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Concina, I. (2024). An Old Material for a New World: Prussian Blue and Its Analogues as Catalysts for Modern Needs. Inorganics, 12(4), Article ID 124.
Open this publication in new window or tab >>An Old Material for a New World: Prussian Blue and Its Analogues as Catalysts for Modern Needs
2024 (English)In: Inorganics, E-ISSN 2304-6740, Vol. 12, no 4, article id 124Article, review/survey (Refereed) Published
Abstract [en]

Prussian blue analogues (PBAs) have recently emerged as effective materials in different functional applications, ranging from energy storage to electrochemical water splitting, thence to more “traditional” heterogeneous catalysis. Their versatility is due to their open framework, compositional variety, and fast and efficient internal charge exchange, coupled with a self-healing ability that makes them unique. This review paper presents and discusses the findings of the last decade in the field of the catalytic and photocatalytic application of PBAs in water remediation (via the degradation of organic pollutants and heavy metal removal) and the catalytic oxidation of organics and production or organic intermediates for industrial synthesis. Analysis of the catalytic processes is approached from a critical perspective, highlighting both the achievements of the research community and the limits still affecting this field.

Place, publisher, year, edition, pages
Multidisciplinary Digital Publishing Institute (MDPI), 2024
Keywords
adsorption, catalysis, Fenton process, persulfate, Prussian blue analogues
National Category
Materials Chemistry Analytical Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-105406 (URN)10.3390/inorganics12040124 (DOI)2-s2.0-85191327353 (Scopus ID)
Projects
SUPERCAP
Funder
Luleå University of Technology
Note

Validerad;2024;Nivå 2;2024-05-13 (hanlid);

Full text license: CC BY

Available from: 2024-05-13 Created: 2024-05-13 Last updated: 2024-05-13Bibliographically approved
Memarian, N., Farahi, E., Tobeiha, N., You, S. & Concina, I. (2024). Understanding Graphitic Carbon Nitride as Photocatalyst: A Case Study on Thermal Engineering of Physical and Chemical Features. Physica Status Solidi (a) applications and materials science, 221(7), Article ID 2300844.
Open this publication in new window or tab >>Understanding Graphitic Carbon Nitride as Photocatalyst: A Case Study on Thermal Engineering of Physical and Chemical Features
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2024 (English)In: Physica Status Solidi (a) applications and materials science, ISSN 1862-6300, E-ISSN 1862-6319, Vol. 221, no 7, article id 2300844Article in journal (Refereed) Published
Abstract [en]

Rationalizing material features according to the adopted synthetic strategy, aiming then to tune them on demand, is among the most relevant purposes of investigation in materials science. Herein, the systematic analysis of the dependence of graphitic carbon nitride (g-C3N4) physical characteristics on the decomposition temperature of urea, rationalizing the impact of synthetic temperature on several characteristics of the materials (degree of N–H condensation, carbon vs nitrogen content, structural parameters, photoluminescence lifetime, surface area, pores volume), is discussed. g-C3N4 nanostructures are fabricated by thermal decomposition of urea at different temperatures under ambient atmosphere, obtaining an almost ideal stoichiometry (C/N = 0.72) when setting the temperature at 600 °C. The samples show structural, textural, compositional, and optical differences directly depending on the fabrication temperature: specific surface area, pore volume and size, intralayer distance, and speed of radiative recombination of photogenerated charges are proportionally enhanced by increasing the synthesis temperature. The role played by all the physicochemical features of the prepared samples in promoting the catalytic degradation of Rhodamine B is investigated, highlighting their synergistic role in enhancing the catalytic efficiency. Significant differences in the dye degradation are recorded when using either UV or solar simulated light, demonstrating that Rhodamine B photosensitization rules the process.

Place, publisher, year, edition, pages
John Wiley & Sons, 2024
Keywords
g-C3N4, intralayer distance, photocatalysis, photoluminescence lifetime, urea thermal decomposition
National Category
Physical Chemistry Materials Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-104513 (URN)10.1002/pssa.202300844 (DOI)2-s2.0-85185129668 (Scopus ID)
Note

Validerad;2024;Nivå 2;2024-04-23 (joosat);

