MATERIALS, ORGANIC & INORGANIC CHEMISTRY
B.Sc. (Cum Honore), Chelyabink State University, 1990
M.Sc., Technion – Israel Institute of Technology, 1994
Ph.D., University of Colorado at Boulder, 2000
Beckman Postdoctoral Fellow, University of Illinois at Urbana-Champaign, 2000-2003
Phone: (801) 587-9335
Office: 3416 Thatcher Building
Ilya Zharov is a member of: Interfacial and Bioanalytical Chemistry (IBAC), Nano Institute of Utah, Nanotechnology Training Program, Global Change & Sustainability Center (GCSC) and Biological Chemistry Program
- Editorial Board Member, Current Smart Materials, 2015 -
- Emerging Investigator, Royal Society of Chemistry, Chemical Communications, 2011
- IUPAC Young Observer Award, 2011
- Feinberg Foundation Visiting Faculty Award, Weizmann Institute of Science, Israel, 2010
- IUPAC Young Observer Award, 2009 (declined)
- Emerging Investigator, Royal Society of Chemistry, Journal of Materials Chemistry, 2007
- NSF CAREER Award, 2007
- Dreyfus New Faculty Award 2003
- Beckman Foundation Postdoctoral Fellowship, 2000
- Link Foundation Graduate Fellowship, 1999
- John B. Eckeley Graduate Fellowship, CU Boulder, 1999
- Lady Davis Graduate Scholarship, Technion, Israel, 1992
Current research in Zharov Group is aimed at design and investigation of novel nanomaterials with applications in alternative energy, sustainability and drug delivery. The work is conducted in three main areas: (1) nanoporous colloidal membranes, (2) hybrid ion-conducting materials and (3) functional inorganic nanoparticles. Within these three areas, several new directions evolved recently or are evolving, including (1) self-assembled porous materials, (2) catalysis with surface-immobilized Au nanoclusters, (3) mixed matrix membranes for pervaporation, (4) carbon-based nanoporous materials for capacitive energy storage, and (5) applications of porous colloidal films in biosensing.
Nanoporous colloidal membranes
Membrane separations provide a number of advantaged in terms of energy consumption, efficiency, speed and environmental safety compared to the traditional separations, such as distillation or chromatography. We develop novel approaches to the preparation of membrane materials. Our earlier work on ionic and molecular transport in colloidal crystals evolved into a new general approach to the preparation of mesoporous membranes by assembly of colloidal nanoparticles. In 2009, we developed the preparation of robust free-standing silica colloidal membranes with a relatively large area and no mechanical defects by sintering silica colloidal crystals. Using this method, we prepared membranes with size selectivity towards macromolecules, pH-responsive membranes and enantioselective membranes. We also discovered that colloidal assembly is not limited to silica and that gold nanospheres also assemble into colloidal crystals that can be sintered to provide mesoporous gold membranes, which can be surface-modify to attain stimuli-responsive behavior. Most recently, we demonstrated that mesoporous membranes with uniform thickness, large area and tunable pore size can be prepared by pressing/sintering silica nanoparticles. Our new direction in this area is using polymer brush nanoparticles to form nanoporous membranes. We discovered that polymer-grafted silica nanoparticles reversibly assemble into nanoporous materials with tunable pore size. We assembled membranes from silica particles grafted with: (1) polymer brushes carrying acidic and basic groups, and (2) polymer brushes carrying neutral groups. The former are stable in most organic solvents and easily disassemble in water, while the latter are water-stable and disassemble in organic solvents. The control over the pore size, high flux, durability, flexibility, time- and cost-efficiency, and the ability to recover the retentate and clean the membranes by disassembly makes them a promising material for ultrafiltration and size-selective separations. We are presently working on introducing active functional groups into the polymer brushes to prepare affinity and nanofiltration membranes with charge rejeciton, as well as using polymer brushes that allow disassembly in response to other stimuli, such as pH and temperature. We are also studying the forces that lead to the formation of the colloidal membranes from the polymer brush nanoparticles.
