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
- Robert W. Parry Teaching Award, University of Utah, 2018
- 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
The Zharov group's focus is on the preparation and investigation of inorganic and hybrid nanomaterials with applications in energy and drug delivery. Current research in Zharov group is divided between three main areas: (1) nanoporous materials for energy and separations, (2) nanoparticles for biomedical applications and catalysis, and (3) nanoconfinement effects on chemical reactivity and on fluid properties and transport. Within these areas, the following projects are ongoing: (1) self-assembly of polymer brush nanoparticles into porous supercrystals, (2) ion-conducting membranes from self-assembly of polymer brush nanoparticles, (3) tailoring the nanoenvironment of diamond-supported noble metal nanoparticles for control of catalysis, (4) degradable silica nanoparticles, (5) investigation of nanoconfinement effect on reactivity of aryl cyanate esters, and (6) fluid-solid interactions inside nanopores. In the first two projects, currently supported by an NSF CHE MSN grant, we are studying polymer brushes on spherical particles and using these brushes to self-assemble novel materials. The third project builds on our expertise in surface chemistry but takes us in a completely new direction of surface-immobilized catalysts. This collaborative effort with Prof. Shumaker-Parry of Chemistry is supported by an NSF grant from the CHE Catalysis program. The fourth project stems from our interest in functional nanoparticles for biomedical applications and builds on our expertise in inorganic chemistry of silicon and boron. This work is an NIH-funded collaboration with Prof. Ghandehari of Pharmaceutics and Pharmaceutical Chemistry at the University of Utah. Finally, the last two projects belong to a completely new direction in our group, and both deal with nanoconfinement effects. One project, funded by the Russian Science Foundation (RSF), is focused on polymerization inside nanopores, while the other, funded by DOE EFRC, deals with fluid behavior inside nanopores.
Self-Assembly of Polymer Brush Nanoparticles into Porous Supercrystals
Our earlier work on ionic and molecular transport in silica colloidal nanopores was followed by the preparation of free-standing colloidal membranes with size selectivity towards macromolecules and pores filled with responsive polymer brushes. However, more recently we decided to shift our attention to colloidal membranes prepared by self-assembly of silica nanoparticles carrying polymer brushes on their surface (“hairy” nanoparticles, HNPs). This approach allows avoiding the limitations related to the preparation of silica colloidal membranes, provides great flexibility in terms of surface chemistry and leads to many fundamental questions of great importance in the areas of self-assembly and polymer-polymer interactions. Our proof-of-concept work showed that HNPs can indeed reversibly assemble into robust mesoporous materials with tunable pore size. This led to our current NFS-funded project which combines experimental work with computation work performed in collaboration with Prof. Michael Grünwald of the Chemistry Department. The project is focused on preparing a series of HNPs with varying architecture and investigating their self-assembly as a function of HNP structural parameters (i.e. size, grafting densities, polymer chemistry, and chain length) and assembly conditions. The structure, mechanical properties and porosity of HNP assemblies are characterized by a range of experimental methods, including transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), and BET analysis. These experimental studies will shed light on correlations between parameters of the polymer brush and properties of the resulting assembled superstructures. Molecular dynamics computer simulations, using coarse-grained pair potentials, provide information about the microscopic structure of the polymer chains that dictate nanoparticle assembly and are used to rationalize experimental findings and to guide the exploration of the parameter space associated with polymer brushes.
Zharov, I.; Khabibullin, A. Acc. Chem. Res. 2014, 47, 440-449.
Khabibullin, A.; Zharov, I. ACS Appl. Mater. Interfaces2014, 6, 7712-7718.
Bohaty, A. K.; Smith, J. J.; Zharov, I. Langmuir2009, 25, 3096-3101.
Ignacio-de Leon, P. A.; Zharov. I. Chem. Commun. 2011,47, 553-555.
Schepelina, O.; Poth, N.; Zharov, I. Adv. Funct. Mater.2010, 20, 1962-1969.
Ignacio-de Leon, P. A.; Zharov. I. Langmuir 2013, 29, 3749-3756.
Khabibullin, A.; Fullwood, E.; Kolbay, P.; Zharov, I. ACS Appl. Mater. Interfaces2014, 6, 17306-17312.
Eygeris, Y.; White, E. V.; Wang, Q.; Carpenter, J. E.; Grünwald, M.; Zharov, I. Submitted to ACS Nano.
Ion-Conducting Membranes from Self-Assembly of Polymer Brush Nanoparticles
As a part of the above NSF-funded project, we are working on novel designs of ion-conducting
materials for fuel cells and lithium 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 crystals. 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 current and future work focuses on developing a new class
of lithium-conducting HNP membrane materials whose lithium conductivity results from
low molecular weight polymer brushes suitable for lithium ion transport and immobilized
on nanoparticles. We found that when such low MW polymer brushes are used, their side
chains can contain as few as two oxygen atoms, e.g. poly(ethoxyethyl methacrylate),
pEEMA and still provide high lithium ion conductivity. In addition, we recently discovered
that nanoporous membranes with relatively high proton conductivity and low swelling,
which makes them particularly suitable for redox batteries, can be prepared by self-assembly
of HNPs of two types, those carrying sulfonated polymer brushes and those carrying
polymer brushes with hydrophobic side chains.