Full text license: CC BY-NC-ND

Available from: 2024-03-07 Created: 2024-03-07 Last updated: 2024-04-23Bibliographically approved
Khasevani, S. G., Nikjoo, D., Chaxel, C., Umeki, K., Sarmad, S., Mikkola, J.-P. & Concina, I. (2023). Empowering Adsorption and Photocatalytic Degradation of Ciprofloxacin on BiOI Composites: A Material-by-Design Investigation. ACS Omega, 8(46), 44044-44056
Open this publication in new window or tab >>Empowering Adsorption and Photocatalytic Degradation of Ciprofloxacin on BiOI Composites: A Material-by-Design Investigation
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2023 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 8, no 46, p. 44044-44056Article in journal (Refereed) Published
Abstract [en]

Binary and ternary composites of BiOI with NH2-MIL-101(Fe) and a functionalized biochar were synthesized through an in situ approach, aimed at spurring the activity of the semiconductor as a photocatalyst for the removal of ciprofloxacin (CIP) from water. Experimental outcomes showed a drastic enhancement of the adsorption and the equilibrium (which increased from 39.31 mg g–1 of bare BiOI to 76.39 mg g–1 of the best ternary composite in 2 h time), while the kinetics of the process was not significantly changed. The photocatalytic performance was also significantly enhanced, and the complete removal of 10 ppm of CIP in 3 h reaction time was recorded under simulated solar light irradiation for the best catalyst of the investigated batch. Catalytic reactions supported by different materials obeyed different reaction orders, indicating the existence of different mechanisms. The use of scavengers for superoxide anion radicals, holes, and hydroxyl radicals showed that although all these species are involved in CIP photodegradation, the latter play the most crucial role, as also confirmed by carrying out the reaction at increasing pH conditions. A clear correlation between the reduction of BiOI crystallite sizes in the composites, as compared to the bare material, and the material performance as both adsorbers and photocatalyst was identified. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2023
National Category
Physical Chemistry Materials Chemistry
Research subject
Energy Engineering; Experimental Physics; Waste Science and Technology
Identifiers
urn:nbn:se:ltu:diva-103204 (URN)10.1021/acsomega.3c06243 (DOI)001108005100001 ()2-s2.0-85178352921 (Scopus ID)
Funder
The Kempe Foundations, SMK-1974Knut and Alice Wallenberg FoundationBio4Energy
Note

Validerad;2023;Nivå 2;2023-12-11 (joosat);

License full text: CC BY

Available from: 2023-12-11 Created: 2023-12-11 Last updated: 2024-03-07Bibliographically approved
Solomon, G., Lecca, M., Bisetto, M., Gilzad Kohan, M., Concina, I., Natile, M. M. & Vomiero, A. (2023). Engineering Cu2O Nanowire Surfaces for Photoelectrochemical Hydrogen Evolution Reaction. ACS Applied Energy Materials, 6(2), 832-840
Open this publication in new window or tab >>Engineering Cu2O Nanowire Surfaces for Photoelectrochemical Hydrogen Evolution Reaction
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2023 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 6, no 2, p. 832-840Article in journal (Refereed) Published
Abstract [en]

Cu2O is a narrow band gap material serving as an important candidate for photoelectrochemical hydrogen evolution reaction. However, the main challenge that hinders its practical exploitation is its poor photostability, due to its oxidation into CuO by photoexcited holes. Here, we thoroughly minimize the photo-oxidation of Cu2O nanowires by growing a thin layer of the TiO2 protective layer and an amorphous layer of the VOx cocatalyst using magnetron sputtering and atomic layer deposition, respectively. After optimization of the protective and the cocatalyst layers, the photoelectrode exhibits a current density of −2.46 mA/cm2 under simulated sunlight (100 mW/cm2) at 0.3 V versus reversible hydrogen electrode, and its performance is stable for an extended illumination time. The chemical stability and the good performance of the engineered photoelectrode demonstrate the potential of using earth-abundant materials as a light-harvesting device for solar hydrogen production.

Place, publisher, year, edition, pages
American Chemical Society, 2023
Keywords
atomic layer deposition, Cu2O photoelectrode, magnetron deposition, photoelectrochemical hydrogen evolution, water splitting
National Category
Materials Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-95364 (URN)10.1021/acsaem.2c03122 (DOI)000908364800001 ()2-s2.0-85146159928 (Scopus ID)
Funder
The Kempe FoundationsLuleå University of TechnologyKnut and Alice Wallenberg Foundation
Note

Validerad;2023;Nivå 2;2023-01-23 (joosat);

