Name: Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate (Video) | JoVE Journal
Uploaded: 2016-02-23T14:00:00.000+00:00
Duration: 8 min 44 s
Description: Learn surfactant-mediated sol-gel synthesis of nanosized monosodium titanate particles ranging 100-150 nanometers. Discover peroxide modification and gold(III) ion-exchange methods for advanced material applications.

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5 minutes

The authors thank the Laboratory Directed Research and Development program at the Savannah River National Laboratory (SRNL) for funding. We thank Dr. Fernando Fondeur for collection and interpretation of the FT-IR spectra and Dr. John Seaman of the Savannah River Ecology Laboratory for the use of the DLS instrument for particle size measurements. We also thank the Dr. Daniel Chan of the University of Washington and the National Institute of Health (Grant #1R01DE021373-01), for funding experiments investigating the ion exchange reactions with Au(III). The Savannah River National Laboratory is operated by Savannah River Nuclear Solutions, LLC for the Department of Energy under contract DE-AC09-08SR22470.

1. Synthesis of Nano-monosodium Titanate (nMST)
<ol>
	<li>Prepare 10 ml of solution #1 by adding 0.58 ml of 25 wt % sodium methoxide solution to 7.62 ml of isopropanol followed by 1.8 ml of titanium isopropoxide.</li>
	<li>Prepare 10 ml of solution #2 by adding 0.24 ml of ultrapure water to 9.76 ml of isopropanol.</li>
	<li>Add 280 ml of isopropanol to a 3-neck 500-ml round bottom flask, followed by 0.44 ml of Triton X-100 (average MW: 625 g/mol). Stir the solution well with a magnetic stir bar.</li>
	<li>Prepare a dual channel syringe pump to deliver solutions #1 and #2 at a rate of 0.333&#160;ml/min.</li>
	<li>Load solutions #1 and #2 into two separate 10-ml syringes fitted with a length of tubing that will allow delivery of the solution from the syringe pump to below the solution level in the 500-ml round bottom flask.</li>
	<li>While stirring, add all of solutions #1 and #2 (10 ml each) to the reaction using the syringe pump programmed in step 1.4.</li>
	<li>After the addition is complete, cap the flask and continue to stir for 24 hr at RT.</li>
	<li>Uncap the flask and heat the reaction mixture to ~82 &#176;C (refluxing isopropanol) for 45-90 min, followed by purging with nitrogen while maintaining heating. As isopropanol is evaporated, add ultrapure water intermittently to replace the evaporated isopropanol.</li>
	<li>After most of the isopropanol has evaporated and the volume of water added is approximately 50 ml, remove the heat and allow the reaction mixture to cool.</li>
	<li>Collect the product by filtering through a 0.1-&#181;m nylon filter paper, and wash several times with water to remove the surfactant and any residual isopropanol. Do not filter to dryness. After washing is complete, transfer the slurry from the filter into a pre-weighed bottle or vial, and store as an aqueous slurry.</li>
	<li>Determine the yield by determining the weight percent solids of the slurry. This can be done by measuring the weight of an aliquot of the slurry before and after drying.</li>
</ol>
2. Au(III) Ion Exchange
<ol>
	<li>Transfer 6.50 g of 4.23 wt % nMST slurry to a 50-ml centrifuge tube. This amount may vary based on the actual weight percent of the nMST slurry produced in step 1.10 above, and determined in step 1.11.</li>
	<li>Weigh out 0.0659 g of HAuCl4&#183;3H2O into a 1-dram glass vial. The target Ti:Au mass ratio is 4:1.</li>
	<li>Dissolve the HAuCl4&#183;3H2O in ~ 1 ml of water, then transfer to the centrifuge tube containing the nMST. Rinse the vial several times with additional water to ensure all of the HAuCl4&#183;3H2O is transferred to the centrifuge tube containing the nMST.</li>
	<li>Dilute the suspension with additional water, as necessary, to bring the total volume to 11 ml. Target a final Au(III) concentration of approximately 15 mM.</li>
	<li>Wrap the centrifuge tube in foil to keep the suspension in the dark, and then tumble the suspension on a shaker rotisserie for a minimum of 4 days.</li>
	<li>Collect the product by centrifuging at 3,000 x g for 15 min to isolate the solids. Wash the solids three times with distilled water by redispersing in water, and reisolate by centrifuging at 3,000 x g for 15 min to remove any unexchanged Au(III).</li>
	<li>Store the final product either as an aqueous suspension by redispersing in water, or as a moist solid by decanting off the final wash water and capping the tube. Store the product in the dark.</li>
</ol>
3. Preparation of the Peroxotitanate
<ol>
	<li>Transfer 5 g of a 9.8 wt % slurry of nMST to a small flask.</li>
	<li>Weigh out 0.154 g of 30 wt % H2O2 solution. The target H2O2:Ti molar ratio is 0.25:1.</li>
	<li>While stirring the nMST suspension well add the 0.154 g of H2O2 solution drop-wise. Upon H2O2 addition, the suspension of white solids immediately turns yellow.</li>
	<li>After the addition is complete stir the reaction at ambient temperature for 24 hr.</li>
	<li>Collect the product by filtering through a 0.1-&#181;m nylon filter, and wash several times with water to remove any unreacted H2O2. Do not filter to dryness. After washing is complete, transfer the slurry from the filter into a pre-weighed bottle or vial, and store as an aqueous slurry.</li>
</ol>

