TWENTY-NINTH ANNUAL SYMPOSIUM
of the
LABORATORY FOR SURFACE MODIFICATION
Thursday, April 2, 2015
9:00 a.m. to 4:30 p.m.
Rutgers, the State University of New Jersey
PROGRAM
Fiber Optics Auditorium
Busch Campus
Piscataway, New Jersey
Laboratory for
Surface Modification
THE STATE UNIVERSITY OF NEW JERSEY
NanoPhysics
Laboratory
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
8:30
Registration, coffee
9:00
Introductory Remarks
Professor Torgny Gustafsson,
Director, Laboratory for Surface Modification
SESSION I:
THEORY OF COMPLEX OXIDES
Chair: Prof. Leonard Feldman
VP Physical Science and Engineering Partnerships
Director, IAMDN
9:05
Coupled Nonpolar-Polar Metal-Insulator Transition in 1:1 SrCrO3/SrTiO3
Superlattices: A First-Principles Study
Yuanjun Zhou* and Karin Rabe
Department of Physics and Astronomy
9:20
Magnetoelectricity in Fe Langasite
Sergey Artyukhin, David Vanderbilt and Sang-Wook Cheong
Department of Physics and Astronomy
9:35
High-Carrier-Density Phase in LaTiO3/SrTiO3 Superlattices
Se Young Park1, Karin M. Rabe1 and Andrew J. Millis2
1
Department of Physics & Astronomy and 2Department of Physics, Columbia
University
9:50 – 10:15 Coffee Break and Poster Session
* = Student Presenter
2
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
SESSION II:
ELECTRONIC PROPERTIES OF NOVEL MATERIALS
Chair: Prof. Richard Lehman
Department of Materials Science and Engineering
10:15 WELCOMING REMARKS
Prof. Ronald Ransome
Dean of Math & Physical Sciences
Interim Vice Dean of Administration
School of Arts and Sciences
10:20 **HIGHLIGHT PRESENTATION**
Electronic Structure of Hybrid Organic Inorganic Perovskites Interfaces
Prof. Antoine Kahn
Department of Electrical Engineering, Princeton University
11:00 Kondo Breakdown In Topological Kondo Insulators
Onur Erten1, Victor Alexandrov2 and Piers Coleman1
1
Condensed Matter Theory, 2Institute for Advanced Studies, Princeton
11:15 Chirality Density Wave of the “Hidden Order” Phase in URu2Si2
H.-H. Kung*1, R. E. Baumbach2, E. D. Bauer2, V. K. Thorsmolle1, W.-L. Zhang1, K.
Haule1, J. A. Mydosh3 and G. Blumberg1
1
Department of Physics and Astronomy, 2Los Alamos National Lab, 3Kamerlingh
Onnes Laboratory, Leiden University
11:30 Topological Insulator with Suppressed Bulk and Dominant Topological
Surface State Conduction
Nikesh Koirala*1, Maryam Salehi2, Jisoo Moon1, Namrata Bansal3 and Seongshik Oh1
1
Department of Physics and Astronomy, 2Department of Materials Science and
Engineering and 3Department of Electrical Engineering
11:45 Charge Transfer at Si-PEDOT:PSS Interface
Xiaoming Wang 1, Mona Zebarjadi 1, 2 and Keivan Esfarjani 1, 2
1
Institute for Advanced Materials, Devices and Nanotechnology and 2Mechanical
Engineering
12:00 – 1:30 Lunch and Poster Session
* = Student Presenter
3
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
POSTER PAPERS:
1)
Temperature Programmed Desorption of Ionic Liquid from Metals
Aleksandra B. Biedron*1, Joseph Bloch3, Sylvie Rangan2, Edward W. Castner, Jr.1 and
Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, Nanotechnology for Clean Energy
IGERT, 2Department of Physics and Astronomy and Laboratory for Surface
Modification, 3NRCN, Beer-Sheva, Israel
2)
Perovskite-Related Oxynitrides as Photoanodes in Photoelectrochemical
Cells
Bin Liu*, Eric Garfunkel, Martha Greenblatt and G. Charles Dismukes
Department of Chemistry and Chemical Biology
3)
Alkyl-Aryl Coupling Catalyzed by Tandem Systems of Pincer-Ligated
Iridium Complexes and Zeolites
Bo Li*1, Long van Dinh1, Akshai Kumar1, Fuat E. Celik2, Alan S. Goldman1
1
Department of Chemistry and Chemical Biology, 2Department of Chemical and
Biochemical Engineering
4)
Generation Dependent Ultrafast Charge Transfer Dynamics in PyreneViologen Dendrons
