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Pavliuk, Mariia V.
Alternative names
Publications (10 of 20) Show all publications
Pavliuk, M. (2019). Accumulative Charge Separation in Photocatalysis: From Molecules to Nanoparticles. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Accumulative Charge Separation in Photocatalysis: From Molecules to Nanoparticles
2019 (English)Doctoral thesis, comprehensive summary (Other academic) [Artistic work]
Abstract [en]

Photochemical energy conversion into solar fuel involves steps of light absorption, charge separation and catalysis. Nature has taught us that the effective accumulation of redox equivalents and charge separation are the key steps in sunlight conversion. The focus of this thesis is to unveil photophysical and photochemical processes that lead to accumulative charge separation. The optimization of electron transfer process will be held by minimization of losses via recombination, and extension of the lifetime of the charge separated state by usage of the electron relay.

The goal is to couple light induced electron transfer process with the multi-electron catalytic process of hydrogen evolution. In this regard, light harvesters (molecules, metal nanostructures) that generate at least two electrons per absorbed photon will be studied. Additionally, semiconductors that generate long-lived charge separated states are utilized to accumulate several redox equivalents necessary for hydrogen evolution.

The hybrid systems produced by the combination of the advantageous properties of molecules, semiconductors, and metal nanoparticles are under the scope of investigation. Metal nanoparticles are advantageous because of their high absorption cross-section. The molecular linkers provide control and flexibility in tuning the connection between the light absorber and the electron relay. Semiconductor nanoparticles offer the desired charge separation properties via prolonging the lifetime sufficiently to perform photocatalysis.

The detailed understanding, investigation and development of the hybrid systems is at the heart of the progress of photochemical solar fuel production.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 88
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1759
Keywords
Accumulative charge separation, Electron transfer, Plasmon dynamics, Time-resolved spectroscopy, Photocatalysis.
National Category
Chemical Sciences
Research subject
Chemistry with specialization in Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-369930 (URN)978-91-513-0543-1 (ISBN)
Public defence
2019-02-22, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2019-01-23 Created: 2018-12-17 Last updated: 2019-02-18
Buvailo, H. I., Makhankova, V. G., Kokozay, V. N., Omelchenko, I. V., Shishkina, S. V., Jezierska, J., . . . Shylin, S. I. (2019). Copper-containing hybrid compounds based on extremely rare [V2Mo6O26]6- POM as water oxidation catalysts. INORGANIC CHEMISTRY FRONTIERS, 6(7), 1813-1823
Open this publication in new window or tab >>Copper-containing hybrid compounds based on extremely rare [V2Mo6O26]6- POM as water oxidation catalysts
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2019 (English)In: INORGANIC CHEMISTRY FRONTIERS, ISSN 2052-1553, Vol. 6, no 7, p. 1813-1823Article in journal (Refereed) Published
Abstract [en]

Herein, we report two approaches to the synthesis of heterometallic complexes (NH4)(2n)(H(2)en)(n){[Cu(en)(2)][alpha-V2Mo6O26]}center dot 4nH(2)O (1), (NH4)(2){[Cu(dien)(H2O)](2)[alpha-V2Mo6O26]}center dot 5H(2)O (2) and (NH4)(2){[Cu(dien)(H2O)](2)[alpha-V2Mo6O26]}center dot 8H(2)O (3) that have been employed in homogeneous photochemical oxidation of water to dioxygen. In these hybrid metalorganic-inorganic compounds, copper-containing complex fragments are covalently bound to the rare vanadium-disubstituted alpha-octamolybdate cluster. They exhibit variable catalytic activity controlled by the local coordination environment of copper reaching a notably high turnover frequency of 0.24 s(-1) for 3 in combination with a relatively low water oxidation overpotential. The complexes have been also used as precursors for the preparation of mixed oxide phases that have proven to be active heterogeneous water oxidation catalysts.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-390977 (URN)10.1039/c9qi00040b (DOI)000475394700021 ()
Funder
Swedish Institute, 23913/2017
Available from: 2019-08-19 Created: 2019-08-19 Last updated: 2019-08-19Bibliographically approved
Shylin, S. I., Pavliuk, M. V., D'Amario, L., Mamedov, F., Sá, J., Berggren, G. & Fritsky, I. O. (2019). Efficient visible light-driven water oxidation catalysed by an iron(IV) clathrochelate complex. Chemical Communications, 55(23), 3335-3338
Open this publication in new window or tab >>Efficient visible light-driven water oxidation catalysed by an iron(IV) clathrochelate complex
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2019 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 55, no 23, p. 3335-3338Article in journal (Refereed) Published
Abstract [en]

