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Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2)

Authorized Users Only
2009
Authors
Stojaković, Đorđe
Rajić, Nevenka
Rakić, Vesna M.
Zabukovec-Logar, Nataša
Kaučič, Venčeslav
Article (Published version)
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Abstract
A zinc phosphate with the composition [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2), containing the doubly protonated 1,2-diaminopropane (abbr. HDAP), was synthesized by hydrothermal crystallization of zinc nitrate, phosphoric acid, 1,2-diaminopropane and trimethylenedipiperidine. The single crystal analysis shows a layered inorganic-organic structure built up of a sandwich-like motif of alternating inorganic layers and HDAP cations (trimethylenedipiperidine not being a constituent of the structure). The HDAP species are found to be disordered and serve as bridges between two adjacent inorganic layers which are separated by 3.95 angstrom. The bridging interaction occurs via a hydrogen-bonding network. The inorganic layer features a pattern of four-membered rings involving two ZnO4 and two PO4 tetrahedra connected by sharing O atoms. Thermal analysis shows that the compound is stable up to 370 degrees C and that the thermal decomposition of HDAP occurs in two steps between 370 and 460 degrees C, caus...ing the collapse of the structure. The first decomposition step corresponds to ammonia removal which proceeds with a high activation energy (E-a = 282 kJ mol (1)). The high E-a value is mainly attributed to strong electrostatic interactions between organic cations and anionic inorganic layers, the disruption of the interactions being the main reason for structural collapse after the HDAP removal.

Keywords:
Hydrothermal crystallization / Layered inorganic-organic structure / Kinetics of thermal degradation / Zinc phosphate / Open-framework solids
Source:
Inorganica Chimica Acta, 2009, 362, 6, 1991-1995
Publisher:
  • Elsevier Science Sa, Lausanne
Funding / projects:
  • Serbian Ministry of Science and Environmental Protection
  • Slovenian Ministry of Higher Education Science and Technology

DOI: 10.1016/j.ica.2008.09.020

ISSN: 0020-1693

WoS: 000265299200048

Scopus: 2-s2.0-64649089049
[ Google Scholar ]
3
3
URI
http://TechnoRep.tmf.bg.ac.rs/handle/123456789/1519
Collections
  • Radovi istraživača / Researchers’ publications (TMF)
Institution/Community
Tehnološko-metalurški fakultet
TY  - JOUR
AU  - Stojaković, Đorđe
AU  - Rajić, Nevenka
AU  - Rakić, Vesna M.
AU  - Zabukovec-Logar, Nataša
AU  - Kaučič, Venčeslav
PY  - 2009
UR  - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/1519
AB  - A zinc phosphate with the composition [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2), containing the doubly protonated 1,2-diaminopropane (abbr. HDAP), was synthesized by hydrothermal crystallization of zinc nitrate, phosphoric acid, 1,2-diaminopropane and trimethylenedipiperidine. The single crystal analysis shows a layered inorganic-organic structure built up of a sandwich-like motif of alternating inorganic layers and HDAP cations (trimethylenedipiperidine not being a constituent of the structure). The HDAP species are found to be disordered and serve as bridges between two adjacent inorganic layers which are separated by 3.95 angstrom. The bridging interaction occurs via a hydrogen-bonding network. The inorganic layer features a pattern of four-membered rings involving two ZnO4 and two PO4 tetrahedra connected by sharing O atoms. Thermal analysis shows that the compound is stable up to 370 degrees C and that the thermal decomposition of HDAP occurs in two steps between 370 and 460 degrees C, causing the collapse of the structure. The first decomposition step corresponds to ammonia removal which proceeds with a high activation energy (E-a = 282 kJ mol (1)). The high E-a value is mainly attributed to strong electrostatic interactions between organic cations and anionic inorganic layers, the disruption of the interactions being the main reason for structural collapse after the HDAP removal.
PB  - Elsevier Science Sa, Lausanne
T2  - Inorganica Chimica Acta
T1  - Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2)
EP  - 1995
IS  - 6
SP  - 1991
VL  - 362
DO  - 10.1016/j.ica.2008.09.020
UR  - conv_3172
ER  - 
@article{
author = "Stojaković, Đorđe and Rajić, Nevenka and Rakić, Vesna M. and Zabukovec-Logar, Nataša and Kaučič, Venčeslav",
year = "2009",
abstract = "A zinc phosphate with the composition [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2), containing the doubly protonated 1,2-diaminopropane (abbr. HDAP), was synthesized by hydrothermal crystallization of zinc nitrate, phosphoric acid, 1,2-diaminopropane and trimethylenedipiperidine. The single crystal analysis shows a layered inorganic-organic structure built up of a sandwich-like motif of alternating inorganic layers and HDAP cations (trimethylenedipiperidine not being a constituent of the structure). The HDAP species are found to be disordered and serve as bridges between two adjacent inorganic layers which are separated by 3.95 angstrom. The bridging interaction occurs via a hydrogen-bonding network. The inorganic layer features a pattern of four-membered rings involving two ZnO4 and two PO4 tetrahedra connected by sharing O atoms. Thermal analysis shows that the compound is stable up to 370 degrees C and that the thermal decomposition of HDAP occurs in two steps between 370 and 460 degrees C, causing the collapse of the structure. The first decomposition step corresponds to ammonia removal which proceeds with a high activation energy (E-a = 282 kJ mol (1)). The high E-a value is mainly attributed to strong electrostatic interactions between organic cations and anionic inorganic layers, the disruption of the interactions being the main reason for structural collapse after the HDAP removal.",
publisher = "Elsevier Science Sa, Lausanne",
journal = "Inorganica Chimica Acta",
title = "Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2)",
pages = "1995-1991",
number = "6",
volume = "362",
doi = "10.1016/j.ica.2008.09.020",
url = "conv_3172"
}
Stojaković, Đ., Rajić, N., Rakić, V. M., Zabukovec-Logar, N.,& Kaučič, V.. (2009). Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2). in Inorganica Chimica Acta
Elsevier Science Sa, Lausanne., 362(6), 1991-1995.
https://doi.org/10.1016/j.ica.2008.09.020
conv_3172
Stojaković Đ, Rajić N, Rakić VM, Zabukovec-Logar N, Kaučič V. Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2). in Inorganica Chimica Acta. 2009;362(6):1991-1995.
doi:10.1016/j.ica.2008.09.020
conv_3172 .
Stojaković, Đorđe, Rajić, Nevenka, Rakić, Vesna M., Zabukovec-Logar, Nataša, Kaučič, Venčeslav, "Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)(2)" in Inorganica Chimica Acta, 362, no. 6 (2009):1991-1995,
https://doi.org/10.1016/j.ica.2008.09.020 .,
conv_3172 .

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