Zheng Gong*1, Jianhua Bao1, Takehiro Kawauchi2 and Piotr Piotrowiak1
1
Department of Chemistry, 2Tokyo Institute of Technology, Department of Chemistry and
Materials Science, Tokyo Institute of Technology
5)
HafSOx Radiation Mechanistic Study with Low Energy Electrons Exposure
Feixiang Luo*1, Boris Yakshinskiy2, Alexei Ermakov1 and Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, 2Department of Physics and Astronomy
and Laboratory for Surface Modification
6)
Characterization of LiFePO4 Cathode Nanocrystals by STEM/EELS
Analysis
Joseph Schneider-Haefner*1, Yuxuan Wang2, Jiye Fang2, Natasha Chernova2, Doug Su3
and Frederic Cosandey1
1
Department of Materials Science and Engineering, 2Materials Science Department,
Binghamton University, 3CFN, Brookhaven National Laboratory
7)
Helium Atom Diffraction of Cyclooctatetraene on Cu (001)
John L. Wieczorek*, Erkan Z. Ciftlikli and B.J. Hinch
Department of Chemistry and Chemical Biology
8)
Nanoscale Synthesis of Nickel Phosphides as Novel HER Electrocatalysts
Ajay R. Kashi*, Anders B. Laursen, Bin Liu, Mariana J. Whitaker, Martha Greenblatt
and G. Charles Dismukes
Department of Chemistry and Chemical Biology
* = Student Presenter
4
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
9)
Ultrasmall Palladium Nanoparticles Supported on Amine-Functionalized
SBA-15 as Efficient Catalysts for Hydrogen Evolution from Formic Acid
Katherine Koh*1, Jung-Eun Seo3, Jin Hee Lee3, Anandarup Goswami1,2, Chang Won
Yoon3 and Tewodros Asefa1,2
1
Department of Chemistry and Chemical Biology, 2Department of Chemical and
Biochemical Engineering, 3Fuel Cell Research Center, Korea Institute of Science and
Technology
10)
The Effect of Fe-Doping on the Electronic Structure and Activity of Nickel
Phosphide, Ni2P a Catalyst for H2 Evolution from Water
Kelly R. Patraju*1, Anders B. Laursen1, Martha Greenblatt1 and G. Charles Dismukes1
1
Department of Chemistry and Chemical Biology
11)
Title Ni5P4 a Game Changing H2 Evolution Catalyst
Anders B. Laursen1, Kelly R. Patraju1, Mariana J. Whitaker1, Tapati Sarkar2, Nan Yao3,
Kandalam V. Ramanujachary4, Martha Greenblatt1 and G. Charles Dismukes1
1
Department of Chemistry and Chemical Biology, 2Uppsala University, Sweden, 3PRISM
Imaging and Analysis Center, Princeton University, 4Department of Chemistry, Rowan
University
12)
Investigation of Propene and Pentene Dimerization by Acid Zeolites
Longfei Chao* and Fuat E. Celik
Department of Chemical and Biochemical Engineering
13)
Biased Photoemission and Ab-Initio Studies of Metal-InsulatorSemiconductor Structures
Malathi Kalyanikar*1, Sylvie Rangan2, Junxi Duan2, Gang Liu3, Stephen Weitzner4,
Robert Bartynski2, Eva Andrei2, Leonard Feldman3, Ismaila Dabo4 and Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, 2Department of Physics and Astronomy
and Laboratory for Surface Modification, 3Institute for Advanced Materials, Devices and
Nanotechnology, 4Department of Material Science and Engineering, Penn State
University
14)
Surface Phonons in the Superlattice of the Topological Insulator Bi2Se3
Maryam Salehi*1, H.-H. Kung2, N. Koirala2, M. Brahlek2, S. Oh2 and G. Blumberg2
1
Department of Material Science and Engineering, 2Department of Physics and
Astronomy and Laboratory for Surface Modification
15)
The Rutgers UltraSTEM
Maureen Joel Lagos and Philip E. Batson
Institute for Advanced Materials, Devices and Nanotechnology, Department of Materials
Science and Engineering, Department of Physics and Astronomy and Laboratory for
Surface Modification
* = Student Presenter
5
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
16)
Capture and Release of Plasmonic Electrons in Ag@hexaniobate
Nanopeapod Assemblies