<ol><li>O'Regan, B., Grätzel, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+low-cost%2C+high-efficiency+solar+cell+based+on+dye-sensitized+colloidal+TiO2+films%5BTitle%5D)+AND+%22Nature%22%5BJournal%5D)">A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films.</a> Nature. 353, 737-740 (1991).</li>
<li>Frank, A. J., Kopidakis, N., van de Lagemaat, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Electrons+in+nanostructured+TiO2+solar+cells%3A+transport%2C+recombination+and+photovoltaic+properties%5BTitle%5D)+AND+%22Coord.+Chem.+Rev%22%5BJournal%5D)">Electrons in nanostructured TiO2 solar cells: transport, recombination and photovoltaic properties.</a> Coord. Chem. Rev. 248 (13-14), 1165-1179 (2004).</li>
<li>Mor, G. K., Varghese, O. K., Paulose, M., Shankar, K., Grimes, C. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+review+on+highly+ordered%2C+vertically+oriented+TiO2+nanotube+arrays%3A+fabrication%2C+material+properties%2C+and+solar+energy+applications%5BTitle%5D)+AND+%22Sol.+Energy+Mater.+Sol.+Cells%22%5BJournal%5D)">A review on highly ordered, vertically oriented TiO2 nanotube arrays: fabrication, material properties, and solar energy applications.</a> Sol. Energy Mater. Sol. Cells. 90 (14), 2011-2075 (2006).</li>
<li>Dosch, R. G. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aDosch%2C+RG+%22Use+of+titanates+in+decontamination+of+defense+waste.+Report+RS-8232-2%2F50318%22">Use of titanates in decontamination of defense waste. Report RS-8232-2/50318</a>. , Sandia National Laboratories. Albuquerque, NM. (1978).</li>
<li>Sylvester, P., Clearfield, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((The+removal+of+strontium+from+simulated+Hanford+tank+wastes+containing+complexants%5BTitle%5D)+AND+%22Sep.+Sci.+Technol%22%5BJournal%5D)">The removal of strontium from simulated Hanford tank wastes containing complexants.</a> Sep. Sci. Technol. 34 (13), 2539-2551 (1999).</li>
<li>Manna, B., Dasgupta, M., Ghosh, U. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Crystalline+hydrous+titanium%28IV%29+oxide+%28CHTO%29%3A+an+arsenic%28III%29+scavenger+from+natural+water%5BTitle%5D)+AND+%22J.+Water+Supply+Res.+T%22%5BJournal%5D)">Crystalline hydrous titanium(IV) oxide (CHTO): an arsenic(III) scavenger from natural water.</a> J. Water Supply Res. T. 53, 483-495 (2004).</li>
<li>Elvington, M. C., Click, D. R., Hobbs, D. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Sorption+behavior+of+monosodium+titanate+and+amorphous+peroxotitanate+materials+under+weakly+acidic+conditions%5BTitle%5D)+AND+%22Sep.+Sci.+Technol%22%5BJournal%5D)">Sorption behavior of monosodium titanate and amorphous peroxotitanate materials under weakly acidic conditions.</a> Sep. Sci. Technol. 45 (1), 66-72 (2010).</li>
<li>Wataha, J. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Titanates+deliver+metal+ions+to+human+monocytes%5BTitle%5D)+AND+%22J.+Mater.+Sci.%3A+Mater.+Med%22%5BJournal%5D)">Titanates deliver metal ions to human monocytes.</a> J. Mater. Sci.: Mater. Med. 21 (4), 1289-1295 (2010).</li>
<li>Chung, W. O., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Peroxotitanate-+and+monosodium+metal-titanate+compounds+as+inhibitors+of+bacterial+growth%5BTitle%5D)+AND+%22J.+Biomed.+Mater.+Res.%2C+Part+A%22%5BJournal%5D)">Peroxotitanate- and monosodium metal-titanate compounds as inhibitors of bacterial growth.</a> J. Biomed. Mater. Res., Part A. 97 (3), 348-354 (2011).</li>
<li>Hobbs, D. T., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Strontium+and+actinide+separations+from+high+level+nuclear+waste+solutions+using+monosodium+titanate+1.+Simulant+testing%5BTitle%5D)+AND+%22Sep.+Sci.+Technol%22%5BJournal%5D)">Strontium and actinide separations from high level nuclear waste solutions using monosodium titanate 1. Simulant testing.</a> Sep. Sci. Technol. 40 (15), 3093-3111 (2005).</li>