Smith, J. J.; Zharov, I. Chem. Mater.2009, 21, 2013-2019.
Khabibullin, A.; Minteer, S. D.; Zharov, I. J. Mater. Chem. A. 2014, 2, 12761-12769.
Green, E.; Lifshitz, M.; Golodnitsky, D.; Zharov.; I. Manuscript in preparation.
Green, E.; Zharov.; I. Manuscript in preparation.
Tailoring the Nanoenvironment of Diamond-Supported Noble Metal Nanoparticles for Control of Catalysis
This is an NFS-funded collaborative project with Prof. Jennifer Shumaker-Parry of
the Chemistry Department. The goal of the project is to create a controlled nanoenvironment
for noble metal nanoparticles supported on synthetic diamond (ND) and silica nanoparticles
(SNPs) using polymer brushes and to investigate the impact of this environment on
catalysis. Our hypothesis is that the catalytic properties of these materials as well
as their stability can be controlled by the structure and properties of the polymer
brushes, prepared by polymerization initiated from the surface of the nanoparticles. While
working on this project we developed a method to prepare novel thiol-ene polymer-coated
ND particles with reactive surfaces that function as a support by immobilizing Au,
Pt and Pd nanoparticles that retain their catalytic activity. More recently, when
attempting to synthesize SNPs with a catalytically active Pd2+ complex immobilized on the silica surface by treating SNPs carrying covalently bound
dmp ligands with Pd(OAc)2 in acetone, we observed instead the formation of small PdNPs uniformly decorating
the silica surface. Our future work will focus on varying the length, grafting density,
polarity, structure and chemical composition of polymer brushes to create a tunable
nanoenvironment for supported noble metal nanoparticles. We will also work on elucidating
the mechanism of PdNP formation on silica surface in the presence of surface ligands.
Quast, A.; Bornstein, M.; Zharov, I.; Shumaker-Parry, J. S. ACS Catalysis2016, 6, 4729–4738.
Bornstein, M.; Quast, A.; Park, R.; Parker, D. M.; Shumaker-Parry, J. S.; Zharov, I. Submitted to Angew. Chemie.
Degradable Silica Nanoparticles
This work is an NIH-funded collaboration with Prof. Ghandehari of Pharmaceutics and
Pharmaceutical Chemistry and Bioengineering at the University of Utah. It focuses
on the preparation of internally functionalized biodegradable silica nanoparticles
with applications in drug delivery, cancer treatment and MRI imaging. Silica nanoparticles
(SNPs) are attractive for applications in delivery of drugs and imaging agents due
to their ease of synthesis and scale up, robust structure, and controllable size and
composition. Degradability is one important factor that limits biomedical applications
of SNPs. Our interest in this area stems from the desire to develop novel theranostic
materials and our approach to this problem is based on our ability to alter the internal
composition of silica nanoparticle with various functional groups. Most recently, we prepared unique hydrolysable silica nanoparticles (ICPTES-Sorbitol
SNPs) by the incorporation of carbamate linkages into the silica matrix.
Dubey, R.; Kushal, S.; Levin, M. D.; Mollard, A.; Oh, P.; Schnitzer, J. E.; Zharov, I.; Olenyuk, B. Z. Bioconj. Chem. 2015, 26, 78-89.
Brozek, E., Zharov, I. Chem. Mater.2009, 21, 1451-1456.
Gao, Z.; Zharov, I. Chem. Mater. 2014,26, 2030-2037.
Gao, Z.; Moghaddam, S. P. H.; Ghandehari, H.; Zharov, I. RSC Adv. 2018, 8, 4914-4920.
Investigation of Nanoconfinement Effect on Reactivity of Aryl Cyanate Esters
This is a Russian Science Foundation (RFS)-funded project which I lead at the A. M. Butlerov Chemistry Institute, Kazan Federal University, Russia. The main objective of this project is to investigate the effect of nanoconfinement on chemical reactions in terms of the mechanisms of this influence via surface-related (strength of substrate-surface interaction, catalysis by surface-grafted functional groups) and size-related (pore geometry) effects. The model reaction used in this work is the thermal polymerization of aryl cyanate esters. Our aim is to gain new understanding of the mechanism of the nanoconfinement effect and to investigate the role of substrate ordering induced by nanoconfinement on its reactivity. To study nanoconfinement effect we use silica colloidal crystals.
Fluid-Solid Interactions Inside Nanopores
This project a critical part of the $10.75M EFRC Center funded by the DOE. The EFRC is organized into four tightly integrated interdisciplinary thrusts: Materials Architecture, Dynamic Characterization, Multiscale Properties and Physical Properties. The goal of this work as a whole is to develop fundamental understanding of confinement and surface interactions in mesoscale media with nanometer-sized pores on the phase behavior, thermodynamic and multiphase flow properties of multicomponent fluid mixtures. I play a role of a Thrust Leader for Materials Architecture and as such will coordinate efforts between materials preparation, characterization, modeling and testing. Our own work will include the preparation of mesoporous silica and carbon materials with different pore sizes and geometries that will serve as model porous media. We will also build model materials of different compositions and with distinct nanopore surface chemistries. Finally, we will participate in studies of nanoconfinement effects on interfacial, thermodynamic, flow, and reactive properties of confined hydrocarbons.
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