Mengdi Liu1, John B. Wiley2 and Piotr Piotrowiak1
1
Department of Chemistry, 2Department of Chemistry, University of New Orleans
17)
Metallic 1T Phase MoS2 Nanosheets as Supercapacitor Electrode Materials
Muharrem Acerce*, Damien Voiry and Manish Chhowalla
Material Science and Engineering
18)
Increasing Visible-Light Photocatalytic Activity via Modification of TiO2
Photocatalysts
Ashley M. Pennington*, Katelyn A. Dagnall, Deniz A. Dindi and Fuat E. Celik
Department of Chemical and Biochemical Engineering
19)
Understanding Electron Energy Loss Mechanisms in EUV Resists Using
REELS and First-Principles Calculations
Sylvie Rangan1, Robert A. Bartynski1, Amrit Narasimhan2 and Robert Brainard2
1
Department of Physics and Astronomy and Laboratory for Surface Modifications,
2
College of Nanoscale Science and Engineering University, Albany
20)
A Click Approach to “STAR” Ruthenium-Sensitizer
Runkun Sun*, Hao Fan and Elena Galoppini
Department of Chemistry, Rutgers, Newark
21)
Selective Electrochemical Deposition of LiCoO2 and Its Properties as an
Electrocatalyst for Water Oxidation/Oxygen Evolution
Shinjae Hwang*, Graeme Gardner, Eric Garfunkel and G. Charles Dismukes
Department of Chemistry and Chemical Biology, Institute for Advanced Materials,
Devices and Nanotechnology
22)
Characterization of Catalysts Using Helium Ion Microscopy and
Temperature Programmed Desorption
Viacheslav Manichev*1, Can Xu1, Hao Wang1, Wenhua Chen1, Leonard Feldman1,2,
Torgny Gustafsson1 and Robert A. Bartynski1
1
Department of Physics and Astronomy and Laboratory for Surface Modification,
2
Institute for Advanced Materials Devices and Nanotechnology
23)
Yeast Cells-Derived Hollow Heteroatom-Doped Carbon Microparticles for
Sustainable Electrocatalysis and Renewable Energy Applications
Xiaoxi Huang*1 and Tewodros Asefa1,2
1
Department of Chemistry and Chemical Biology, 2 Department of Chemical and
Biochemical Engineering
24)
Functionalization of Nanostructured MgZnO with Improved Coverage and
pH Resistance
Yuan Chen*1, Sylvie Rangan2, H.T.Yi2, Elena Galoppini1, Robert Bartynski2 and Vitaly
Podzorov2
1
Department of Chemistry, Rutgers, Newark, 2Department of Physics and Astronomy and
Laboratory for Surface Modification
* = Student Presenter
6
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
SESSION III:
SURFACES, INTERFACES AND NOVEL METHODS
Chair: Prof. John Brennan
Department of Chemistry and Chemical Biology
1:30
**HIGHLIGHT PRESENTATION**
Imaging Strain-Driven Surface Evolution with LEEM
Dr. James B. Hannon
Carbon Electronics, IBM T.J. Watson Research Center
2:10
Magnetic Charge and Magnetoelectricity in Hexagonal Manganites and
Ferrites
Meng Ye* and David Vanderbilt
Department of Physics and Astronomy
2:25
Investigation of Active Sites for Water Oxidation by Manganese Oxides
Paul F. Smith*, Benjamin Deibert, Shivam Kaushik, Graeme Gardner, Hao Wang, Jing
Li and G. Charles Dismukes
Department of Chemistry and Chemical Biology
2:40
Coverage Dependent Stability of the c(4x2) Phase of L-Alaninate/Cu(001)
Erkan Ciftlikli and B.J. Hinch
1
Department of Chemistry and Chemical Biology
2:55 – 3:10 Afternoon Break
* = Student Presenter
7
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
SESSION IV:
INTERACTIONS ON AND WITH ADVANCED OXIDES
Chair: Prof. Robert Bartynski
Department of Physics and Astronomy
3:10
The Solid State Conversion Reaction of Epitaxial CoO Films Studied by
STM and ARXPS
Ryan Thorpe, Sylvie Rangan, Adrian Howansky and Robert A. Bartynski
Department of Physics and Astronomy and Laboratory for Surface Modification
3:25
Structural Changes in Lithium Cobalt Oxides Induced by Water Oxidation
Catalysis
Graeme Gardner*1, Jafar Al-Sharab2, Yong Bok Go1, Martha Greenblatt1 and G.