<li>Ramirez-Salgdo, J., Djrado, E., Fabry, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Synthesis+of+sodium+titanate+composites+by+sol-gel+method+for+use+in+gas+potentiometric+sensors%5BTitle%5D)+AND+%22J.+Eur.+Ceram.+Soc%22%5BJournal%5D)">Synthesis of sodium titanate composites by sol-gel method for use in gas potentiometric sensors.</a> J. Eur. Ceram. Soc. 24 (8), 2477-2483 (2004).</li>
<li>Yang, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Study+on+composition%2C+structure+and+formation+process+of+nanotube+Na2Ti2O4%28OH%292%5BTitle%5D)+AND+%22Dalton+Trans%22%5BJournal%5D)">Study on composition, structure and formation process of nanotube Na2Ti2O4(OH)2.</a> Dalton Trans. 2003 (20), 3898-3901 (2003).</li>
<li>Chen, W., Guo, X., Zhang, S., Jin, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((TEM+study+on+the+formation+mechanism+of+sodium+titanate+nanotubes%5BTitle%5D)+AND+%22J.+Nanopart.+Res%22%5BJournal%5D)">TEM study on the formation mechanism of sodium titanate nanotubes.</a> J. Nanopart. Res. 9 (6), 1173-1180 (2007).</li>
<li>Meng, X., Wang, D., Liu, J., Zhang, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Preparation+and+characterization+of+sodium+titanate+nanowires+from+brookite+nanocrystallites%5BTitle%5D)+AND+%22Mater.+Res.+Bull%22%5BJournal%5D)">Preparation and characterization of sodium titanate nanowires from brookite nanocrystallites.</a> Mater. Res. Bull. 39 (14-15), 2163-2170 (2004).</li>
<li>Yada, M., Goto, Y., Uota, M., Torikai, T., Watari, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Layered+sodium+titanate+nanofiber+and+microsphere+synthesized+from+peroxotitanic+acid+solution%5BTitle%5D)+AND+%22J.+Eur.+Ceram.+Soc%22%5BJournal%5D)">Layered sodium titanate nanofiber and microsphere synthesized from peroxotitanic acid solution.</a> J. Eur. Ceram. Soc. 26 (4-5), 673-678 (2006).</li>
<li>Stewart, T. A., Nyman, M., deBoer, M. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Delaminated+titanate+and+peroxotitanate+photocatalysts%5BTitle%5D)+AND+%22Appl.+Catal.+B%22%5BJournal%5D)">Delaminated titanate and peroxotitanate photocatalysts.</a> Appl. Catal. B. 105 (1-2), 69-76 (2011).</li>
<li>Rejman, J., Oberle, V., Zuhorn, I. S., Hoekstra, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Size-dependent+internalization+of+particles+via+the+pathways+of+clathrin-+and+caveolae-mediated+endocytosis%5BTitle%5D)+AND+%22Biochem.+J%22%5BJournal%5D)">Size-dependent internalization of particles via the pathways of clathrin- and caveolae-mediated endocytosis.</a> Biochem. J. 377 (1), 159-169 (2004).</li>
<li>Formation of nanosized metal particles on a titanate carrier. US patent application. , Application 20,150,071,980 Available from:
 <a target="_blank" href="http://www.patentsencyclopedia.com/app/20150071980">http://www.patentsencyclopedia.com/app/20150071980</a> (2015).</li>
<li>Elvington, M. C., Tosten, M., Taylor-Pashow, K. M. L., Hobbs, D. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Synthesis+and+characterization+of+nanosize+sodium+titanates%5BTitle%5D)+AND+%22J.+Nanopart.+Res%22%5BJournal%5D)">Synthesis and characterization of nanosize sodium titanates.</a> J. Nanopart. Res. 14, 1114(2012).</li>
<li>Duff, M. C., Hunter, D. B., Hobbs, D. T., Fink, S. D., Dai, Z., Bradley, J. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Mechanisms+of+strontium+and+uranium+removal+from+high-level+radioactive+waste+simulant+solutions+by+the+sorbent+monosodium+titanate%5BTitle%5D)+AND+%22Environ.+Sci.+Technol%22%5BJournal%5D)">Mechanisms of strontium and uranium removal from high-level radioactive waste simulant solutions by the sorbent monosodium titanate.</a> Environ. Sci. Technol. 38 (19), 5201-5207 (2004).</li>
