| 1. |
- Trublet, Mylene
(author)
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Titanium(IV) Phosphates : The Next Generation of Wastewater Sorbents
- 2018
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Doctoral thesis (other academic/artistic)abstract
- Treatment of industrial waters containing heavy metal ions is essential before being discharged into the environment. Consequently, European regulations have been established to control and limit the amount of heavy metals released. There is a need to develop efficient water treatment techniques that can remove contaminants with respect to these EU regulations.Ion-exchange is one of the processes that is being investigated due to fast kinetics, high treatment capacity and its ability to remove heavy metal ions present in trace amounts. Titanium phosphates (TiP) are a group of inorganic ion-exchangers that have demonstrated to be particularly selective towards transition metal ions in aqueous solutions. Two types of ion-exchange units are present in TiP material, which are –HPO4 and –H2PO4 groups. Their structural characteristic is highly dependent on the synthesis conditions, which include the source of titanium, temperature, reaction time and P2O5:TiO2 ratio. Most of the studies have been performed on amorphous TiP containing a mixture of both exchange units, with –HPO4 groups being predominant; as crystalline TiP and –H2PO4 based TiP are often obtained in difficult conditions, high temperature (up to 250 °C) and/or long reaction time (up to 30 days) and/or using autoclave. Despite promising properties depicted in batch conditions, very few data in continuous flow systems (fixed-bed columns) have been reported.In this work, amorphous TiP composed of entirely –H2PO4 ion-exchange units (TiP1) was synthesized at mild conditions using a TiOSO4 solution and HCl/deionized water as post-synthesis treatments. The sorbent was characterized using a range of techniques (solid-state 31P MAS NMR, Raman, XRD, TGA, BET, Elemental analysis, EXAFS and XANES,) and tested in batch and column set-ups towards single and multi-component waters. The chemical formula of TiP1 was established as TiO(OH)(H2PO4)·H2O and it was found that the synthesis of TiP1 was also dependent on the TiO2/H2SO4 content in the primary titanium solution.The material displayed a high maximum exchange capacity of ca. 6.4 meq.g-1, expressed as the sodium uptake. The actual ion-exchange capacity towards divalent metal ions was calculated to be ca. 3.4 meq.g-1 in batch condition and up to 4.1 meq.g-1 in fixed-bed column, which is to date the highest recorded for TiP materials. Kinetics of the exchange processes have been studied and the equilibrium was reached within 5-20 minutes. Modeling of the breakthrough curves was achieved using the Thomas model, indicating that the rate driving forces of the processes follow second-order reversible kinetics. The TiP1 sorbent has shown to maintain a high selectivity towards heavy metal ions in multi-component systems (including closed-mine waters) when column studies were performed. The sorption behavior of TiP1 in batch experiments correlates very well with data obtained in fixed-bed column conditions, confirming that prediction of the sorption behavior on the basis of batch data is conceivable.Another important aspect of this work also involves the mild syntheses of crystalline α-TiP, Ti(HPO4)·H2O, and LTP (Linked Titanium Phosphate) composed of α-TiP and TiP1, where the structural characteristics of these materials were investigated using solid-state NMR, XRD, TGA, EXAFS and XANES.
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| 2. |
- Maslova, Marina, et al.
(author)
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Aluminum adsorption on titanium phosphate and silica-modified titanium phosphates
- 2009
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In: The Natural History of Aluminium : From Non-Selection to Natural Selection. ; , s. 41-
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Conference paper (other academic/artistic)abstract
- Synthesis, characterization and sorption affinities of titanium phosphate (TiP) and titanium phosphate silicates (TiPSi) in relation to various metal ions were recently reported by our group. In this work, we explored further adsorption properties of these materials with respect to aluminium ions in aqueous solutions. Sorption of Al3+(aq) increases with pH and reaches ca. 13 mg/g at pH close to neutral conditions and it can be described by an ion-exchange mechanism. Surface speciation of aluminium was studied by 27Al and 31P solid state NMR. These and other spectroscopic data were correlated with adsorption macroscopic measurements. Purification of process and drinking waters is one of the potential applications of these cheap adsorbents manufactured by decomposition of mineral sphene, CaTiOSiO4, which is abundant up to 5 % in tailings of apatite ores in Kola peninsula.
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| 3. |
- Maslova, Marina, et al.