Charles Dismukes1
1
Department of Chemistry and Chemical Biology and 2Materials Science and
Engineering
3:40
Zinc(II) Tetraphenylporphyrin Adsorption on Au(111): An Interplay
Between Molecular Self-Assembly and Surface Stress
Charles Ruggieri*1, Sylvie Rangan, 1 Robert A. Bartynski 1 and Elena Galoppini2
1
Department of Physics and Astronomy and Laboratory for Surface Modification,
2
Chemistry Department, Rutgers Newark
3:55
Water Absorption in Thermally Grown Oxides on SiC and Si
Can Xu*1,2, Gang Liu2, Boris Yakshinskiy2, Leszek Wielunski2, Torgny Gustafsson2,
Joseph Bloch1,3, Sarit Dhar4 and Leonard C. Feldman1,2
1
Institute for Advanced Materials, Devices and Nanotechnology, 2Department of Physics
and Astronomy and Laboratory for Surface Modification, 3NRCN, Beer-Sheva, 84190,
Israel, 4Department of Physics, Auburn University
4:10
Presentation of Theodore E. Madey Student Awards:
Best Poster Presentation
Best Oral Presentation
* = Student Presenter
8
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
ABSTRACTS FOR TALKS
9:05
Coupled Nonpolar-Polar Metal-Insulator Transition in 1:1 SrCrO3/SrTiO3
Superlattices: A First-Principles Study
Yuanjun Zhou* and Karin Rabe
Department of Physics and Astronomy
Using first principles calculations, we determined the epitaxial-strain dependence of the
ground state of the 1:1 SrCrO3/SrTiO3 superlattice. The superlattice layering leads to
significant changes in the electronic states near the Fermi level, derived from Cr t2g
orbitals. An insulating phase is found when the tensile strain is greater than 2.2% relative
to unstrained cubic SrTiO3. The insulating character is shown to arise from Cr t2g orbital
ordering, which is produced by an in-plane polar distortion that couples to the superlattice
d-bands and is stabilized by epitaxial strain. This effect can be used to engineer the band
structure near the Fermi level in transition metal oxide superlattices.
9:20
Magnetoelectricity in Fe Langasite
Sergey Artyukhin, David Vanderbilt and Sang-Wook Cheong
Department of Physics and Astronomy
Materials with coexisting and interacting switchable ferroic orders - multiferroics -- are
the subject of intense investigations due to their existing and potential applications in
spintronics and information storage technology. Here we investigate the much debated
magnetically induced polarization and magneto-electric effect in the hexagonal Felangasite Ba3NbFe3Si2O14 with distorted triangular layers of magnetic Fe ions. We
propose a simple model for these phenomena, and discuss how application of the
magnetic field induces a toroidal moment, responsible for the peculiar magnetoelectric
effect in this material.
9:35
High-Carrier-Density Phase in LaTiO3/SrTiO3 Superlattices
Se Young Park1, Karin M. Rabe1 and Andrew J. Millis2
1
Department of Physics & Astronomy and 2Department of Physics, Columbia
University
We investigate superlattices composed of alternating layers of Mott insulating LaTiO3
and band insulating SrTiO3 from first principles, using the density functional theory plus
U (DFT+U) method. For values of U above a critical threshold, we find that melting of
the Mott-insulating phase can extend from the interface into the LaTiO3 layer, resulting in
a sheet carrier density exceeding the density of 0.5 electrons per in-plane unit cell found
in previous studies. The critical U for the melting transition is larger than the critical
Coulomb correlation required for the insulating LaTiO3, suggesting the existence of a
high sheet carrier density phase in LaTiO3/SrTiO3 superlattices. The effects of in-plane
strain and varying layer thickness on the melting transition are discussed. For insulating
superlattices, we study the strain dependence of the polarization and its relation to nearinterface local atomic distortions.
