| 1. |
- Abebe, Mihret, et al.
(författare)
-
Spherical and Porous Particles of Calcium Carbonate Synthesized with Food Friendly Polymer Additives
- 2015
-
Ingår i: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 15:8, s. 3609-3616
-
Tidskriftsartikel (refereegranskat)abstract
- Porous calcium carbonate particles were synthesized by adding solutions of Ca2+ to solutions of CO32- containing polymeric additives. Under optimized conditions well-defined aggregates of the anhydrous polymorph vaterite formed. A typical sample of these micrometer-sized aggregates had: a pore volume of 0.1 cm(3)/g, a pore width of similar to 10 nm, and a specific surface area of similar to 25-30 m(2)/ g. Only one mixing Order (calcium to carbonate) allowed the formation of vaterite, which was ascribed to the buffering capacity and relatively high pH of the CO32- solution. Rapid addition of the calcium chloride solution and rapid stirring promoted the formation of vaterite, due to the high supersaturation levels achieved. With xanthan gum, porous and micrometer-sized vaterite aggregates could be synthesized over a wide range of synthetic conditions. For the Other food grade polymers, hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), and sodium carboxyl methylcellulose, several intensive and extensive synthetic parameters had to be optimized to obtain pure vaterite and porous aggregates. HPMC and MC allowed well-defined spherical micrometer-sited particles to form. We expect that these spherical and porous particles of vaterite could be relevant to model studies as well as a controlled delivery of particularly large molecules.
|
|
| 2. |
- Asfaw, Habtom D., et al.
(författare)
-
Boosting the thermal stability of emulsion–templated polymers via sulfonation : an efficient synthetic route to hierarchically porous carbon foams
- 2016
-
Ingår i: ChemistrySelect. - : Wiley. - 2365-6549. ; 1:4, s. 784-792
-
Tidskriftsartikel (refereegranskat)abstract
- Hierarchically porous carbon foams with specific surface areas exceeding 600 m2 g−1 can be derived from polystyrene foams that are synthesized via water-in-oil emulsion templating. However, most styrene-based polymers lack strong crosslinks and are degraded to volatile products when heated above 400 oC. A common strategy employed to avert depolymerization is to introduce potential crosslinking sites such as sulfonic acids by sulfonating the polymers. This article unravels the thermal and chemical processes leading up to the conversion of sulfonated high internal phase emulsion polystyrenes (polyHIPEs) to sulfur containing carbon foams. During pyrolysis, the sulfonic acid groups (-SO3H) are transformed to sulfone (-C-SO2-C-) and then to thioether (-C−S-C-) crosslinks. These chemical transformations have been monitored using spectroscopic techniques: in situ IR, Raman, X-ray photoelectron and X-ray absorption near edge structure spectroscopy. Based on thermal analyses, the formation of thioether links is associated with increased thermal stability and thus a substantial decrease in volatilization of the polymers.
|
|
| 3. |
- Atluri, Rambabu, et al.
(författare)
-
Self-Assembly Mechanism of Folate-Templated Mesoporous Silica
- 2013
-
Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 29:38, s. 12003-12012
-
Tidskriftsartikel (refereegranskat)abstract
- A method to form ordered mesoporous silica based on the use of folate supramolecular templates has been developed. Evidence based on in situ small-angle X-ray scattering (SAXS), electron microscopy, infrared spectroscopy, and in situ conductivity measurements are used to investigate the organic inorganic interactions and synthesis mechanism. The behavior of folate molecules in solution differs distinctively from that of surfactants commonly used for the preparation of ordered mesoporous silica phases, notably with the absence of a critical micellar concentration. In situ SAXS studies reveal fluctuations in X-ray scattering intensities consistent with the condensation of the silica precursor surrounding the folate template and the growth of the silica mesostructure in the initial stages. High-angle X-ray diffraction shows that the folate template is well-ordered within the pores even after a few minutes of synthesis. Direct structural data for the self-assembly of folates into chiral tetramers within the pores of mesoporous silica provide evidence for the in register stacking of folate tetramers, resulting in a chiral surface of rotated tetramers, with a rotation angle of 30 degrees. Additionally, the self-assembled folates within pores were capable of adsorbing a considerable amount of CO2 gas through the cavity space of the tetramers. The study demonstrates the validity of using a naturally occurring template to produce relevant and functional mesoporous materials.
|
|
| 4. |
- Atluri, Rambabu, et al.
