Chemical Communications: Volume 48 - Number 13 - 11 February 2012 - Pages 1825-1932
Chemical Communications: Volume 48 - Number 13 - 11 February 2012 - Pages 1825-1932
Chemical Communications: Volume 48 - Number 13 - 11 February 2012 - Pages 1825-1932
Chemical Communications
Downloaded on 28 May 2012 Published on 10 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CC16050H
www.rsc.org/chemcomm
ISSN 1359-7345
COMMUNICATION Rafael Luque and Dionysios D. Dionysiou et al. Facile preparation of controllable size monodisperse anatase titania nanoparticles
ChemComm
Cite this: Chem. Commun., 2012, 48, 18601862 www.rsc.org/chemcomm
COMMUNICATION
Received 28th September 2011, Accepted 31st October 2011 DOI: 10.1039/c1cc16050h Monodisperse anatase titania nanoparticles with controllable sizes (typically 10300 nm) can be synthesized using an ecient and straightforward protocol via ne tuning of the ionic strength in the devised solgel methodology. Nanocrystalline titanium dioxide (TiO2) materials have been extensively investigated and utilised in many technological applications due to their excellent physicochemical properties, such as thermal and chemical stability, relatively high photocatalytic activity, low toxicity and cost. These have found a wide range of applications in various areas, including cosmetics and sunscreen formulations,1 catalysis,2,3 ceramics,4 dye-sensitized solar cells,5,6 and solar-based drinking water treatment.7 The uniformity of nanoparticles is of remarkable importance because the materials properties are generally directly related to particular characteristics such as size and shape.8 In addition, uniform nanoparticles are potentially required in the area of nanotoxicology to study the eect of nanoparticle size. Thus, a controllable and simple methodology to design monodisperse titania nanoparticles can lead to highly ecient performing materials. Recently, a great deal of research eorts have been devoted to the preparation of monodisperse TiO2 particles. Eiden-Assmann et al.9 discussed that particle size and distribution could be controlled by the ionic strength. These authors prepared monodisperse TiO2 particles (4200 nm in diameter) using nitrates, KCl, NaCl, CsCl, and LiCl solutions under an inert atmosphere. Larger monodisperse TiO2 particles (4500 nm in diameter) could be also obtained by using NaCl and HCl, controlling particle sizes with dierent concentrations of salt solutions.10 Functional uorescent TiO2 based monodisperse nanoparticles (470 nm in diameter) were also reported to be obtained employing EuCl3 to control ionic strength with dierent concentrations of salt solutions.11 Eun et al.12 reported that monodisperse TiO2 hollow spheres (440 mm of diameter) were synthesized utilising embedded functional nanoparticles in a
a
Environmental Engineering and Science Program, School of Energy, Environmental, Biological and Medical Engineering, University of Cincinnati, OH 45221-0012, USA. E-mail: dionysios.d.dionysiou@uc.edu; Fax: +1 513 556 4162; Tel: +1 513 556 0724 b Departamento de Quimica Organica, Facultad de Ciencias, Universidad de Cordoba, Campus de Excelencia Agroalimentario (CeiA3) de Rabanales, Ctra Nnal IV-A, Km 396, E-14014, Cordoba, Spain. E-mail: q62alsor@uco.es
microuidic device. In most cases, the reported methodologies make use of the ability to ne tune the ionic strength to control size and distribution of particles. However, most of the reported monodisperse TiO2 nanoparticles possess large sizes (generally 4200 nm), are amorphous and involve rather time consuming and complex preparation protocols. A simplied and facile protocol for the development of small size titania monodisperse particles can potentially constitute a signicant advance in the controllable design of such nanomaterials for more specic applications (e.g. nanotoxicity and nanosafety studies). In continuation of our recent research endeavours in the development of simple and ecient nano-titania materials for photocatalysis and environmental remediation,2,3,13 we report here an ecient, environmentally friendly and facile solgel approach for the controllable synthesis of monodisperse and highly uniform TiO2 nanoparticles of various sizes in the 10300 nm range employing dierent concentrations of a CaCl2 solution. The prepared TiO2 nanoparticles were calcined at 500 1C for 1 h to yield nanocrystalline anatase TiO2. Materials were characterised by several techniques including X-ray diraction (XRD), Environmental Scanning Electron Microscopy (ESEM), Transmission Electron Microscopy (TEM), High resolution TEM (HR-TEM), and Dynamic Light Scattering (DLS) to examine the formation of the small titania nanoparticles. The proposed methodology comprises of three simple steps. Firstly, 50 mL MeOH was added in a bottle-type reactor (120 mL) and mixed for 10 min with 200 mL of dierent concentrations of CaCl2 solutions, typically in the range of 0.05 to 0.15 M. 850 mL of the titanium precursor (titanium(IV) isopropoxide, TTIP, 97%, Sigma-Aldrich) was added dropwise (Scheme 1). The resulting solution was stirred for 24 h at room temperature, yielding white solutions of dierent densities depending on the salt concentration (Fig. 1). The synthesized TiO2 nanoparticles were subsequently ltered o using a membrane lter (0.02 mm pore size, Whatman Anodisc Filter Membranes) and then collected upon washing of the lters with MilliQ grade water, drying and calcination in a multi-segment programmable high temperature furnace (Paragon Model HT-22-D, Thermcraft Inc., Winston-Salem, NC) at 500 1C for 1 h (Scheme 1). SEM characterisation of dierent monodisperse titania nanoparticles is depicted in Fig. 1. Images clearly demonstrate the homogeneity and monodispersity of spherical-shaped nanoparticles ranging from 300 to about 30 nm in diameter.
