Unit:
Κατεύθυνση Ανόργανη Χημεία και ΤεχνολογίαLibrary of the School of Science
Author:
Zarkadoulas Athanasios
Dissertation committee:
Χ. Μητσοπούλου, Καθηγήτρια, Τμήμα Χημείας, ΕΚΠΑ
Ι. Παπαευσταθίου, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Π. Παρασκευοπούλου, Επίκουρη Καθηγήτρια, Τμήμα Χημείας, ΕΚΠΑ
Σ. Κοΐνης, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Κ. Μεθενίτης, Αναπληρωτής Καθηγητής, Τμήμα Χημείας ΕΚΠΑ
Α. Χρυσανθόπουλος, Επίκουρος Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Κ. Μπεθάνης, Επίκουρος Καθηγητής, Τμήμα Βιοτεχνολογίας, Γεωπονικό Πανεπιστήμιο Αθηνών
Original Title:
Photocatalytic and electrocatalytic hydrogen production with dithiolene complexes
Translated title:
Photocatalytic and electrocatalytic hydrogen production with dithiolene complexes
Summary:
The present thesis has been undertaken in the Laboratory of Inorganic Chemistry of National and Kapodistrian University of Athens. It covers literature reports on the application of dithiolene complexes as catalysts in electrocatalytic hydrogen evolution, and some bio–inspired supramolecular systems for homogeneous photocatalytic hydrogen evolution. Experimentally, the preparation, characterization, and investigation of series of nickel bis–dithiolene complexes is reported. These compounds have similar structural and electronic properties that can be tuned in order to establish structure – activity relationship. During this thesis, the first series of complexes is of the type [Ni(S2C2–p–C6H5–R)(S2C2–p–C6H5–R′)], where R = R′ = H, R = OMe and R′ = H, R = R′ = OMe. Crystal structures for compounds with R = OMe and R′ = H, and monoanionic R = R′ = OMe. The second series of complexes consists of the monoanionic compounds (NBu4)[Ni(bdt)2], (NBu4)[Ni(tdt)2], and (NBu4)[Ni(mnt)2], where bdt, tdt, and mnt denote benzene–1,2–dithiolate, toluene–3,4–dithiolate, and maleonitriledithiolate, respectively. The heteroleptic complex (NBu4)[Ni(S2C2Ph2)(mnt)] has been prepared and its crystal structure has been determined, along with three neutral alkyl–bridged bis–dithiolene compounds [Ni(bdt)2C3], [Ni(S2C2Ph2)2C3], and [Ni(S2C2–p–C6H4OMe)2C3], where C3 denotes a –CH2CH2CH2– bridge. All complexes have been characterized with spectroscopic and physicochemical methods, namely absorption spectroscopy, IR spectroscopy, 1H–NMR spectroscopy, and cyclic voltammetry. The complexes have been employed as proton reducing catalysts in organic media (DMF or MeCN) with organic acids (TFA etc) as the proton source.
Main subject category:
Science
Keywords:
photocatalysis, electrocatalysis, dithiolene, nickel, hydrogen
Number of index pages:
15
Number of references:
166