Funder: ICMATE-CNR (B93C22000630006); Swedish Foundations

Available from: 2023-01-23 Created: 2023-01-23 Last updated: 2023-01-23Bibliographically approved
Solomon, G., Gilzad Kohan, M., Mazzaro, R., Jugovac, M., Moras, P., Morandi, V., . . . Vomiero, A. (2023). MoS2 Nanosheets Uniformly Anchored on NiMoO4 Nanorods, a Highly Active Hierarchical Nanostructure Catalyst for Oxygen Evolution Reaction and Pseudo-Capacitors. Advanced sustainable systems, 7(2), Article ID 2200410.
Open this publication in new window or tab >>MoS2 Nanosheets Uniformly Anchored on NiMoO4 Nanorods, a Highly Active Hierarchical Nanostructure Catalyst for Oxygen Evolution Reaction and Pseudo-Capacitors
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2023 (English)In: Advanced sustainable systems, E-ISSN 2366-7486, Vol. 7, no 2, article id 2200410Article in journal (Refereed) Published
Abstract [en]

Hierarchical nanostructures have attracted considerable research attention due to their applications in the catalysis field. Herein, we design a versatile hierarchical nanostructure composed of NiMoO4 nanorods surrounded by active MoS2 nanosheets on an interconnected nickel foam substrate. The as-prepared nanostructure exhibits excellent oxygen evolution reaction performance, producing a current density of 10 mA cm−2 at an overpotential of 90 mV, in comparison with 220 mV necessary to reach a similar current density for NiMoO4. This behavior originates from the structural/morphological properties of the MoS2 nanosheets, which present numerous surface-active sites and allow good contact with the electrolyte. Besides, the structures can effectively store charges, due to their unique branched network providing accessible active surface area, which facilitates intermediates adsorptions. Particularly, NiMoO4/MoS2 shows a charge capacity of 358 mAhg−1 at a current of 0.5 A g−1 (230 mAhg−1 for NiMoO4), thus suggesting promising applications for charge-storing devices.

Place, publisher, year, edition, pages
John Wiley & Sons, 2023
Keywords
electrocatalysts, hierarchical nanostructures, hydrous catalysts, magnetron sputtering, oxygen evolution reaction, pseudo capacitors, water splitting
National Category
Energy Engineering Materials Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-88421 (URN)10.1002/adsu.202200410 (DOI)000894620200001 ()2-s2.0-85144090100 (Scopus ID)
Funder
Knut and Alice Wallenberg FoundationEU, Horizon 2020, 654002Luleå University of TechnologyThe Kempe Foundations
Note

Validerad;2023;Nivå 2;2023-03-03 (hanlid);

Funder: European Commission Graphene Flagship Core3 (881603); EUROFEL-ROADMAP ESFRI;

This article has previously appeared as a manuscript in a thesis.

Available from: 2021-12-15 Created: 2021-12-15 Last updated: 2024-03-27Bibliographically approved
Banari, M., Memarian, N., Concina, I. & Vomiero, A. (2023). UV photodetector study based on Ce: ZnO nanostructures with different concentration of Ce dopant. Optical materials (Amsterdam), 146, Article ID 114576.
Open this publication in new window or tab >>UV photodetector study based on Ce: ZnO nanostructures with different concentration of Ce dopant
2023 (English)In: Optical materials (Amsterdam), ISSN 0925-3467, E-ISSN 1873-1252, Vol. 146, article id 114576Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Elsevier, 2023
National Category
Other Physics Topics
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-102656 (URN)10.1016/j.optmat.2023.114576 (DOI)
Note

Validerad;2023;Nivå 2;2023-11-22 (joosat);

Available from: 2023-11-22 Created: 2023-11-22 Last updated: 2023-11-22Bibliographically approved
Gilzad Kohan, M., Dobryden, I., Forchheimer, D., Concina, I. & Vomiero, A. (2022). In-depth photocarrier dynamics in a barrier variable iron-oxide and vertically aligned reduced-graphene oxide composite. NPJ 2D MATERIALS AND APPLICATIONS, 6(1), Article ID 57.
Open this publication in new window or tab >>In-depth photocarrier dynamics in a barrier variable iron-oxide and vertically aligned reduced-graphene oxide composite
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2022 (English)In: NPJ 2D MATERIALS AND APPLICATIONS, E-ISSN 2397-7132, Vol. 6, no 1, article id 57Article in journal (Refereed) Published
Abstract [en]