(author)
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Formation of titanium phosphate composites during phosphoric acid decomposition of natural sphene
- 2008
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In: Journal of Solid State Chemistry. - : Elsevier BV. - 0022-4596 .- 1095-726X. ; 181:12, s. 3357-3365
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Journal article (peer-reviewed)abstract
- Decomposition of mineral sphene, CaTiOSiO4, by H3PO4 is investigated in detail. During the dissolution process, simultaneous calcium leaching and formation of titanium phosphate (TiP) take place. The main product of decomposition is a solid titanium phosphate-silica composite. The XRD, solid-sate NMR, IR, TGA, SEM and BET data were used to identify and characterize the composite as a mixture of crystalline Ti(HPO4)2H2O and silica. When 80% phosphoric acid is used the decomposition degree is higher than 98% and calcium is completely transferred into the liquid phase. Formation of Ti(HPO4)2H2O proceeds via formation of meta-stable titanium phosphate phases, Ti(H2PO4)(PO4)2H2O and Ti(H2PO4)(PO4).The sorption affinities of TiP composites were examined in relation to caesium and strontium ions. A decrease of H3PO4 concentration leads to formation of composites with greater sorption properties. The maximum sorption capacity of TiP is observed when 60% H3PO4 is used in sphene decomposition.The work demonstrates a valuable option within the Ti(HPO4)2H2O-SiO2 composite synthesis scheme, to use phosphoric acid flows for isolation of CaHPO42H2O fertilizer.
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| 4. |
- Maslova, Marina, et al.
(author)
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Synthesis, characterization, and sorption properties of amorphous titanium phosphate and silica-modified titanium phosphates
- 2008
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 47:23, s. 11351-11360
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Journal article (peer-reviewed)abstract
- Amorphous titanium hydroxyphosphate with formula Ti(OH)1.36(HPO4)1.322.3H2O and a new silica-modified titanium hydroxyphosphate with a general formula Ti(OH)2x(HPO4)2-xySiO2nH2O are synthesized and characterized using IR, TG, XRD, SEM, solid-state NMR, and BET techniques. It is concluded that SiO2 is evenly distributed within the titanium phosphate (TiP) agglomerates and that neither the separate silica phase nor the titanium silicates are formed during the synthesis of silica-modified titanium hydroxyphosphate. Correlations between the texture, ion-exchange properties of the amorphous titanium hydroxyphosphate, and the amount of SiO2 present within the TiP matrix are established. Sorption properties of silica-modified titanium hydroxyphosphate toward Cs+ and Sr2+ are studied in a series of samples with an increasing amount of silica, at different pH, and in NaCl solutions with a varying ionic strength. It is found that sorption of Cs+ does not depend practically on the amount of SiO2 present, whereas the Sr2+ uptake drastically decreases with an increase of silica amount. The effects of pH and of the electrolyte concentration on the sorption behavior of titanium phosphate are discussed in terms of ionic hydration shell and titanium phosphate structural specificity. The kinetics of sorption processes is also investigated, and the diffusion coefficients for cesium and strontium are obtained.
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| 5. |
- Maslova, Marina, et al.
(author)
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Synthesis of titanium phosphates from unconventional solid precursor and their ion-exchange and electrochemical properties
- 2021
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In: Journal of Materials Science. - : Springer. - 0022-2461 .- 1573-4803. ; 56:16, s. 9929-9950
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Journal article (peer-reviewed)abstract
- A new low-cost and simple synthesis of titanium phosphate functional materials of desired composition has been developed. The route of material transformation is unconventional solid precursor-sorbent-anode material. The synthesis is based on the heterogeneous interaction between phosphoric acid and the solid (NH4)2TiO(SO4)2·H2O precursor. The influence of the synthesis conditions on the titanium phosphate composition has been thoroughly studied using NMR, FTIR spectroscopy, XRD, and DTA techniques, and mechanism of TiP formation has been established. Optimal synthesis conditions to provide obtaining of a pure TiO(OH)(H2PO4)·H2O (TiHP) phase have been found. In contrast to existing methods that require rigid synthesis conditions and high reagent consumption, the new synthesis lasts 4 h and no special equipment is needed. The sorption and electrochemical capabilities of TiHP have been investigated. The obtained material exhibits the highest sorption capacity toward Cs+ and Sr2+ ions among other TiP-based ion exchangers. Furthermore, TiHP has been tested as a sorbent for treatment of multicomponent liquid radioactive waste and distribution coefficients of the radionuclides have been found to be 105 mL·g–1. New approach to the synthesis of precursor for Li-ion batteries has been proposed. The substitution of protons of the dihydrogen phosphate group in TiHP by lanthanum (III) cations and subsequent calcination at 900 °C result in formation of nanoparticles of the final powder and provide the good electrochemical characteristics of obtained electrode material.
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| 6. |
- Maslova, Marina V., et al.