A water-stable FeIV clathrochelate complex catalyzes fast and homogeneous photochemical oxidation of water to dioxygen with a turnover frequency of 2.27 s−1 and a maximum turnover number of 365. An FeV intermediate generated under catalytic conditions is trapped and characterised using EPR and Mössbauer spectroscopy.

Keywords
Artificial photosynthesis, water oxidation, iron catalyst, photochemical water oxidation, electrochemical water oxidation
National Category
Physical Chemistry
Research subject
Chemistry with specialization in Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-379606 (URN)10.1039/C9CC00229D (DOI)000461397500002 ()30801592 (PubMedID)
Funder
EU, Horizon 2020, 778245Swedish Institute
Available from: 2019-03-18 Created: 2019-03-18 Last updated: 2019-04-12Bibliographically approved
Pavliuk, M. V., Alvarez, S. G., Hattori, Y., Messing, M. E., Czapla-Masztafiak, J., Szlachetko, J., . . . Sá, J. (2019). Hydrated Electron Generation by Excitation of Copper Localized Surface Plasmon Resonance. Journal of Physical Chemistry Letters, 10(8), 1743-1749
Open this publication in new window or tab >>Hydrated Electron Generation by Excitation of Copper Localized Surface Plasmon Resonance
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2019 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 10, no 8, p. 1743-1749Article in journal (Refereed) Published
Abstract [en]

Hydrated electrons are important in radiation chemistry and charge transfer reactions, with applications that include chemical damage of DNA, catalysis, and signaling. Conventionally, hydrated electrons are produced by pulsed radiolysis, sonolysis, two-ultraviolet-photon laser excitation of liquid water, or photodetachment of suitable electron donors. Here we report a method for the generation of hydrated electrons via single-visible-photon excitation of localized surface plasmon resonances (LSPRs) of supported sub-3 nm copper nanoparticles in contact with water. Only excitations at the LSPR maximum resulted in the formation of hydrated electrons, suggesting that plasmon excitation plays a crucial role in promoting electron transfer from the nanoparticle into the solution. The reactivity of the hydrated electrons was confirmed via proton reduction and concomitant H-2 evolution in the presence of a Ru/TiO2 catalyst.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Physical Chemistry Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-383191 (URN)10.1021/acs.jpclett.9b00792 (DOI)000465507700014 ()30920838 (PubMedID)
Funder
Swedish Research CouncilStiftelsen Olle Engkvist Byggmästare
Note

De två första författarna delar förstaförfattarskapet.

Available from: 2019-07-24 Created: 2019-07-24 Last updated: 2019-07-24Bibliographically approved
Shylin, S. I., Pavliuk, M. V., D'Amario, L., Fritsky, I. O. & Berggren, G. (2019). Photoinduced hole transfer from tris(bipyridine)ruthenium dye to a high-valent iron-based water oxidation catalyst. Faraday discussions (Online), 215, 162-174
Open this publication in new window or tab >>Photoinduced hole transfer from tris(bipyridine)ruthenium dye to a high-valent iron-based water oxidation catalyst
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2019 (English)In: Faraday discussions (Online), ISSN 1359-6640, E-ISSN 1364-5498, Vol. 215, p. 162-174Article in journal (Refereed) Published
Abstract [en]