Support: DOE ER 046169, ONR N00014-11-0666
* = Student Presenter
9
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
10:20 **HIGHLIGHT PRESENTATION**
Electronic Structure of Hybrid Organic Inorganic Perovskites Interfaces
Prof. Antoine Kahn
Department of Electrical Engineering, Princeton University
Hybrid Organic Inorganic Perovskites (HOIP) have recently led to stunningly rapid
progress in photovoltaics. HOIP solar cells include interfaces with organic and inorganic
electron and hole transport layers (ETL, HTL), which must be carefully optimized in
order to insure high efficiency devices. This talk first reviews measurements of the
electronic structure of HOIPs, specifically methylammonium lead halides (MAPbX,
X=Br3, I3, I3-xClx), with evaluation of their valence and conduction band edges, ionization
energy and electron affinity (IE, EA) [1]. We then turn to HOIP interfaces. The electronic
structure of “conventional” TiO2/HOIP/organic HTL and “inverted” NiOx/HOIP/organic
ETL cells are given. Results show the role of interface energetics in terms of carrier lossless extraction from, or confinement in, the perovskite layer [2]. The shift of the HOIP
Fermi level from the top of the gap in TiO2/HOIP to the lower half of the gap in
NiOx/HOIP [3] is discussed for its implications in terms of density of gap states in these
materials.
[1] P. Schulz et al., Energ. & Envir. Sci. 7, 1377 (2014)
[2] E. Edri et al., J. Phys. Chem. Lett., 5, 429 (2014)
[3] P. Schulz et al., Adv. Mat. Interf. (under review)
11:00 Kondo Breakdown In Topological Kondo Insulators
Onur Erten1, Victor Alexandrov2 and Piers Coleman1
1
Condensed Matter Theory, 2Institute for Advanced Studies, Princeton
Motivated by the observation of light surface states of SmB6, we examine the effects of
surface Kondo breakdown in topological Kondo insulators. We present both numerical
and analytic results, which show that the decoupling of the localized moments at the
surface disturbs the compensation between light and heavy electrons and dopes the Dirac
cone. Dispersion of these uncompensated surface states are dominated by inter-site
hopping, which leads to a much lighter quasiparticles. These surface states are also highly
durable against effects of magnetism and decreasing the thickness of the sample.
* = Student Presenter
10
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
11:15 Chirality Density Wave of the “Hidden Order” Phase in URu2Si2
H.-H. Kung*1, R. E. Baumbach2, E. D. Bauer2, V. K. Thorsmolle1, W.-L. Zhang1, K.
Haule1, J. A. Mydosh3 and G. Blumberg1
1
Department of Physics and Astronomy, 2Los Alamos National Lab, 3Kamerlingh
Onnes Laboratory, Leiden University
The heavy fermion superconductor URu2Si2 displays a second-order phase transition
into the so called “hidden order” (HO) state at THO=17.5K before entering an
unconventional superconducting state below Tc=1.5K. We use polarization resolved
Raman spectroscopy to specify the symmetries of the low energy excitations. Below
THO, the response function develops a gap of about 6meV, and a sharp in-gap mode
centered at 1.6meV in the chiral symmetry channel. The symmetry dependence of this
mode suggests that the HO parameter breaks local vertical and diagonal reflection
symmetries. This results in the uranium 5f states with distinct chiral properties,
ordering to a commensurate chirality density wave ground state.