Solid ionic conductors are used in a variety of energy conversion and storage devices, such as fuel cells and lithium batteries, which are of critical importance in the area of alternative energy. We are working on novel designs of ion conducting materials for fuel cells and lithium batteries. A key component in these devices is an ion conducting membrane that separates fuels while conducting protons from the anode to the cathode in the case of fuel cells, or separates electrodes while conducting lithium ions in the batteries. Our earlier work on sulfonated silica colloidal materials and proton conductivity in these materials led to a novel design for ion-conducting membranes, based on pore-filled colloidal materials. These membranes possess a number of attractive properties, including high proton conductivity, mechanical stability, high water retention and non-swelling. In addition, this system allows for systematic studies of proton conductivity and fuel cell performance as a function of polymer composition. Our present and future work focuses on developing a new class of lithium-conducting membrane materials. We are exploring two types of such materials, (1) nanoporous colloidal membranes whose lithium conductivity results from pore-filling with low molecular weight polymer brushes suitable for lithium ion transport, and (2) membranes formed from polymer brush nanoparticles impregnated with lithium salts. Our preliminary results indicate high lithium ion conductivity and interesting dependence of the conductivity on the polymer brush structure. We plan to continue to work on the design and fundamental studies of these materials.
Functional inorganic nanoparticles
In this research area, we are working on theranostic anticancer agents that will utilize boron neutron capture (BNC) as the cancer-fighting method. Earlier, we prepared dendritic BNC-integrin antagonists. More recently, we focused on the preparation of nanoparticle BNC materials. In this approach, we use dye-impregnated silica nanoparticles carrying boron-containing polymer brushes on their surface, silica nanoparticles containing boron atoms as a part of the nanoparticle oxide structure, or boron nanoparticles surface-modified to render them biocompatible. In the course of our work, we discovered that a number of reactive functional groups can be incorporated inside the organically modified silica (ORMOSIL) particles, and that these groups can undergo further chemical transformations. We also discovered a simple and efficient new method for the preparation of mesoporous silica nanoparticles. This work was also a part of our ongoing collaboration with Kazan Federal University in Russia. In the course of this collaboration, we prepared a variety of silica nanoparticles surface-modified or internally-modified with supramolecular receptors. Our future work will focus on the preparation of internally functionalized silica nanoparticles with applications in drug delivery, cancer treatment and MRI imaging, as well as biodegradable silica particles. This work will be performed in collaboration with biomedical research groups at the University of Utah, U Penn and PRISM Research Institute, San Diego.
Catalysis with surface-immobilized Au nanoclusters
Metals are some of the most important catalysts used in oil refining of petroleum, automobile exhausts, hydrogenation and many other processes. The metal clusters are particularly active catalysis because a large the fraction of their metal atoms are found at the surfaces, but they are also more challenging to handle and to control their catalytic activity. The goal of this work is to create controlled nanoenvironments for noble metal nanoparticles supported on nanodiamond and to investigate the impact of the nanoenvironment on catalysis. This work has started recently in collaboration with Prof. Shumaker-Parry in our Department. We were able to immobilize AuNPs on the surface of nanodiamonds by coating the support with a thin polymeric film.[i] We also demonstrated that polymer brushes can be grown on the nanodiamond surface using ATRP. We decorate the nanodiamond surface with polymer brushes to create a tunable nanoenvironment for the metallic nanoparticles and study its effect on catalysis. Our investigations will provide insight into the influence of the local environment on the diffusion of reactants to the surface of the catalytic nanoparticles and will enable the use of a tunable nanoenvironment to impart selectivity.
- Newton, M. R.; Bohaty, A. K.; White, H. S.; Zharov, I. Chemically Modified Opals as Thin Permselective Nanoporous Membranes. J. Am. Chem. Soc.2005, 127, 7268-7269.
- Cichelli, J.; Zharov, I. Chiral Selectivity in Surface-Modified Nanoporous Opal Films. J. Am. Chem. Soc.2006, 128, 8130-8131.
- Schepelina, O.; Zharov, I. Polymer-Modified Opal Nanopores. Langmuir2006, 22, 10523-10527.
- Wang, G.; Bohaty, A. K.; Zharov, I.; White, H. S. Photon-Gated Transport at the Glass Nanopore Electrode. J. Am. Chem. Soc. 2006, 128, 13553-13558.
- Cichelli, J.; Zharov, I. Chiral Permselectivity in Nanoporous Opal Films Surface-Modified with Chiral Selector Moieties. J. Mater. Chem.2007, 17, 1870-1875 (journal cover).
- Schepelina, O.; Zharov, I. PNIPAAM-Modified Nanoporous Colloidal Films with Positive and Negative Temperature Gating. Langmuir2007, 23, 12704-12709.
- Schepelina, O.; Zharov, I. Poly(2-(dimethylamino)ethyl methacrylate)-Modified Nanoporous Colloidal Films with pH and Ion Response. Langmuir2008, 24, 14188-14194.