An efficient water oxidation system is a prerequisite for developing solar energy conversion devices. Using advanced time-resolved spectroscopy, we study the initial catalytic relevant electron transfer events in the light-driven water oxidation system utilizing [Ru(bpy)(3)](2+) (bpy = 2,2 '-bipyridine) as a light harvester, persulfate as a sacrificial electron acceptor, and a high-valent iron clathrochelate complex as a catalyst. Upon irradiation by visible light, the excited state of the ruthenium dye is quenched by persulfate to afford a [Ru(bpy)(3)](3+)/SO4- pair, showing a cage escape yield up to 75%. This is followed by the subsequent fast hole transfer from [Ru(bpy)(3)](3+) to the Fe-IV catalyst to give the long-lived Fe-V intermediate in aqueous solution. In the presence of excess photosensitizer, this process exhibits pseudo-first order kinetics with respect to the catalyst with a rate constant of 3.2(1) x 10(10) s(-1). Consequently, efficient hole scavenging activity of the high-valent iron complex is proposed to explain its high catalytic performance for water oxidation.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2019
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-392589 (URN)10.1039/c8fd00167g (DOI)000477683600011 ()30951052 (PubMedID)
Funder
EU, Horizon 2020, 778245Swedish Institute, 23913/2017
Available from: 2019-09-06 Created: 2019-09-06 Last updated: 2019-09-06Bibliographically approved
Pavliuk, M. V., Abdellah, M. & Sá, J. (2018). Hydrogen evolution with CsPbBr3 perovskite nanocrystals under visible light in solution. MATERIALS TODAY COMMUNICATIONS, 16, 90-96
Open this publication in new window or tab >>Hydrogen evolution with CsPbBr3 perovskite nanocrystals under visible light in solution
2018 (English)In: MATERIALS TODAY COMMUNICATIONS, ISSN 2352-4928, Vol. 16, p. 90-96Article in journal (Refereed) Published
Abstract [en]

Direct proton photo-reduction to molecular hydrogen with a lead-halide perovskite photosystem is presented. The concept uses CsPbBr3 nanocrystals and Ru@TiO2 nanoparticles as light harvesters and catalyst, respectively. The photo-system attains charge transfer from donor to acceptor via collision events, established via static and ultrafast spectroscopy. The photo-system exhibits a photon-to-hydrogen efficiency of ca. 0.4%, a respectable efficiency for a system relying on effective collisions for the transference of electrons.

Keywords
Inorganic perovskites nanocrystals, H-2 evolution, Ultrafast spectroscopy, Charge transfer via collision
National Category
Materials Chemistry Physical Chemistry Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-364171 (URN)10.1016/j.mtcomm.2018.05.001 (DOI)000443035000012 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist Byggmästare
Available from: 2018-11-06 Created: 2018-11-06 Last updated: 2018-12-17Bibliographically approved
Hattori, Y., Abdellah, M., Rocha, I., Pavliuk, M. V., Fernandes, D. L. A. & Sá, J. (2018). Light-induced ultrafast proton-coupled electron transfer responsible for H-2 evolution on silver plasmonics. Materials Today, 21(6), 590-593
Open this publication in new window or tab >>Light-induced ultrafast proton-coupled electron transfer responsible for H-2 evolution on silver plasmonics
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2018 (English)In: Materials Today, ISSN 1369-7021, E-ISSN 1873-4103, Vol. 21, no 6, p. 590-593Article in journal (Refereed) Published
Abstract [en]

Light-driven proton-coupled electron transfer (PCET) reactions on nanoplasmonics would bring temporal control of their reactive pathways, in particular, prolong their charge separation state. Using a silver nano-hybrid plasmonic structure, we observed that optical excitation of Ag-localized surface plasmon instigated electron injection into TiO2 conduction band and oxidation of isopropanol alcoholic functionality. Femtosecond transient infrared absorption studies show that electron transfer from Ag to TiO2 occurs in ca. 650 fs, while IPA molecules near the Ag surface undergo an ultrafast bidirectional PCET step within 400 fs. Our work demonstrates that ultrafast PCET reaction plays a determinant role in prolonging charge separation state, providing an innovative strategy for visible-light photocatalysis with plasmonic nanostructures.