Reference: Kung et al., "Chirality density wave of the `hidden order’ phase in URu2Si2",
Science, 347, 1339 (2015)
11:30 Topological Insulator with Suppressed Bulk and Dominant Topological
Surface State Conduction
Nikesh Koirala*1, Maryam Salehi2, Jisoo Moon1, Namrata Bansal3 and Seongshik Oh1
1
Department of Physics and Astronomy, 2Department of Materials Science and
Engineering and 3Department of Electrical Engineering
Topological insulators (TIs) hold much promise in applications and exploration of
novel physics due to their exotic topological surface states (TSSs) and insulating bulk.
In real TI materials such as Bi2Se3 major bottleneck in such pursuits are: (1) the bulk is
conducting rather than insulating and (2) carrier mobility is low, both of which arise
due to crystal defects. Here by minimizing these defects in Bi2Se3 thin films by
growing them on atomically engineered buffer layer, we have simultaneously
suppressed bulk conduction and achieved record high mobility TSSs conduction
channel. These high quality TIs may pave a way to a new generation of experiments
and applications in TI research.
* = Student Presenter
11
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
11:45 Charge Transfer at Si-PEDOT:PSS Interface
Xiaoming Wang 1, Mona Zebarjadi 1, 2 and Keivan Esfarjani 1, 2
1
Institute for Advanced Materials, Devices and Nanotechnology and 2Mechanical
Engineering
Here we present both semi-classical and first-principle calculations of charge transfer at
silicon and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate)
interface, which shows that PEDOT:PSS is an effective hole injector for transferring
holes to silicon channel, this kind of doping can preserve the mobility of silicon, which is
preferred for thermoelectrics. The results provide us a guidance to design high
performance thermoelectric materials.
1:30
**HIGHLIGHT PRESENTATION**
Imaging Strain-Driven Surface Evolution with LEEM
Dr. James B. Hannon
Carbon Electronics, IBM T.J. Watson Research Center
During heteroepitaxial growth, lattice mismatch between the growing film and the
substrate inevitably leads to interfacial strain. Understanding how surfaces react to
interfacial strain has many practical applications, from enhancing transistor performance
to preventing delamination. Interfacial strain can also lead to the formation of novel
`self-organized’ structures such as quantum dots. In this talk I will review experiments in
which low-energy electron microscopy (LEEM) was used to image the evolution of
surfaces during growth in real time. One advantage of LEEM is that the real-space
surface evolution can be directly modeled, giving powerful insight into the
thermodynamics and kinetics of thin film growth. I will begin with a review of
experiments on Si surfaces at elevated temperature. In these 2D systems, strain arises
because the surface support two different surface phases [1]. I will also review recent
experiments [2] on 3D growth at the Si(001) surface in which strain drives a massive
surface restructuring.
[1] “Anomalous Spiral Motion of Steps near Dislocations on Silicon Surfaces," J.B.
Hannon, V.B. Shenoy, and K.W. Schwarz, Science 313 (2006) 5791.
[2] “Strain-Driven Mound Formation of Substrate under Epitaxial Nanoparticles,” T.
Gupta et al, Nano Lett., 15 (2015) 34.
* = Student Presenter
12
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
2:10
Magnetic Charge and Magnetoelectricity in Hexagonal Manganites and
Ferrites
Meng Ye* and David Vanderbilt
Department of Physics and Astronomy
Magnetoelectric (ME) materials are of fundamental interest and broad potential
applications. Commonly the dominant contribution to the ME response is the latticemediated one, which is proportional to the dynamical magnetic charge Zm. A previous
study has shown that exchange striction acting on noncollinear spins induces much larger
magnetic charges than when Zm is driven by spin-orbit coupling. In hexagonal
manganites RMnO3 and ferrites RFeO3 (R=Ho-Lu), the spins of transition-metal ions
form a 120° arrangement through super-exchange. Here we present a theoretical study of
the magnetic charges, and of the spin-lattice and spin-electronic ME constants, in these
hexagonal manganites and ferrites, clarifying the conditions under which exchange
striction leads to enhanced Zm and anomalously large in-plane spin-lattice ME effects.
2:25
Investigation of Active Sites for Water Oxidation by Manganese Oxides
Paul F. Smith*, Benjamin Deibert, Shivam Kaushik, Graeme Gardner, Hao Wang, Jing
Li and G. Charles Dismukes
Department of Chemistry and Chemical Biology
Manganese oxides occur as minerals in at least 30 different crystal structures, providing
a “high throughput” system to explore the significance of atomic positions on many
applications. The primary descriptor for catalytic oxidation of water is shown to be
structural distortions from Mn3+ content, as a result of surveying eight polymorphs.