This journal is
c
1860
View Online
Fig. 2 Particle size distribution by using dynamic light scattering (DLS). Scheme 1 Devised protocol for the preparation of size controlled monodisperse titania nanoparticles.
To obtain monodisperse nanoparticles by the solgel method, a careful control of nucleation and nanoparticle growth is necessary. The concentration of CaCl2 solution could be eectively varied as a critical parameter in the preparation of various nanomaterials. The ionic strength of the solution, which may aect the nucleation and growth of particles, has indeed been reported to be directly related to the concentration of salt.9 Both controllable and promisingly small nanoparticle sizes could be obtained using the proposed methodology via simple increase of the CaCl2 concentration in the synthesis (from 0.05 to 0.11 M, Fig. 1). Images for smaller particles (o25 nm) could not be obtained due to the resolution limitations of SEM.
Light scattering measurements of these experiments pointed out that titania nanoparticles as small as 810 nm could be synthesized (Fig. 2). However, the isolation and observation of such small size nanoparticles by dierent methodologies (especially in the solid state and after calcination) is highly challenging, even when stabilising agents such as PVP, ionic liquids and related capping chemicals were utilised in post-synthesis steps.
Fig. 1 ESEM micrographs of monodisperse titania nanoparticles with dierent sizes before (a, c, e) and after calcination (b, d, f). Nanoparticle sizes: 348 38 nm (top images); 60 6.8 nm (center images); 32 4.7 nm (bottom images).
Fig. 3 TEM micrographs of monodisperse titania nanoparticles of dierent sizes before (a, c) and after calcination (b, d, e).
This journal is
1861
View Online
TEM micrographs compiled in Fig. 3 highlight the homogeneous distribution of sizes in the synthesized nanoentities. Most remarkably, materials exhibited very similar sizes before and after calcination which show an almost negligible nanoparticle aggregation during the calcination process at 500 1C. The observation of smaller titania nanoparticles by TEM was also possible by using polyvinylpyrrolidone (PVP) as stabilising agent (Fig. 4). Nanoparticle sizes visualized in these experiments (1215 nm) were in good agreement with data obtained in light scattering measurements (Fig. 2). The selected-area electron diraction (SAED) patterns showed the polycrystalline diraction rings corresponding to the indices of the lattice planes of a TiO2 anatase phase14 (Fig. 4b) and the measured lattice spacing (0.35 nm) of TiO2 conrmed the lattice distance of anatase (101) planes in the HR-TEM image14,15 (Fig. 4c). The TiO2 phase was also conrmed as anatase by XRD analysis, which showed the typical diractions of the phase regardless of the dierent investigated conditions of salt concentration (Fig. 5), in good agreement with results of SAED and HR-TEM and previous literature reports.1416 In summary, we have developed an ecient, straightforward and environmentally benign approach to the design of controllable monodisperse crystalline titania nanoparticles of dierent sizes (10300 nm) by simply ne-tuning the ionic strength in the materials synthesis. We envisage this facile approach to be extended to the preparation of related nanoscale materials (e.g. ZnO, ZrO2) in view of future applications and studies of the materials in dye-sensitized solar cells, nanotoxicity and nanosafety.
Fig. 5 XRD patterns of the various synthesized monodisperse titania nanoparticles. All materials show the distinct diraction lines of the anatase phase.
Rafael Luque gratefully acknowledges support from Ministerio de Ciencia e Innovacion, Gobierno de Espana through a Ramon y Cajal contract (ref. RYC-2009-04199) and project CTQ2011-28954-C02-02 as well as funding from Consejeria de Ciencia e Innovacion, Junta de Andalucia (project P10-FQM6711) and the concession of a short stay fellowship under Incentivos para Actividades de caracter cientico y tecnico to RL (ref. IAC-2010-2-4512) at the EPA in Cincinnati. This work was also partially funded by the Cyprus Research Promotion Foundation through Desmi 20092010 which is co-funded by the Republic of Cyprus and the European Regional Development Fund of the EU under contract number NEA IPODOMI/STRATH/0308/09.
Fig. 4 TEM (a), selected-area electron diraction pattern (b) and HR-TEM (c) micrographs of small size monodisperse titania nanoparticles, imaged as black dots obtained using a 0.125 M solution of CaCl2. Average nanoparticle size: 13.5 nm.
1862
This journal is