Place, publisher, year, edition, pages
ELSEVIER SCI LTD, 2018
National Category
Physical Chemistry Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-362849 (URN)10.1016/j.mattod.2018.05.002 (DOI)000441765700016 ()
Funder
Swedish Research Council, 2015-03764Stiftelsen Olle Engkvist Byggmästare, 2016/367
Available from: 2018-10-15 Created: 2018-10-15 Last updated: 2018-10-18Bibliographically approved
Sá, J., Fernandes, D. L. A., Pavliuk, M. V. & Szlachetko, J. (2017). Controlling dark catalysis with quasi half-cycle terahertz pulses. Catalysis Science & Technology, 7(5), 1050-1054
Open this publication in new window or tab >>Controlling dark catalysis with quasi half-cycle terahertz pulses
2017 (English)In: Catalysis Science & Technology, ISSN 2044-4753, E-ISSN 2044-4761, Vol. 7, no 5, p. 1050-1054Article in journal (Refereed) Published
Abstract [en]

This study reports the changes in the platinum electronic structure induced by a strong electric field originated from quasi half-cycle THz pulses, which forces the C-O molecule to dissociate. The changes could be rationalized via a simple analysis of the local density-of-states and easily characterised via high resolution X-ray absorption spectroscopy (HR-XAS). Thus, conferring half-cycle THz pulses the capability of triggering dark catalytic processes required to follow real time catalytic bond rupture or formation, i.e., time-resolved measurements using THz as the pump and HR-XAS as the probe.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-320254 (URN)10.1039/c6cy02651f (DOI)000396137800004 ()
Note

Correction in: CATALYSIS SCIENCE & TECHNOLOGY, Volume: 9, Issue: 2, Pages: 517-517, DOI: 10.1039/c8cy90096e

Available from: 2017-04-19 Created: 2017-04-19 Last updated: 2019-02-25Bibliographically approved
Czapla-Masztafiak, J., Nogueira, J. J., Lipiec, E., Kwiatek, W. M., Wood, B. R., Deacon, G. B., . . . Sá, J. (2017). Direct Determination of Metal Complexes' Interaction with DNA by Atomic Telemetry and Multiscale Molecular Dynamics. Journal of Physical Chemistry Letters, 8(4), 805-811
Open this publication in new window or tab >>Direct Determination of Metal Complexes' Interaction with DNA by Atomic Telemetry and Multiscale Molecular Dynamics
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2017 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 8, no 4, p. 805-811Article in journal (Refereed) Published
Abstract [en]

The lack of molecular mechanistic understanding of the interaction between metal complexes and biomolecules hampers their potential medical use. Herein we present a robust procedure combining resonant X-ray emission spectroscopy and multiscale molecular dynamics simulations, which allows for straightforward elucidation of the precise interaction mechanism at the atomic level. The report unveils an unforeseen hydrolysis process and DNA binding of [Pt{N(p-HC6F4)CH2}(2)py(2)] (Pt103), which showed potential cytotoxic activity in the past. Pt103 preferentially coordinates to adjacent adenine sites, instead of guanine sites as in cisplatin, because of its hydrogen bond ability. Comparison with previous research on cisplatin suggests that selective binding to guanine or adenine may be achieved by controlling the acidity of the compound.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2017
National Category
Physical Chemistry Medicinal Chemistry
Identifiers
urn:nbn:se:uu:diva-319563 (URN)10.1021/acs.jpclett.7b00070 (DOI)000394484100016 ()28151686 (PubMedID)
Funder
Australian Research Council, FT120100926
Available from: 2017-04-06 Created: 2017-04-06 Last updated: 2018-01-13Bibliographically approved
Pavliuk, M. V., Cieślak,, A. M., Abdellah, M., Budinská, A., Pullen, S., Sokolowski, K., . . . Sá, J. (2017). Hydrogen evolution with nanoengineered ZnO interfaces decorated using a beetroot extract and a hydrogenase mimic. Sustainable Energy & Fuels, 1, 69-73
Open this publication in new window or tab >>Hydrogen evolution with nanoengineered ZnO interfaces decorated using a beetroot extract and a hydrogenase mimic
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2017 (English)In: Sustainable Energy & Fuels, ISSN 2398-4902, Vol. 1, p. 69-73Article in journal (Refereed) Published
Abstract [en]

Herein, we report a nano-hybrid photo-system based on abundant elements for H2 production with visible light. The photo-system's proficiency relates to the novel ZnO nanocrystals employed. The ZnO carboxylate oligoethylene glycol shell enhances charge separation and accumulates reactive electrons for the photocatalytic process. 

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2017
Keywords
H2 evolution
National Category
Physical Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-335979 (URN)10.1039/c6se00066e (DOI)000422769100006 ()
Available from: 2017-12-11 Created: 2017-12-11 Last updated: 2018-12-17Bibliographically approved
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