Paradoxically, oxidation of Mn4(OMe)4(nic)4 yields a catalytically active oxide with
many characteristics of an inactive, all-Mn4+ polymorph. We show this new material
contains 50% metastable Mn3+, and that preventing Mn3+ from disproportionation is an
effective strategy towards designing better catalysts. The optimized structure for Mn3+
will be presented following comparison of Mn3+-containing polymorphs (Mn2O3,
Mn3O4, β-MnOOH, γ-MnOOH).
2:40
Coverage Dependent Stability of the c(4x2) Phase of L-Alaninate/Cu(001)
Erkan Ciftlikli1 and B.J. Hinch1
1
Department of Chemistry and Chemical Biology
L-Alanine dissociatively adsorbs on Cu(001) at ambient temperatures producing a c(4x2)
phase of alaninate [NH2C(CH3)HCOO] species. At saturation, 0.25ML L-Ala/Cu(001) is
stable upon annealing up to 453-463K. The onset of nucleation of the c(4x2) phase
occurs in early stages of RT deposition when the alaninate coverage is as low as 0.01
ML. However, in contrast to the thermally stable saturated c(4x2) surface, at subsaturation coverages the surfaces exhibit slow loss of the ordered phase. Helium
reflectivity measurements show a reduction of c(2x4) diffraction intensities even at RT.
We will discuss the kinetics of the nucleation and dissolution processes occurring on the
L-Ala/Cu(001) surfaces.
* = Student Presenter
13
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
3:10
The Solid State Conversion Reaction of Epitaxial CoO Films Studied by
STM and ARXPS
Ryan Thorpe, Sylvie Rangan, Adrian Howansky and Robert A. Bartynski
Department of Physics and Astronomy and Laboratory for Surface Modification
Cobalt (II) oxide is a promising electrode material for Li-ion conversion batteries,
undergoing the following reversible redox reaction upon exposure to lithium:
2Li + CoO ↔ Li2O + Co0.
In order to characterize the phase progression and morphology of the Li-CoO reaction,
epitaxial CoO(100) and (111) films were exposed to lithium in UHV. The early stages of
the reaction were then characterized with STM, while the diffusion of Li into the films
and concomitant reduction of CoO was quantified using ARXPS. For CoO(111) films,
the conversion reaction spread from step edges and defect sites across the surface of the
film and then proceeded in a layer-by-layer fashion into the bulk. Conversely, the LiCoO(100) reaction proceeded deep into the film at preferential reaction sites before
spreading across the rest of the surface.
3:25
Structural Changes in Lithium Cobalt Oxides Induced by Water Oxidation
Catalysis
Graeme Gardner*1, Jafar Al-Sharab2, Yong Bok Go1, Martha Greenblatt1 and G.
Charles Dismukes1
1
Department of Chemistry and Chemical Biology and 2Materials Science and
Engineering
Lithium cobalt oxide has long been the archetypal compound for use in rechargeable
lithium ion batteries, due to the redox flexibility of Co and lability of Li from the
layered rhombohedral crystal. However, it has been observed that the degredation in
lifetime is associated with sub-surface structural reorganization to a cubic phase. In the
past few years, LiCoO2 has also been explored in water oxidation catalysis. In fact the
low-temperature cubic phase is highly active compared to the high-temperature layered
phase. However, in electrochemically driven water oxidation, it is observed that layered
LiCoO2 also undergoes reconstruction associated with Li loss as in battery cycling,
resulting in an active cubic surface phase.