(author)
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Extended study on the synthesis of amorphous titanium phosphates with tailored sorption properties
- 2012
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In: Journal of Non-Crystalline Solids. - : Elsevier BV. - 0022-3093 .- 1873-4812. ; 358:22, s. 2943-2950
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Journal article (peer-reviewed)abstract
- The influence of concentrations of both TiO2 and H2SO4 in the syntheses of amorphous titanium phosphates (TiP) is reported. IR, XRD, TGA, BET and NMR techniques were used to characterise the isolated TiP products. The concentration of sulphuric acid in the initial synthesis plays a major role in the structural diversity and sorption properties of the final ionites. In the primary solutions, Ti(IV) is in monomeric, polymeric and colloidal forms. Upon addition of H3PO4 the presence of monomeric titanium ensures formation of the Ti(HPO4)2 phase. The polymeric Ti(IV) is responsible for formation of the titanium hydroxo-phosphate phase, Ti(OH)2(HPO4), whilst the colloidal form of Ti(IV) appears to have a role in coagulation of a minor Ti(OH)4 phase in an amorphous TiP. It is found that TiP ion-exchange capacities gradually increase with an increase of both TiO2 and H2SO4 concentrations and reach a maximum value of 3.8 mg-eq g− 1 when TiO2 is 70–100 g L− 1 and H2SO4 is 480–560 g L− 1. Analyses of compositional, structural and sorption data allowed 3D correlation diagrams to be built that can facilitate fabrication of TiP with tailored sorption properties.
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| 7. |
- Trublet, Mylene, et al.
(author)
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Mild syntheses and surface characterization of amorphous TiO(OH)(H2PO4)·H2O ion-exchanger
- 2016
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In: Materials Chemistry and Physics. - : Elsevier BV. - 0254-0584 .- 1879-3312. ; 183, s. 467-475
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Journal article (peer-reviewed)abstract
- This work focuses on the synthesis of titanium phosphate (TiP1) ion-exchanger containing solely H2PO4-groups. Based on the elemental analyses, TG, 31P MAS NMR, XRD and Raman data, the formula TiO(OH)(H2PO4)·H2O is assigned to TiP1. The synthesis requires a mild heating at 70–80 °C for a short period of time, followed by filtration and HCl-washing of the TiP1 powder. The layered nature and low crystallinity of this sorbent is confirmed by powder XRD technique. The existence of micro and mesopores in the material is established using BET method. The Na+ capacity of TiP1 is determined to be 6.3 meq g−1 which is the highest value reported for H2PO4-based sorbents. The presence of H2PO4 groups is expected to considerably increase both the pH-working range of the TiP1 sorbent and its exchange capacity towards divalent metal ions. All data for TiP1 are compared to the data for amorphous TiP containing mostly HPO4 groups.
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| 8. |
- Trublet, Mylene, et al.
(author)
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Sorption performances of TiO(OH)(H2PO4)·H2O in synthetic and mine waters
- 2017
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In: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 7:4, s. 1989-2001
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Journal article (peer-reviewed)abstract
- ¨The sorption properties toward Cu2+, Zn2+, Ni2+, Mn2+ and Co2+ ions, in synthetic and industrial waters with pH of 3.9–7.2, and the chemical stability of a titanium phosphate ion-exchanger synthesized at mild conditions and containing solely –H2PO4 groups, TiO(OH)(H2PO4)·H2O (TiP1) are investigated. TiP1 displays the highest Na+ uptake (6.3 meq. g−1) among TiP ion-exchangers and a maximum sorption capacity of ca. 1.55 mmol g−1 (i.e. 3.1 meq. g−1) for the studied ions, which is higher than the ones reported for exchangers composed predominantly of –HPO4 groups. The sorption isotherms were best described by the Temkin model while the Langmuir and the Freundlich models appear to be insufficient in describing all data. TiP1 shows fast kinetics with an equilibrium reached within 10–20 minutes and diffusion processes play a role in the initial period of sorption that is overpowered by chemisorption reactions in the overall rate controlling step. The selectivity order of the metal ions on TiP1 is determined as: Cu2+ > Zn2+ ≫ Mn2+ > Co2+, Ni2+, following the order of stability of MOH+ complexes and the corresponding activation parameters for a water molecule exchange in [M(H2O)6]2+ ions. The surface sorption data are in good correlation with the EDS data for these systems, supporting the idea of chemical sorption with no metal hydroxide precipitation. Additional sorption studies show that the quality of industrial waters after sorption reaches the EU recommendation for drinking water. The faster kinetics and the higher exchange capacity reveal that the presence of –H2PO4 groups strongly enhances the sorption properties of titanium phosphate sorbents.
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