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Study of the water photolysis process in the presence of complex compounds of copper and ruthenium

Author: Marin Ion
Degree:doctor of chemistry
Speciality: 02.00.04 - Physical chemistry
Scientific adviser: Gheorghe Duca
doctor habilitat, professor, Moldova State University
Institution: Institute of Chemistry of the ASM


The thesis was presented on the 11 September, 2020
Approved by NCAA on the 30 October, 2020


Adobe PDF document1.48 Mb / in romanian


CZU 541.145(043.2)

Adobe PDF document 7.97 Mb / in romanian
176 pages


photolysis, water, hydrogen, oxygen, photo-anode, titanium dioxide, ruthenium, copper, electrochemistry, photo-electrochemical cells, DFT


6 Thesis structure: (introduction, four chapters, general conclusions and recommendations, bibliography of 145 titles, 6 annexes, 142 pages of basic text, 88 figures, 25 tables and 81 equations). The results are published in 14 scientific papers.

The field of study: 144.01 – Physical Chemistry.

The aim of scientific work: study of the water photolysis process in the presence of new obtained sensitizers, electron traps, catalysts, photocatalysts based on coordinative compounds of copper and ruthenium in new elaborated photoelectrochemical applications.

Specific objectives: elucidation of the photophysical, electrochemical properties and application potential of newly synthesized molecular systems based on bidentate and tridentate pyridine ligands complexed with ruthenium and copper, and conceptualization of the mechanism of water photolysis reactions on semiconductor photovoltaic surfaces.

Scientific originality and novelty: fundamental examination of the water photolysis processes in the presence of new synthesized additives. The elaboration of the modelled photocatalytic system challenge obtaining and characterisation of several classes of new molecular systems: 2 types of electron traps based on Ru(II) and Ru(III) complexed with biquinolinopyridine ligands; 3 new chalconic dyes; 1 water oxidation compound; 1 water reduction compound and other 13 derivatives and novel intermediates with donor and acceptor functional groups.

Obtained scientific results: the original photoactive molecular systems as sensitizers and photocatalysts based on copper and ruthenium newly obtained and photoactive properties proven contributed to developing the mechanism concept of water photolysis in bisectional photoelectrochemical cells for the applications of obtaining hydrogen from water.

Theoretical significance: consists in more in-depth knowledge of the synthesis, purification and characterization methods by modern physicochemical methods (IR, mass, UV- Vis, NMR, X-ray diffraction, cyclic voltammetry and DFT molecular modelling) which allows the development and synthesis of more efficient components for the water photolysis process.

Applicative value: sensitized semiconductor surfaces with coordinative compounds with bidentate and tridentate pyridine ligands demonstrate significant photo-activity in water decomposition, providing valuable results (η = 7.2%, ΔEmax = 1.14 V) in the conversion of solar energy into photovoltaic current and chemical energy.

Implementation of scientific results: The obtained results suggest the possibility of using the new obtained chromophores and photocatalysts in photoelectrochemical cells for water photolysis.