanodiscs as well as the intercalation of graphene oxide and clays using a simple diamondoid derivative or polyhedral oligomeric silsesquioxanes (POSS).The thesis also contains a study on fabrication of new complex materials by the Langmuir-Schaefer method based on metal decorated POSS.The target of this work was the design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications

ARTS repository - University of Groningen

   University of GroningenDesign and development of novel layered nanostructured hybrid materials for environmental,medical, energy and catalytic applicationsPotsi, GeorgiaIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2016Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Potsi, G. (2016). Design and development of novel layered nanostructured hybrid materials forenvironmental, medical, energy and catalytic applications. [Thesis fully internal (DIV), University ofGroningen]. University of Groningen.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 09-09-2023Propositions / Stellingen Accompanying the thesis Design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications Georgia Potsi 1. Synthesis of hybrids is a smart way to use relatively cheap starting materials like clays and convert them to ones with extraordinary properties suitable for various applications. [chapter 3,5 and 7of the thesis] 2. Both adamantylamine and POSS can be used succesfully as pillars for layered materials. [chapter 3 and 6 of the thesis] 3. Adanantylamine molecules enhance the proexisting cytotoxic properties of clays and GO. [chapter 3 of the thesis] 4. CNDs appear to be prommising materials for biomedicine applications. [chapter 4 of the thesis]  5. Active sites on the surface of clays play significant role during the procedure of catalysis. [chapter 6 of the thesis] 6. The beauty of chemistry is that I can design my own molecular world. (Ben Feringa) 7. Science never solves a problem without creating ten more (George Bernard Shaw) 8. Science, my lad, is made up of mistakes, but they are mistakes which it is useful to make, because they lead little by little to the truth (Jules Verne) 9. Criticism is something we can avoid easily by saying nothing, doing nothing and being nothing (Aristotle) 10. When you are working on five projects you have better chance to publish one. 11. Sometimes projects don’t work, but sometimes changing your perspective can lead to findings more exciting to what you have been expecting in the beginning. 

English

   University of GroningenDesign and development of novel layered nanostructured hybrid materials for environmental,medical, energy and catalytic applicationsPotsi, GeorgiaIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2016Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Potsi, G. (2016). Design and development of novel layered nanostructured hybrid materials forenvironmental, medical, energy and catalytic applications. University of Groningen.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 08-06-2022Propositions / Stellingen Accompanying the thesis Design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications Georgia Potsi 1. Synthesis of hybrids is a smart way to use relatively cheap starting materials like clays and convert them to ones with extraordinary properties suitable for various applications. [chapter 3,5 and 7of the thesis] 2. Both adamantylamine and POSS can be used succesfully as pillars for layered materials. [chapter 3 and 6 of the thesis] 3. Adanantylamine molecules enhance the proexisting cytotoxic properties of clays and GO. [chapter 3 of the thesis] 4. CNDs appear to be prommising materials for biomedicine applications. [chapter 4 of the thesis]  5. Active sites on the surface of clays play significant role during the procedure of catalysis. [chapter 6 of the thesis] 6. The beauty of chemistry is that I can design my own molecular world. (Ben Feringa) 7. Science never solves a problem without creating ten more (George Bernard Shaw) 8. Science, my lad, is made up of mistakes, but they are mistakes which it is useful to make, because they lead little by little to the truth (Jules Verne) 9. Criticism is something we can avoid easily by saying nothing, doing nothing and being nothing (Aristotle) 10. When you are working on five projects you have better chance to publish one. 11. Sometimes projects don’t work, but sometimes changing your perspective can lead to findings more exciting to what you have been expecting in the beginning. 

Design and development of novel layered nanostructured hybrid materials for environmental, medical, energy and catalytic applications

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