<li>Puangpetch, T., Sreethawong, T., Chavadej, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Hydrogen+production+over+metal-loaded+mesoporous-assembled+SrTiO3+nanocrystal+photocatalysts%3A+effects+of+metal+type+and+loading%5BTitle%5D)+AND+%22Int.+J.+Hydrogen+Energy%22%5BJournal%5D)">Hydrogen production over metal-loaded mesoporous-assembled SrTiO3 nanocrystal photocatalysts: effects of metal type and loading.</a> Int. J. Hydrogen Energy. 35 (13), 6531-6540 (2010).</li>
<li>Fan, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Facile+method+to+synthesize+mesoporous+multimetal+oxides+%28ATiO3%2C+A+%3D+Sr%2C+Ba%29+with+large+specific+surface+areas+and+crystalline+pore+walls%5BTitle%5D)+AND+%22Chem.+Mater%22%5BJournal%5D)">Facile method to synthesize mesoporous multimetal oxides (ATiO3, A = Sr, Ba) with large specific surface areas and crystalline pore walls.</a> Chem. Mater. 22 (4), 1276-1278 (2010).</li>
<li>Rossmanith, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Porous+anatase+nanoparticles+with+high+specific+area+prepared+by+miniemulsion+technique%5BTitle%5D)+AND+%22Chem.+Mater%22%5BJournal%5D)">Porous anatase nanoparticles with high specific area prepared by miniemulsion technique.</a> Chem. Mater. 20 (18), 5768-5780 (2008).</li>
<li>Wu, Y., Zhang, Y., Xu, J., Chen, M., Wu, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((One-step+preparation+of+PS%2FTiO2+nanocomposite+particles+via+miniemulsion+polymerization%5BTitle%5D)+AND+%22J.+Colloid+Interface+Sci%22%5BJournal%5D)">One-step preparation of PS/TiO2 nanocomposite particles via miniemulsion polymerization.</a> J. Colloid Interface Sci. 343 (1), 18-24 (2010).</li>
<li>Jiang, C., Ichihara, M., Honmaa, I., Zhou, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Effect+of+particle+dispersion+on+high+rate+performance+of+nano-sized+Li4Ti5O12+anode%5BTitle%5D)+AND+%22Electrochim.+Acta%22%5BJournal%5D)">Effect of particle dispersion on high rate performance of nano-sized Li4Ti5O12 anode.</a> Electrochim. Acta. 52 (23), 6470-6475 (2007).</li>
<li>Bouras, P., Stathatos, E., Lianos, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Pure+versus+metal-ion-doped+nanocrystalline+titania+for+photocatalysis%5BTitle%5D)+AND+%22Appl.+Catal.+B%22%5BJournal%5D)">Pure versus metal-ion-doped nanocrystalline titania for photocatalysis.</a> Appl. Catal. B. 73 (1-2), 51-59 (2007).</li>
<li>Bonino, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Ti-Peroxo+species+in+the+TS-1%2FH2O2%2FH2O+system%5BTitle%5D)+AND+%22J.+Phys.+Chem.+B%22%5BJournal%5D)">Ti-Peroxo species in the TS-1/H2O2/H2O system.</a> J. Phys. Chem. B. 108 (11), 3573-3583 (2004).</li>
<li>Bordiga, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Resonance+Raman+effects+in+TS-1%3A+the+structure+of+Ti%28IV%29+species+and+reactivity+towards+H2O%2C+NH3+and+H2O2%3A+an+in+situ+study%5BTitle%5D)+AND+%22Phys.+Chem.+Chem.+Phys%22%5BJournal%5D)">Resonance Raman effects in TS-1: the structure of Ti(IV) species and reactivity towards H2O, NH3 and H2O2: an in situ study.</a> Phys. Chem. Chem. Phys. 2003 (5), 4390-4393 (2003).</li>
<li>Vacque, V., Sombret, B., Huvenne, J. P., Legrand, P., Suc, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Characterization+of+the+O-O+peroxide+band+by+vibrational+spectroscopy%5BTitle%5D)+AND+%22Spectrochim.+Acta+Part+A%22%5BJournal%5D)">Characterization of the O-O peroxide band by vibrational spectroscopy.</a> Spectrochim. Acta Part A. 53 (1), 55-66 (1997).</li>
</ol>