(författare)
-
Structural variations in mesoporous materials with cubic Pm(3)over-barn symmetry
- 2010
-
Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 133:1-3, s. 27-35
-
Tidskriftsartikel (refereegranskat)abstract
- The fine structural details of mesoporous materials possessing Pmn symmetry prepared with varying amphiphilic surfactants under acid and alkaline conditions are investigated using electron crystallography and sorption studies. The structural data derived is used to understand the parameters that govern the formation of cavity–windows and to propose synthetic strategies in order to control independently the size of the cavities and cavity–windows. Results support that whilst attainment of Pmn cubic packing is due to the overall surfactant geometry, the formation of cavity–windows is associated with the hydration layer formed at the interphase between the surfactant and the silica wall. The charge density at the micelle surface may be tailored using two strategies: (i) using dicationic gemini surfactants at low pHs resulting in an increase in the hydration layer; or (ii) by using co-structure directing agents such as organoalkoxysilanes which reduce the hydration layer surrounding the micelles. The latter leads to the formation of higher cavity sizes and may be useful for tuning fine structural details of mesoporous materials when considering their use in important applications such as gas separation.
|
|
| 5. |
- Atluri, Rambabu, 1981-, et al.
(författare)
-
Structural variations in mesoporous materials with cubic Pm3n symmetry
- 2010
-
Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 133:1-3, s. 27-35
-
Tidskriftsartikel (refereegranskat)abstract
- The fine structural details of mesoporous materials possessing Pm3n symmetry prepared with varying amphiphilic surfactants under acid and alkaline conditions are investigated using electron crystallography and sorption studies. The structural data derived is used to understand the parameters that govern the formation of cavity-windows and to propose synthetic strategies in order to control independently the size of the cavities and cavity-windows. Results support that whilst attainment of Pm3n cubic packing is due to the overall surfactant geometry, the formation of cavity-windows is associated with the hydration layer formed at the interphase between the surfactant and the silica wall. The charge density at the micelle surface may be tailored using two strategies: (i) using dicationic gemini surfactants at low pHs resulting in an increase in the hydration layer; or (ii) by using co-structure directing agents such as organoalkoxysilanes which reduce the hydration layer surrounding the micelles. The latter leads to the formation of higher cavity sizes and may be useful for tuning fine structural details of mesoporous materials when considering their use in important applications such as gas separation.
|
|
| 6. |
- Aziz, Baroz, 1980-, et al.
(författare)
-
Quantification of chemisorption and physisorption of carbon dioxide on porous silica modified by propylamines : Effect of amine density
- 2012
-
Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 159, s. 42-49
-
Tidskriftsartikel (refereegranskat)abstract
- Detailed molecular aspects of carbon dioxide sorption on porous silica with different amounts of tethered and cross-linked n-propylamine groups were investigated. Infrared spectroscopy was applied to directly quantify physisorbed and chemisorbed CO2 on the amine modified silicas. The fractions of physisorbed CO2 and various chemisorbed species were determined as functions of CO2 pressure and the amine density on the modified silica. Physisorbed CO2 was a minor portion of the total CO2 uptake at low pressures, but it’s contribution increased to ∼35% at 1 bar of CO2 when the propylamine surface density was low or medium (0.87-1.67 NH2/nm2). Chemisorption of CO2 dominated when the propylamine content was high (2.74 NH2/nm2). The quantities of propylammonium propylcarbamate ion pairs increased with increasing propylamine content. At low or medium amine surface densities (0.87-1.67 NH2/nm2) this increase was approximately proportional to the amine density, but the quantity of ion pairs increased very significantly when the propylamine content was high (2.74 NH2/nm2). This dependency on amine density is consistent with the idea that a sufficiently close proximity of propylamine groups allows a formation of ion pairs. The relative fractions of carbamic acid and silylpropylcarbamate were significant for materials on which ion pairs could not form. Furthermore, the quantities of carbamic acid increased with increasing amine densities suggesting that the ion pairs have a role to stabilize the labile carbamic acid through hydrogen bonds.
|
|
| 7. |
- Bacsik, Zoltán, et al.
(författare)
-
Adsorption of Carbonyl Sulfide on Propylamine Tethered to Porous Silica
- 2018
-
Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 34:26, s. 7708-7713
-
Tidskriftsartikel (refereegranskat)abstract
- Carbonyl sulfide (COS) reacts slowly with amines in the aqueous solutions used to absorb CO2 from natural gas and flue gas and can also deactivate certain aqueous amines. The effects of COS on amines tethered to porous silica, however, have not been investigated before. Hence, the adsorption of COS on aminopropyl groups tethered to porous silica was studied using in situ IR spectroscopy. COS chemisorbed mainly and reversibly as propylammonium propylthiocarbamate ion pairs [R-NH(C= O)S- +H3N-R] under dry conditions. In addition, a small amount of another chemisorbed species formed slowly and irreversibly. Nevertheless, the CO2 capacities of the adsorbents were fully retained after COS was desorbed.
|
|
| 8. |
- Bacsik, Zoltan, et al.
