Lukin, Stipe

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  • Lukin, Stipe (3)

Author's Bibliography

Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes

Milanović, Igor; Biliškov, Nikola; Užarević, Krunoslav; Lukin, Stipe; Etter, Martin; Halasz, Ivan

(2021)

TY  - JOUR
AU  - Milanović, Igor
AU  - Biliškov, Nikola
AU  - Užarević, Krunoslav
AU  - Lukin, Stipe
AU  - Etter, Martin
AU  - Halasz, Ivan
PY  - 2021
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/9088
AB  - Metallic amidoboranes are widely investigated candidates for solid-state hydrogen storage, and much focus shifted recently toward bimetallic amidoboranes. Bimetallic amidoboranes are expected to introduce novel and enhanced physicochemical properties regarding storage and stability. However, these materials are still scarce and mostly grouped around magnesium- or aluminum-containing compounds. We present here a rapid and green mechanochemical solvent-free synthesis of two novel calcium-containing bimetallic amidoboranes, Li2Ca(NH2BH3)4 and Na2Ca(NH2BH3)4, from metal hydrides and ammonia borane. The insight into mechanochemical syntheses is provided by the in situ tandem synchrotron X-ray diffraction and thermal monitoring. The in situ data reveal how the choice of alkali metal hydride governs the course of reactions and their thermal profiles. In situ monitoring of thermal dehydrogenation of these materials is conducted by mass spectrometry and infrared spectroscopy, showing how the course of thermal decomposition varies depending on the structure of the amidoborane, resulting however in the same final products. These new hydrogen-rich bimetallic amidoboranes are structurally characterized by high-resolution powder X-ray diffraction, and they both show potential for hydrogen storage applications: high theoretical gravimetric capacities and low desorption temperatures of hydrogen without the significant presence of harmful gases. We also show how the choice of the milling reactor material can be decisive for the efficiency and overall success of the mechanochemical synthetic procedure, which may impact the design of milling syntheses for other thermally labile chemical systems. © 2021 American Chemical Society.
T2  - ACS Sustainable Chemistry & Engineering
T1  - Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes
VL  - 9
IS  - 5
SP  - 2089
EP  - 2099
DO  - 10.1021/acssuschemeng.0c06839
ER  - 
@article{
author = "Milanović, Igor and Biliškov, Nikola and Užarević, Krunoslav and Lukin, Stipe and Etter, Martin and Halasz, Ivan",
year = "2021",
abstract = "Metallic amidoboranes are widely investigated candidates for solid-state hydrogen storage, and much focus shifted recently toward bimetallic amidoboranes. Bimetallic amidoboranes are expected to introduce novel and enhanced physicochemical properties regarding storage and stability. However, these materials are still scarce and mostly grouped around magnesium- or aluminum-containing compounds. We present here a rapid and green mechanochemical solvent-free synthesis of two novel calcium-containing bimetallic amidoboranes, Li2Ca(NH2BH3)4 and Na2Ca(NH2BH3)4, from metal hydrides and ammonia borane. The insight into mechanochemical syntheses is provided by the in situ tandem synchrotron X-ray diffraction and thermal monitoring. The in situ data reveal how the choice of alkali metal hydride governs the course of reactions and their thermal profiles. In situ monitoring of thermal dehydrogenation of these materials is conducted by mass spectrometry and infrared spectroscopy, showing how the course of thermal decomposition varies depending on the structure of the amidoborane, resulting however in the same final products. These new hydrogen-rich bimetallic amidoboranes are structurally characterized by high-resolution powder X-ray diffraction, and they both show potential for hydrogen storage applications: high theoretical gravimetric capacities and low desorption temperatures of hydrogen without the significant presence of harmful gases. We also show how the choice of the milling reactor material can be decisive for the efficiency and overall success of the mechanochemical synthetic procedure, which may impact the design of milling syntheses for other thermally labile chemical systems. © 2021 American Chemical Society.",
journal = "ACS Sustainable Chemistry & Engineering",
title = "Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes",
volume = "9",
number = "5",
pages = "2089-2099",
doi = "10.1021/acssuschemeng.0c06839"
}
Milanović, I., Biliškov, N., Užarević, K., Lukin, S., Etter, M.,& Halasz, I.. (2021). Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes. in ACS Sustainable Chemistry & Engineering, 9(5), 2089-2099.
https://doi.org/10.1021/acssuschemeng.0c06839
Milanović I, Biliškov N, Užarević K, Lukin S, Etter M, Halasz I. Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes. in ACS Sustainable Chemistry & Engineering. 2021;9(5):2089-2099.
doi:10.1021/acssuschemeng.0c06839 .
Milanović, Igor, Biliškov, Nikola, Užarević, Krunoslav, Lukin, Stipe, Etter, Martin, Halasz, Ivan, "Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes" in ACS Sustainable Chemistry & Engineering, 9, no. 5 (2021):2089-2099,
https://doi.org/10.1021/acssuschemeng.0c06839 . .
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Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation

Lukin, Stipe; Stolar, Tomislav; Lončarić, Ivor; Milanović, Igor; Biliškov, Nikola; Michiel, Marco di; Friščić, Tomislav; Halasz, Ivan

(2020)

TY  - JOUR
AU  - Lukin, Stipe
AU  - Stolar, Tomislav
AU  - Lončarić, Ivor
AU  - Milanović, Igor
AU  - Biliškov, Nikola
AU  - Michiel, Marco di
AU  - Friščić, Tomislav
AU  - Halasz, Ivan
PY  - 2020
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/9638
AB  - Here we describe real-time, in situ monitoring of mechanochemical solid-state metathesis between silver nitrate and the entire series of sodium halides, on the basis of tandem powder X-ray diffraction and Raman spectroscopy monitoring. The mechanistic monitoring reveals that reactions of AgNO3 with NaX (X = Cl, Br, I) differ in reaction paths, with only the reaction with NaBr providing the NaNO3 and AgX products directly. The reaction with NaI revealed the presence of a novel, short-lived intermediate phase, while the reaction with NaCl progressed the slowest through the well-defined Ag2ClNO3 intermediate double salt. While the corresponding iodide and bromide double salts were not observed as intermediates, all three are readily prepared as pure compounds by milling equimolar mixtures of AgX and AgNO3. The in situ observation of reactive intermediates in these simple metathesis reactions reveals a surprising resemblance of reactions involving purely ionic components to those of molecular organic solids and cocrystals. This study demonstrates the potential of in situ reaction monitoring for mechanochemical reactions of ionic compounds as well as completes the application of these techniques to all major compound classes.
T2  - Inorganic Chemistry
T1  - Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation
VL  - 59
IS  - 17
SP  - 12200
EP  - 12208
DO  - 10.1021/acs.inorgchem.0c01196
ER  - 
@article{
author = "Lukin, Stipe and Stolar, Tomislav and Lončarić, Ivor and Milanović, Igor and Biliškov, Nikola and Michiel, Marco di and Friščić, Tomislav and Halasz, Ivan",
year = "2020",
abstract = "Here we describe real-time, in situ monitoring of mechanochemical solid-state metathesis between silver nitrate and the entire series of sodium halides, on the basis of tandem powder X-ray diffraction and Raman spectroscopy monitoring. The mechanistic monitoring reveals that reactions of AgNO3 with NaX (X = Cl, Br, I) differ in reaction paths, with only the reaction with NaBr providing the NaNO3 and AgX products directly. The reaction with NaI revealed the presence of a novel, short-lived intermediate phase, while the reaction with NaCl progressed the slowest through the well-defined Ag2ClNO3 intermediate double salt. While the corresponding iodide and bromide double salts were not observed as intermediates, all three are readily prepared as pure compounds by milling equimolar mixtures of AgX and AgNO3. The in situ observation of reactive intermediates in these simple metathesis reactions reveals a surprising resemblance of reactions involving purely ionic components to those of molecular organic solids and cocrystals. This study demonstrates the potential of in situ reaction monitoring for mechanochemical reactions of ionic compounds as well as completes the application of these techniques to all major compound classes.",
journal = "Inorganic Chemistry",
title = "Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation",
volume = "59",
number = "17",
pages = "12200-12208",
doi = "10.1021/acs.inorgchem.0c01196"
}
Lukin, S., Stolar, T., Lončarić, I., Milanović, I., Biliškov, N., Michiel, M. d., Friščić, T.,& Halasz, I.. (2020). Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation. in Inorganic Chemistry, 59(17), 12200-12208.
https://doi.org/10.1021/acs.inorgchem.0c01196
Lukin S, Stolar T, Lončarić I, Milanović I, Biliškov N, Michiel MD, Friščić T, Halasz I. Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation. in Inorganic Chemistry. 2020;59(17):12200-12208.
doi:10.1021/acs.inorgchem.0c01196 .
Lukin, Stipe, Stolar, Tomislav, Lončarić, Ivor, Milanović, Igor, Biliškov, Nikola, Michiel, Marco di, Friščić, Tomislav, Halasz, Ivan, "Mechanochemical Metathesis between AgNO3 and NaX (X = Cl, Br, I) and Ag2XNO3 Double-Salt Formation" in Inorganic Chemistry, 59, no. 17 (2020):12200-12208,
https://doi.org/10.1021/acs.inorgchem.0c01196 . .
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In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation

Biliskov, Nikola; Borgschulte, Andreas; Uzarevic, Krunoslav; Halasz, Ivan; Lukin, Stipe; Milošević, Sanja S.; Milanović, Igor; Grbović-Novaković, Jasmina

(2017)

TY  - JOUR
AU  - Biliskov, Nikola
AU  - Borgschulte, Andreas
AU  - Uzarevic, Krunoslav
AU  - Halasz, Ivan
AU  - Lukin, Stipe
AU  - Milošević, Sanja S.
AU  - Milanović, Igor
AU  - Grbović-Novaković, Jasmina
PY  - 2017
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/1870
AB  - For the first time, in situ monitoring of uninterrupted mechanochemical synthesis of two bimetallic amidoboranes, M2Mg(NH2BH3)(4) (M=Li, Na), by means of Raman spectroscopy, has been applied. This approach allowed real-time observation of key intermediate phases, and a straightforward follow-up of the reaction course. Detailed analysis of time-dependent spectra revealed a two-step mechanism through MNH2BH3 center dot NH3BH3 adducts as key intermediate phases which further reacted with MgH2, giving M2Mg(NH2BH3)(4) as final products. The intermediates partially take a competitive pathway toward the oligomeric M(BH3NH2BH2NH2BH3) phases. The crystal structure of the novel bimetallic amidoborane Li2Mg(NH2BH3)(4) was solved from high-resolution powder diffraction data and showed an analogous metal coordination to Na2Mg(NH2BH3)(4), but a significantly different crystal packing. Li2Mg(NH2BH3)(4) thermally dehydrogenates releasing highly pure H-2 in the amount of 7 wt.%, and at a lower temperature then its sodium analogue, making it significantly more viable for practical applications.
T2  - Chemistry. A European Journal
T1  - In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation
VL  - 23
IS  - 64
SP  - 16274
EP  - 16282
DO  - 10.1002/chem.201702665
ER  - 
@article{
author = "Biliskov, Nikola and Borgschulte, Andreas and Uzarevic, Krunoslav and Halasz, Ivan and Lukin, Stipe and Milošević, Sanja S. and Milanović, Igor and Grbović-Novaković, Jasmina",
year = "2017",
abstract = "For the first time, in situ monitoring of uninterrupted mechanochemical synthesis of two bimetallic amidoboranes, M2Mg(NH2BH3)(4) (M=Li, Na), by means of Raman spectroscopy, has been applied. This approach allowed real-time observation of key intermediate phases, and a straightforward follow-up of the reaction course. Detailed analysis of time-dependent spectra revealed a two-step mechanism through MNH2BH3 center dot NH3BH3 adducts as key intermediate phases which further reacted with MgH2, giving M2Mg(NH2BH3)(4) as final products. The intermediates partially take a competitive pathway toward the oligomeric M(BH3NH2BH2NH2BH3) phases. The crystal structure of the novel bimetallic amidoborane Li2Mg(NH2BH3)(4) was solved from high-resolution powder diffraction data and showed an analogous metal coordination to Na2Mg(NH2BH3)(4), but a significantly different crystal packing. Li2Mg(NH2BH3)(4) thermally dehydrogenates releasing highly pure H-2 in the amount of 7 wt.%, and at a lower temperature then its sodium analogue, making it significantly more viable for practical applications.",
journal = "Chemistry. A European Journal",
title = "In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation",
volume = "23",
number = "64",
pages = "16274-16282",
doi = "10.1002/chem.201702665"
}
Biliskov, N., Borgschulte, A., Uzarevic, K., Halasz, I., Lukin, S., Milošević, S. S., Milanović, I.,& Grbović-Novaković, J.. (2017). In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation. in Chemistry. A European Journal, 23(64), 16274-16282.
https://doi.org/10.1002/chem.201702665
Biliskov N, Borgschulte A, Uzarevic K, Halasz I, Lukin S, Milošević SS, Milanović I, Grbović-Novaković J. In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation. in Chemistry. A European Journal. 2017;23(64):16274-16282.
doi:10.1002/chem.201702665 .
Biliskov, Nikola, Borgschulte, Andreas, Uzarevic, Krunoslav, Halasz, Ivan, Lukin, Stipe, Milošević, Sanja S., Milanović, Igor, Grbović-Novaković, Jasmina, "In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2Mg(NH2BH3)(4) and Na2Mg(NH2BH3)(4) and Their Thermal Dehydrogenation" in Chemistry. A European Journal, 23, no. 64 (2017):16274-16282,
https://doi.org/10.1002/chem.201702665 . .
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