The authors have nothing to disclose.

The presence of extraneous water, for example from impure reagents, can alter the outcome of the reaction, leading to larger or more polydisperse particles. Therefore, care should be taken to ensure dry reactants are used. The titanium isopropoxide and sodium methoxide should be stored in a desiccator when not in use. High purity isopropanol should also be used for the synthesis.
Temperature was found to play a key role in the conversion of the product from a gel to particulate form. TEM image...

Titanium dioxide and alkali metal titanates are widely used in a variety of applications such as pigments in paint and skin care products and as photocatalysts in energy conversion and utilization.1-3 Sodium titanates have been shown to be effective materials to remove a range of cations over a wide range of pH conditions through cation exchange reactions.4-7
In addition to the applications just described, micron-sized sodium titanates and sodium peroxotitanates have recently been shown to also serve as a therapeutic metal delivery platform. In this application, therapeutic metal ions such as Au(III), Au(I), and Pt(II) are exchanged for the sodium ions of monosodium titanate (MST). In vitro tests with the noble metal-exchanged titanates indicate suppression of the growth of cancer and bacterial cells by an unknown mechanism.8,9
Historically, sodium titanates have been produced using both sol-gel and hydrothermal synthetic techniques resulting in fine powders with particle sizes ranging from a few to several hundred microns.4,5,10,11 More recently, synthetic methods have been reported that produced nanosize titanium dioxide, metal-doped titanium oxides, and a variety of other metal titanates. Examples include sodium titanium oxide nanotubes (NaTONT) or nanowires by reaction of titanium dioxide in excess sodium hydroxide at elevated temperature and pressure,12-14 sodium titanate nanofibers by reaction of peroxotitanic acid with excess sodium hydroxide at elevated temperature and pressure,15 and sodium and cesium titanate nanofibers by delamination of acid-exchanged micron-sized titanates.16
The synthesis of nanosize sodium titanates and sodium peroxotitanates is of interest to enhance ion exchange kinetics, which are typically controlled by film diffusion or intraparticle diffusion. These mechanisms are largely controlled by the particle size of the ion exchanger. In addition, as a therapeutic metal delivery platform, the particle size of the titanate material would be expected to significantly affect the nature of the interaction between the metal-exchanged titanate and the cancer and bacterial cells. For example, bacterial cells, which are typically on the order of 0.5 &#8211; 2 &#181;m, would likely have different interactions with micron size particles versus nanosized particles. In addition, non-phagocytic eukaryotic cells have been shown to only internalize particles with a size of less than 1 micron.17 Thus, the synthesis of nanosize sodium titanates is also of interest to facilitate metal delivery and cellular uptake from the titanate delivery platform. Reducing the size of sodium titanates and peroxotitanates will also increase the effective capacity in metal ion separations and enhance photochemical properties of the material.16,18 This paper describes a protocol developed to synthesize nanosize monosodium titanate (nMST) under mild sol-gel conditions.19 The preparation of the corresponding peroxide modified nMST; along with an ion-exchange reaction to load the nMST with Au(III) are also described.

