Mechanochemical Synthesis and Thermal Dehydrogenation of Novel Calcium-Containing Bimetallic Amidoboranes
Само за регистроване кориснике
2021
Чланак у часопису (Објављена верзија)
,
© 2021 American Chemical Society
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Приказ свих података о документуАпстракт
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 co...urse 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.
Кључне речи:
Hydrogen storage / Ball milling / Reaction monitoring / Real-time PXRD / Temperature-dependent IR spectroscopy / Bimetallic amidoboranes / TPD-MSИзвор:
ACS Sustainable Chemistry and Engineering, 2021, 9, 5, 2089-2099Финансирање / пројекти:
- Ministry of Environment and Energy, the Ministry of Science and Education, the Environmental Protection and Energy Efficiency Fund, and the Croatian Science Foundation under the project "New Materials for Energy Storage"
- Синтеза, процесирање и карактеризација наноструктурних материјала за примену у области енергије, механичког инжењерства, заштите животне стредине и биомедицине (RS-45012)
- COST Action [CA18112]
- DESY [I-20181094 EC]
- Croatian Science Foundation - European Union from the European Social Fund [PZS-2019-02-4129]
DOI: 10.1021/acssuschemeng.0c06839
ISSN: 2168-0485
WoS: 000618670600011
Scopus: 2-s2.0-85100798407
Институција/група
VinčaTY - 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 and 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 and 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 and 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 and 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 and Engineering, 9, no. 5 (2021):2089-2099, https://doi.org/10.1021/acssuschemeng.0c06839 . .