Instantaneous physico-chemical analysis of suspension-based nanomaterials

High-throughput manufacturing of nanomaterial-based products demands robust online characterization and quality control tools capable of continuously probing the in-suspension state. But existing analytical techniques are challenging to deploy in production settings because they are primarily geared toward small-batch ex-situ operation in research laboratory environments. Here we introduce an approach that overcomes these limitations by exploiting surface complexation interactions that emerge when a micron-scale chemical discontinuity is established between suspended nanoparticles and a molecular tracer. The resulting fluorescence signature is easily detectable and embeds surprisingly rich information about composition, quantity, size, and morphology of nanoparticles in suspension independent of their agglomeration state. We show how this method can be straightforwardly applied to enable continuous sizing of commercial ZnO nanoparticles, and to instantaneously quantify the anatase and rutile composition of multicomponent TiO2 nanoparticle mixtures pertinent to photocatalysis and solar energy conversion.

[1]  M. Pileni The role of soft colloidal templates in controlling the size and shape of inorganic nanocrystals , 2003, Nature materials.

[2]  A. Testino,et al.  Optimizing the photocatalytic properties of hydrothermal TiO2 by the control of phase composition and particle morphology. a systematic approach. , 2007, Journal of the American Chemical Society.

[3]  R. Renganathan,et al.  Cyanobacterial chlorophyll as a sensitizer for colloidal TiO2. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[4]  Stanislaus S. Wong,et al.  Size- and shape-dependent transformation of nanosized titanate into analogous anatase titania nanostructures. , 2006, Journal of the American Chemical Society.

[5]  Saif A. Khan,et al.  Dynamically tunable nanoparticle engineering enabled by short contact-time microfluidic synthesis with a reactive gas , 2013 .

[6]  Michio Matsumura,et al.  Morphology of a TiO2 Photocatalyst (Degussa, P-25) Consisting of Anatase and Rutile Crystalline Phases , 2001 .

[7]  P. Yager,et al.  A rapid diffusion immunoassay in a T-sensor , 2001, Nature Biotechnology.

[8]  A. Walsh,et al.  Band alignment of rutile and anatase TiO₂. , 2013, Nature materials.

[9]  S Funk,et al.  Unexpected adsorption of oxygen on TiO2 nanotube arrays: influence of crystal structure. , 2007, Nano letters.

[10]  S. Zakeeruddin,et al.  Structure of Nanocrystalline TiO2 Powders and Precursor to Their Highly Efficient Photosensitizer , 1997 .

[11]  Dhananjay Dendukuri,et al.  Continuous-flow lithography for high-throughput microparticle synthesis , 2006, Nature materials.

[12]  S. Pratsinis,et al.  OH Surface Density of SiO 2 and TiO 2 by Thermogravimetric Analysis , 2003 .

[13]  Aron Walsh,et al.  Band alignment of rutile and anatase TiO 2 , 2013 .

[14]  B. Finlayson,et al.  Quantitative analysis of molecular interaction in a microfluidic channel: the T-sensor. , 1999, Analytical chemistry.

[15]  Saif A. Khan,et al.  Plasmonic nanoshell synthesis in microfluidic composite foams. , 2010, Nano letters.

[16]  Erik K Richman,et al.  The nanomaterial characterization bottleneck. , 2009, ACS nano.

[17]  Klavs F. Jensen,et al.  Microfluidic Synthesis of Titania Shells on Colloidal Silica , 2007 .

[18]  G. Whitesides,et al.  Microfabrication inside capillaries using multiphase laminar flow patterning , 1999, Science.

[19]  Vicki H. Grassian,et al.  When Size Really Matters: Size-Dependent Properties and Surface Chemistry of Metal and Metal Oxide Nanoparticles in Gas and Liquid Phase Environments† , 2008 .

[20]  Afshin Mashadi-Hossein,et al.  Concentration gradient immunoassay. 2. Computational modeling for analysis and optimization. , 2007, Analytical chemistry.

[21]  Hiroyuki Nakamura,et al.  Preparation of titania particles utilizing the insoluble phase interface in a microchannel reactor. , 2002, Chemical communications.

[22]  Stephen Mann,et al.  Coupled synthesis and self-assembly of nanoparticles to give structures with controlled organization , 1999, Nature.

[23]  S. Ehrman,et al.  Photocatalytic activity of a surface-modified anatase and rutile titania nanoparticle mixture. , 2009, Journal of colloid and interface science.

[24]  Fanxu Meng,et al.  Catalytic Cracking of Supercritical n-Dodecane over Wall-Coated HZSM-5 Zeolites with Micro- and Nanocrystal Sizes , 2012 .

[25]  Paul Yager,et al.  Concentration gradient immunoassay. 1. An immunoassay based on interdiffusion and surface binding in a microchannel. , 2007, Analytical chemistry.

[26]  Victor S Batista,et al.  Synergistic effect between anatase and rutile TiO2 nanoparticles in dye-sensitized solar cells. , 2009, Dalton transactions.

[27]  Henry J. Snaith,et al.  The renaissance of dye-sensitized solar cells , 2012, Nature Photonics.

[28]  Dhananjay Dendukuri,et al.  The Synthesis and Assembly of Polymeric Microparticles Using Microfluidics , 2009 .

[29]  Kimihisa Yamamoto,et al.  Quantum size effect in TiO2 nanoparticles prepared by finely controlled metal assembly on dendrimer templates. , 2008, Nature nanotechnology.

[30]  C. Albrecht,et al.  Distinctive toxicity of TiO2 rutile/anatase mixed phase nanoparticles on Caco-2 cells. , 2012, Chemical research in toxicology.

[31]  A. Navrotsky,et al.  Energetics of nanocrystalline TiO2 , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[32]  B. Kasprzyk-Hordern Chemistry of alumina, reactions in aqueous solution and its application in water treatment. , 2004, Advances in colloid and interface science.

[33]  G. Lowry,et al.  Towards a definition of inorganic nanoparticles from an environmental, health and safety perspective. , 2009, Nature nanotechnology.

[34]  A. Fujishima,et al.  TiO2 photocatalysis and related surface phenomena , 2008 .

[35]  D. Tenne,et al.  Enhanced Dye Fluorescence in Novel Dye–ZnO Nanocomposites , 2010 .

[36]  Paul Yager,et al.  Diffusion-based analysis of molecular interactions in microfluidic devices , 2004, Proceedings of the IEEE.

[37]  A. deMello Control and detection of chemical reactions in microfluidic systems , 2006, Nature.