<table><tbody><tr><td>Titanium(IV) isopropoxide</td><td>Sigma Aldrich</td><td>377996</td><td>99.999% trace metals basis</td></tr><tr><td>Isopropyl alcholol, 99.9%</td><td>Sigma Aldrich</td><td>650447</td><td>HPLC grade (Chomasolv)</td></tr><tr><td>Sodium methoxide in methanol</td><td>Sigma Aldrich</td><td>156256</td><td>25 wt%</td></tr><tr><td>Triton X-100</td><td>Sigma Aldrich</td><td>T9284</td><td>BioXtra</td></tr><tr><td>hydrogen tetrachloroaurate(III) trihydrate</td><td>Sigma Aldrich</td><td>G4022</td><td>ACS reagent grade</td></tr><tr><td>hydrogen peroxide (30&amp;nbsp;wt%)</td><td>Fisher</td><td>H325</td><td>Certified ACS</td></tr><tr><td>10-ml syringes</td><td>Fisher</td><td>14-823-16E</td><td></td></tr><tr><td>Dual channel syringe pump</td><td>Cole Parmer</td><td>EW-74900-10</td><td>Or equivalent programmable dual channel syringe pump</td></tr><tr><td>Tygon tubing 1/8 inch ID, 1/4 inch OD</td><td>Cole Parmer</td><td>EW-0640776</td><td></td></tr><tr><td>Tygon tubing 1/16 inch ID, 1/8 inch OD</td><td>Cole Parmer</td><td>EW-0740771</td><td></td></tr><tr><td>0.1-&amp;micro;m Nylon filter</td><td>Fisher</td><td>R01SP04700</td><td></td></tr><tr><td>Labquake shaker rotisserie</td><td>Thermo Scientific</td><td>4002110Q</td><td></td></tr></tbody></table>

synthesis and reaction chemistry of nanosize monosodium titanate

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

MST is synthesized using a sol-gel method in which tetraisopropoxytitanium(IV) (TIPT), sodium methoxide, and water are combined and reacted in isopropanol to form seed particles of MST.4 Micron-sized particles are then grown by controlled addition of additional quantities of the reagents. The resultant particles feature an amorphous core and an outer fibrous region having dimensions of about 10 nm wide by 50 nm in length.20
Figure 1A shows a typical parti...