(författare)
-
Ammonium-Carbamate-Rich Organogels for the Preparation of Amorphous Calcium Carbonates
- 2017
-
Ingår i: Minerals. - : MDPI AG. - 2075-163X. ; 7:7
-
Tidskriftsartikel (refereegranskat)abstract
- Amine-CO2 chemistry is important for a range of different chemical processes, including carbon dioxide capture. Here, we studied how aspects of this chemistry could be used to prepare calcium carbonates. Chemically crosslinked organogels were first prepared by reacting hyperbranched polyethylene imine (PEI) dissolved in DMSO with carbon dioxide. The crosslinks of the organogel consisted of ammonium-carbamate ion pairs as was shown by IR spectroscopy. These carbamate-rich organogels were subsequently subjected to aqueous solutions of calcium acetate, and amorphous calcium carbonate (ACC) precipitated. The ACC did not crystalize during the mixing for up to 20 h, as was shown by a combination of IR spectroscopy, X-ray diffraction, scanning electron microscopy, and thermal analysis. Some PEI had been included or adsorbed on the ACC particles. Traces of calcite were observed in one sample that had been subjected to water in a work-up procedure.
|
|
| 9. |
- Bacsik, Zoltan, et al.
(författare)
-
Effects of carbon dioxide captured from ambient air on the infrared spectra of supported amines
- 2016
-
Ingår i: Vibrational Spectroscopy. - : Elsevier BV. - 0924-2031 .- 1873-3697. ; 87, s. 215-221
-
Tidskriftsartikel (refereegranskat)abstract
- Amino groups in highly dense coatings of amines on solid supports react with CO2 of ambient air and form ammonium-carbamate ion pairs. These ion pairs change the properties of the amine-modified supports. In numerous studies, the corresponding infrared (IR) spectra have been misinterpreted. The presumption has been that such ion pairs would not form in ambient air, and therefore IR bands have been assigned to moieties of the support and the amines. Here, we discuss common misunderstandings of the IR spectra of amine-modified supports and highlight that proper sample handling is necessary before employing different characterization techniques. We exemplify by performing an IR spectroscopic study of a propylamine-modified porous silica. Such amine-modified supports are relevant to applications in gas separation, catalysis, controlled drug delivery and adsorption of pollutants from water.
|
|
| 10. |
- Bacsik, Zoltan, et al.
(författare)
-
Mechanisms and Kinetics for Sorption of CO(2) on Bicontinuous Mesoporous Silica Modified with n-Propylamine
- 2011
-
Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 27:17, s. 11118-11128
-
Tidskriftsartikel (refereegranskat)abstract
- We studied equilibrium adsorption and uptake kinetics and identified molecular species that formed during sorption of carbon dioxide on amine-modified silica. Bicontinuous silicas (AMS-6 and MCM-48) were postsynthetically modified with (3-aminopropyl)triethoxysilane or (3-aminopropyl)methyldiethoxysilane, and amine-modified AMS-6 adsorbed more CO(2) than did amine-modified MCM-48. By in situ FTIR spectroscopy, we showed that the amine groups reacted with CO(2) and formed ammonium carbamate ion pairs as well as carbamic acids under both dry and moist conditions. The carbamic acid was stabilized by hydrogen bonds, and ammonium carbamate ion pairs formed preferably on sorbents with high densities of amine groups. Under dry conditions, silylpropylcarbamate formed, slowly, by condensing carbamic acid and silanol groups. The ratio of ammonium carbamate ion pairs to silylpropylcarbamate was higher for samples with high amine contents than samples with low amine contents. Bicarbonates or carbonates did not form under dry or moist conditions. The uptake of CO(2) was enhanced in the presence of water, which was rationalized by the observed release of additional amine groups under these conditions and related formation of ammonium carbamate ion pairs. Distinct evidence for a fourth and irreversibly formed moiety was observed under sorption of CO(2) under dry conditions. Significant amounts of physisorbed, linear CO(2) were detected at relatively high partial pressures of CO(2), such that they could adsorb only after the reactive amine groups were consumed.
|
|