A key requirement for semiconductors operating in light-harvesting devices, is to efficiently convert the absorbed photons to electronic excitations while accommodating low loss pathways for the photogenerated carrier’s transport. The quality of this process corresponds to different relaxation phenomena, yet primarily it corresponds to minimized thermalization of photoexcited carriers and maximum transfer of electron-hole pairs in the bulk of semiconductor. However, several semiconductors, while providing a suitable platform for light-harvesting applications, pose intrinsic low carrier diffusion length of photoexcited carriers. Here we report a system based on a vertical network of reduced graphene oxide (rGO) embedded in a thin-film structure of iron oxide semiconductor, intended to exploit fast electron transport in rGO to increase the photoexcited carrier transfer from the bulk of the semiconductor to rGO and then to the external circuit. Using intermodulation conductive force microscopy, we locally monitored the fluctuation of current output, which is the prime indication of successful charge transfer from photoexcited semiconductor to rGO and efficient charge collection from the bulk of the semiconductor. We reveal the fundamental properties of vertical rGO and semiconductor junction in light-harvesting systems that enable the design of new promising materials for broad-band optical applications.

Place, publisher, year, edition, pages
Springer Nature, 2022
National Category
Physical Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-93220 (URN)10.1038/s41699-022-00333-5 (DOI)000849458700001 ()2-s2.0-85137588426 (Scopus ID)
Funder
Luleå University of TechnologyThe Kempe FoundationsEU, Horizon 2020, 65400Knut and Alice Wallenberg FoundationVinnova
Note

Validerad;2022;Nivå 2;2022-09-27 (joosat);

Funder: Swedish Foundations Consolidator Fellowship

Available from: 2022-09-27 Created: 2022-09-27 Last updated: 2022-09-27Bibliographically approved
Khasevani, S. G., Nikjoo, D., Ojwang, D. O., Nodari, L., Sarmad, S., Mikkola, J.-P., . . . Concina, I. (2022). The beauty of being complex: Prussian blue analogues as selective catalysts and photocatalysts in the degradation of ciprofloxacin. Journal of Catalysis, 410, 307-319
Open this publication in new window or tab >>The beauty of being complex: Prussian blue analogues as selective catalysts and photocatalysts in the degradation of ciprofloxacin
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2022 (English)In: Journal of Catalysis, ISSN 0021-9517, E-ISSN 1090-2694, Vol. 410, p. 307-319Article in journal (Refereed) Published
Abstract [en]

We investigate the performance of four Prussian blue analogues (PBAs) as catalysts for the selective degradation of ciprofloxacin in water, under both dark and illumination conditions. We show that no light is actually needed to induce a selective degradation of the molecular target, while light irradiation spurs the process, without, however, resulting in the commonly reported photolysis-supported breaking down. We present a systematic characterization of the PBAs aiming at interpreting the catalytic outcomes in the light of a classic coordination chemistry analysis, empowered by the most recent findings in literature. We show that varying the transition metal binding the N atom of the cyanide bridge is key to promote photoinduced charge generation and transfer, which effectively disrupts the molecular target. The analysis of the materials before and after the irradiation with solar simulated light results in a change of the lattice parameters, indicating the possibility of a light-induced spin cross-over.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Prussian blue analogues, Ciprofloxacin degradation, Photocatalysis, Auto-catalytic reactions, Mössbauer spectroscopy
National Category
Materials Chemistry Physical Chemistry
Research subject
Engineering Materials; Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-90488 (URN)10.1016/j.jcat.2022.04.029 (DOI)000799277700002 ()2-s2.0-85129740965 (Scopus ID)
Funder
The Kempe Foundations, (SMK-1947)ÅForsk (Ångpanneföreningen's Foundation for Research and Development), (18-459)Swedish Energy Agency, (45517-1)
Note

Validerad;2022;Nivå 2;2022-05-11 (sofila)

Available from: 2022-05-02 Created: 2022-05-02 Last updated: 2022-06-20Bibliographically approved
Solomon, G., Landström, A., Rotta Loria, S., Bolli, E., Mezzetti, A., Facibeni, A., . . . Concina, I. (2022). Tunable physics through coordination chemistry: formation on oxide surface of Ti and Al chelates with 3-hydroxyflavone capable of electron injection and light emission. Dalton Transactions, 51(48), 18489-18501
Open this publication in new window or tab >>Tunable physics through coordination chemistry: formation on oxide surface of Ti and Al chelates with 3-hydroxyflavone capable of electron injection and light emission
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2022 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 51, no 48, p. 18489-18501Article in journal (Refereed) Published
Abstract [en]