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

The overall goal of the following experiment is to prepare nanosized sodium titanate materials including peroxide-modified and gold(III)loaded materials. This is achieved by first performing a surfactant-mediated sol-gel synthesis to prepare nanosized monosodium titanate particles in the range of 100 to 150 nanometers. As a second step, the nanosized monosodium titanate can be treated with hydrogen peroxide which converts a portion of the material to a peroxotitanate form.Next, an ion-exchange reaction can be performed to prepare metal-loaded titanates for various applications. An example is the addition of a solution of gold(III)chloride to the nanotitanate to produce the corresponding gold(III)exchanged titanate. Results are obtained that show spherical particles in the range of 100 to 150 nanometers can be prepared using the method, based on electron microscopy imaging and dynamic light scattering measurements.We first had the idea for this method when we began looking at the application of titanates in the biomedical field where particle size becomes more important. This method can be extended to materials normally synthesized using sol-gel techniques, allowing materials with a range of different particle sizes to be prepared. Nanosized particles, monosodium titanate, provide the opportunity to improve ion exchange performance due to their higher surface area to volume ratio.Use of metal exchange titanates as bactericides can be enhanced with nanosized materials. To begin the synthesis of nano monosodium titanate, or nMST, first add 0.58 milliliters of 25 weight percent sodium methoxide solution to 7.62 milliliters of isopropanol followed by 1.8 milliliters of titanium isopropoxide. Label the solution number one.Next, add 0.24 milliliters of ultra-pure water to 9.76 milliliters of isopropanol to make solution number two. Add 0.44 milliliters of Triton X-100 to 280 milliliters of isopropanol in a three-neck flask and stir well with a magnetic stirrer. Fit the syringe ends with tubing of sufficient length to deliver the solutions below the level of the liquid in the flask and load solutions one and two into two separate syringes.Next, place the syringes into a dual-channel syringe pump and deliver the solutions at a rate of 0.333 milliliters per minute to the flask. After addition, cap the flask and continue stirring for 24 hours at room temperature. Afterwards, uncap the flask and heat the mixture to reflux for 45 to 90 minutes.Purge the flask with nitrogen and add ultra-pure water in portions to replace evaporated isopropanol as heating is continued. After most of the isopropanol has evaporated and the volume of water added has reached approximately 50 milliliters, remove the heat from the flask and allow the mixture to cool. Filter the product through a 0.1 micron nylon filter paper and wash it several times with water.Finally, transfer the slurry from the filter into a pre-weighed bottle and store it at ambient temperature. To determine the yield, weigh an aliquot of the aqueous slurry before and after drying. To perform the exchange with gold(III)ions, first transfer 6.50 grams of the 4.23 weight percent slurry of nMST to a 50 milliliter centrifuge tube.Next, add about one milliliter of water to 0659 grams of hydrogen tetrachloro gold(III)trihydrate in a one dram glass vial. Transfer the solution to the centrifuge tube. Continue by rinsing the glass vial with water and adding it to the tube.Repeat this several times to ensure that all of the gold reagent is transferred. Add water to the tube to bring the total volume up to 11 milliliters. Wrap the tube in foil and then tumble it on a shaker for a minimum of four days.After tumbling the mixture, centrifuge the tube for 15 minutes. Discard the supernatant and re-suspend the solids in distilled water. Centrifuge the sample again and repeat the washing procedure twice more.Finally, re-suspend the solids in water and store in the dark at room temperature. To prepare peroxotitanate, begin by adding five grams of a 9.8 weight percent slurry of nMST to a flask and stir the slurry magnetically. Continue by adding dropwise 0.154 grams of a 30 weight percent hydrogen peroxide solution to the flask, which induces a color change from white to yellow.Continue stirring the mixture at ambient temperature for 24 hours. Next, filter the product through a 0.1 micron nylon filter paper and was the product several times with water to remove any un-reacted hydrogen peroxide. Finally, transfer the slurry from the filter into a pre-weighed bottle and store the aqueous slurry of peroxotitanate at ambient temperature.Shown here is a typical particle size distribution as measured by dynamic light scattering using the established sol-gel method. Note that this synthesis produces a multimodal distribution of particles with the majority around one micrometer. When reaction conditions that aimed to reduce the particle size of the monosodium titanate were employed, which involved removing the seeding step and using more dilute reagents, this resulted in a bimodal distribution of particle sizes centered at 50 to 100 nanometers and 500 nanometers after 24 hours.After 48 hours, a trimodal distribution of particles measuring up to 1000 nanometers was observed, as demonstrated in this graph. Importantly, the addition of Triton X-100 during the synthesis of nMST is critical for producing an almost uniform particle size distribution as measured by dynamic light scattering. Transmission and scanning electron microscopy showed that the Triton X-100 produced nMST particles at a more uniform size and morphology when compared to those of monosodium titanate.The surface modification of nMST particles by hydrogen peroxide was confirmed by the appearance of an absorption band at 883 wave numbers in its Fourier transform infrared spectrum. After its development, this technique paved the way for researchers in the field of biological applications of inorganic materials to explore the use of nanotitanates to deliver therapeutic metals and the metal exchange titanates to service bactericides. After watching this video, you should have good understanding of how to prepare nanoscale particles of monosodium titanate along with the peroxide-modified and metal-loaded forms.Remember that working with flammable solvents and reagents can be extremely hazardous. Precautions should be taken to prevent the buildup of flammable vapors. It is recommended that sol-gel synthesis be carried out in a chemical fume hood.

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Research

JoVE Journal

Chemistry

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Learn surfactant-mediated sol-gel synthesis of nanosized monosodium titanate particles ranging 100-150 nanometers. Discover peroxide modification and gold(III) ion-exchange methods for advanced material applications.

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

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