- Smith, J. J.; Abbaraju, R, R.; Zharov, I. Proton Transport in Assemblies of Silica Colloidal Spheres. J. Mater. Chem.2008, 18, 5335-5338.
- Abelow, A. E.; Zharov, I. Poly(L-alanine)-Modified Nanoporous Colloidal Films. Soft Matter2009, 5, 457-462.
- Bohaty, A. K.; Smith, J. J.; Zharov, I. Free-Standing Silica Colloidal Nanoporous Membranes. Langmuir2009, 25, 3096-3101.
- Brozek, E., Zharov, I. Internal Functionalization and Surface Modification of Vinylsilsesquioxane Nanoparticles. Chem. Mater.2009, 21, 1451-1456.
- Smith, J. J.; Zharov, I. Preparation and Proton Conductivity of Self-Assembled Sulfonated Polymer-Modified Silica Colloidal Crystals. Chem. Mater.2009, 21, 2013-2019.
- Mollard, A.; Ibragimova, D.; Antipin, I. S.; Stoikov, I. I.; Zharov, I. Molecular Transport in Thiacalixarene-Modified Nanoporous Colloidal Films. Micropor. Mesopor. Mater. 2010, 131, 378-384.
- Schepelina, O.; Poth, N.; Zharov, I. pH-Responsive Nanoporous Silica Colloidal Membranes. Adv. Funct. Mater.2010, 20, 1962-1969.
- Ignacio-de Leon, P. A.; Zharov. I. Size-Selective Transport in Colloidal Nano-Frits. Chem. Commun.2011, 47, 553-555.
- Gao, Z.; Walton, N.; Malugin, A.; Ghandehari, H.; Zharov, I. Preparation of Dopamine-Modified Boron Nanoparticles. J. Mater. Chem. 2012, 22, 877-882.
- Abelow, A. E.; Zharov, I. Reversible Nanovalves in Inorganic Materials. J. Mater. Chem. 2012, 22, 21810-21818.
- Ignacio-de Leon, P. A.; Zharov. I. SiO2@Au Core-Shell Nanospheres Self-Assemble to Form Colloidal Crystals That Can Be Sintered and Surface Modified to Produce pH-Controlled Membranes. Langmuir2013, 29, 3749-3756. Langmuir Most Read article in March 2013; Nature Research Highlight, Community Choice, Nature2013, 496, 401.
- Gao, Z.; Zharov, I. Tannic Acid-Templated Mesoporous Silica Nanoparticles with Large Pores. Chem. Mater. 2014,26, 2030-2037.
- Khabibullin, A.; Zharov, I. Nanoporous Membranes with Tunable Pore Size by Pressing/Sintering Silica Colloidal Spheres. ACS Appl. Mater. Interfaces2014, 6, 7712-7718.
- Khabibullin, A.; Minteer, S. D.; Zharov, I. The Effect of Sulfonic Acid Group Content in Pore-Filled Silica Colloidal Membranes on Their Proton Conductivity and Direct Methanol Fuel Cell Performance. J. Mater. Chem. A. 2014, 2, 12761-12769.
- Khabibullin, A.; Fullwood, E.; Kolbay, P.; Zharov, I. Reversible Assembly of Tunable Nanoporous Membranes from “Hairy” Silica Nanoparticles. ACS Appl. Mater. Interfaces 2014, 6, 17306-17312.
- Khabibullin, A.; Zharov, I. Surface-Modified Silica Colloidal Crystals: Nanoporous Materials with Controlled Molecular Transport. Acc. Chem. Res.2014, 47, 440-449.
- Dubey, R.; Kushal, S.; Levin, M. D.; Mollard, A.; Oh, P.; Schnitzer, J. E.; Zharov, I.; Olenyuk, B. Z. Tumor Targeting, Trifunctional Dendritic Wedge. Chem. 2015, 26, 78-89 (journal cover).
- Green, E.; Fullwood, E.; Selden, J.; Zharov, I. Functional Membranes via Nanoparticle Self-Assembly. Chem. Commun. 2015, 51, 7770-7780 (journal cover).
- Khabibullin, A.; Smith, J. J.; Minteer, S. D.; Zharov, I. Preparation and Properties of DMFC Membranes from Polymer-Brush Nanoparticles. Solid State Ionics2016, 288, 154-159.
- Quast, A.; Bornstein, M.; Zharov, I.; Shumaker-Parry, J. S. Robust Polymer-Coated Diamond Supports for Noble Metal Nanoparticle Catalysts. ACS Catalysis2016, 6, 4729–4738.