The optoelectronic features of 3-hydroxyflavone (3HF) self-assembled on the surface of an n-type semiconducting metal oxide (TiO2) and an insulator (Al2O3) are herein investigated. 3HF molecules use the coordinatively unsaturated metal ions present on the oxide surface to form metal complexes, which exhibit different behaviors upon light irradiation, depending on the nature of the metal ion. Specifically, we show that the photoluminescence of the surface species can be modulated according to the chemical properties of the complex (i.e. the binding metal ion), resulting in solid-state emitters in a high quantum yield (about 15%). Furthermore, photoinduced charge injection can be promoted or inhibited, providing a multifunctional hybrid system.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2022
National Category
Physical Chemistry Materials Chemistry
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-94377 (URN)10.1039/d2dt02195a (DOI)000890056000001 ()36421057 (PubMedID)2-s2.0-85143358695 (Scopus ID)
Note

Validerad;2023;Nivå 2;2023-02-10 (joosat);

Licens fulltext: CC BY License

Available from: 2022-11-30 Created: 2022-11-30 Last updated: 2023-02-24Bibliographically approved
Solomon, G., Gilzad Kohan, M., Vagin, M., Rigoni, F., Mazzaro, R., Natile, M. M., . . . Vomiero, A. (2021). Decorating vertically aligned MoS2 nanoflakes with silver nanoparticles for inducing a bifunctional electrocatalyst towards oxygen evolution and oxygen reduction reaction. Nano Energy, 81, Article ID 105664.
Open this publication in new window or tab >>Decorating vertically aligned MoS2 nanoflakes with silver nanoparticles for inducing a bifunctional electrocatalyst towards oxygen evolution and oxygen reduction reaction
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2021 (English)In: Nano Energy, ISSN 2211-2855, E-ISSN 2211-3282, Vol. 81, article id 105664Article in journal (Refereed) Published
Abstract [en]

Catalysts capable of improving the performance of oxygen evolution reaction (OER) and oxygen reduction reactions (ORR) are essential for the advancement of renewable energy technologies. Herein, Ag-decorated vertically aligned MoS2 nanoflakes are developed via magnetron co-sputtering and investigated as electrocatalyst towards OER and ORR. Due to the presence of silver, the catalyst shows more than 1.5 times an increase in the roughness-normalized rate of OER, featuring a very low Tafel slope (58.6 mv dec−1), thus suggesting that the catalyst surface favors the thermodynamics of hydroxyl radical (OH•) adsorption with the deprotonation steps being the rate-determining steps. The improved performance is attributed to the strong interactions between OOH intermediates and the Ag surface which reduces the activation energy. Rotating ring disk electrode (RRDE) analysis shows that the net disk currents on the Ag-MoS2 sample are two times higher at 0.65 V compared to MoS2, demonstrating the co-catalysis effect of silver doping. Based on the rate constant values, Ag-MoS2 proceeds through a mixed 4 electron and a 2 + 2 serial route reduction mechanism, in which the ionized hydrogen peroxide is formed as a mobile intermediate. The presence of silver decreases the electron transfer number and increases the peroxide yield due to the interplay of a 2 + 2 electron reduction pathway. A 2.5–6 times faster conversion rate of peroxide to OH- observed due to the presence of silver, indicating its effective cocatalyst nature. This strategy can help in designing a highly active bifunctional catalyst that has great potential as a viable alternative to precious-metal-based catalysts.Graphica

Place, publisher, year, edition, pages
Elsevier, 2021
Keywords
Oxygen evolution reaction (OER), Oxygen reduction reaction (ORR), Electrocatalys, tBifunctional catalyst, Magnetron co-sputtering
National Category
Other Physics Topics
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-82322 (URN)10.1016/j.nanoen.2020.105664 (DOI)000620327900002 ()2-s2.0-85098781620 (Scopus ID)
Funder
Vinnova, 2015-01513Knut and Alice Wallenberg FoundationEU, Horizon 2020, 654002, 785219The Kempe FoundationsLuleå University of TechnologySwedish Research Council, 2019-05577
Note

Validerad;2021;Nivå 2;2021-01-12 (alebob);

Finansiär: MIUR-PON TARANTO (ARS01_00637)

Available from: 2021-01-12 Created: 2021-01-12 Last updated: 2022-01-14Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-1785-7177

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