* = Student Presenter
14
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
3:40
Zinc(II) Tetraphenylporphyrin Adsorption on Au(111): An Interplay
Between Molecular Self-Assembly and Surface Stress
Charles Ruggieri*1, Sylvie Rangan, 1 Robert A. Bartynski 1 and Elena Galoppini2
1
Department of Physics and Astronomy, 2Chemistry Department, Rutgers Newark
The interaction between zinc(II) tetraphenylporphyrin (ZnTPP) molecules and the
Au(111) surface is investigated using scanning tunnel microscopy, from initial adsorption
sites to monolayer self-assembly, with a particular emphasis on its relation to the surface
atomic structure reorganization. Coverage-dependent ZnTPP adsorption behavior is
discussed for sub-monolayer to near-monolayer coverages. Moreover alteration of the
Au(111) surface reconstruction domain size is observed, caused by an adsorbate-induced
reduction of the Au(111) surface stress anisotropy. This behavior is not universal for the
monolayer –ZnTPP/Au(111) system as a monolayer prepared from the desorption of a
ZnTPP multilayer does not alter the domain size of the Au(111) surface. In this case, the
additional thermal energy leads to a complete rearrangement of the self-assembled
structure, and the surface stress anisotropy returns to its value for the clean surface.
3:55
Water Absorption in Thermally Grown Oxides on SiC and Si
Can Xu*1,2, Gang Liu2, Boris Yakshinskiy2, Leszek Wielunski2, Torgny Gustafsson2,
Joseph Bloch1,3, Sarit Dhar4 and Leonard C. Feldman1,2
1
Institute for Advanced Materials, Devices and Nanotechnology, 2Department of Physics
and Astronomy and Laboratory for Surface Modification, 3NRCN, Beer-Sheva, 84190,
Israel, 4Department of Physics, Auburn University
The structure and chemical compatibility of In2Se3 (a band insulator) and Bi2Se3 (a 3D
topological insulator) suggests possible promising applications of In2Se3/Bi2Se3 devices.
Indiffusion of In into Bi2Se3 will affect the transport properties. We have grown
In2Se3/Bi2Se3 thin films on sapphire by Molecular Beam Epitaxy at different
temperatures. Our Medium Energy Ion Scattering data show that higher growth
temperature increases In diffusion while the Bi2Se3 mobility decreases.
* = Student Presenter
15
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
ABSTRACTS FOR POSTERS
1)
Temperature Programmed Desorption of Ionic Liquid from Metals
Aleksandra B. Biedron*1, Joseph Bloch3, Sylvie Rangan2, Edward W. Castner, Jr.1 and
Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, Nanotechnology for Clean Energy
IGERT, 2Department of Physics and Astronomy and Laboratory for Surface
Modification, 3NRCN, Beer-Sheva, Israel
Ionic liquids (ILs) are a broad new class of materials with unique properties that hold
great promise for a range of applications. This work examines chemical and thermal
properties of the interaction of ILs with copper and gold substrates, focusing on the
interface. Ultrathin films were prepared by physical vapor deposition and characterized
with temperature programed desorption. Desorption spectra suggest dissociative IL
reactions with copper, although not with the more noble metal gold.
2)
Perovskite-Related Oxynitrides as Photoanodes in Photoelectrochemical
Cells
Bin Liu*, Eric Garfunkel, Martha Greenblatt and G. Charles Dismukes
Department of Chemistry and Chemical Biology
We are aiming to develop a tandem photoelectrochemical (PEC) cell, in which two
solar absorbers (semiconductors) in conjunction with two catalysts (oxygen and
hydrogen evolution catalysts) will be used to split water, to significantly increase the
solar-to-hydrogen conversion efficiency up to 10%. However, the lack of stable
semiconductors suitable as photoanode is the first problem that we encountered and
aim to solve. We propose to use perovskite oxynitrides (ABO3-xNx) as the photoanode
materials. In this poster, I will summarize the current state of the art in terms of
syntheses and critical properties of oxynitrdes from published articles and our own
research.
* = Student Presenter
16
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
3)
Alkyl-Aryl Coupling Catalyzed by Tandem Systems of Pincer-Ligated
Iridium Complexes and Zeolites
Bo Li*1, Long van Dinh1, Akshai Kumar1, Fuat E. Celik2, Alan S. Goldman1
1
Department of Chemistry and Chemical Biology, 2Department of Chemical and
Biochemical Engineering
Our approach to the development of a system for the catalysis of alkyl-aryl coupling was
based on pincer-iridium-catalyzed acceptorless dehydrogenation of an alkyl group,
followed by Friedel-Crafts coupling of the resulting olefin with arene, as show in the
scheme below. Further dehydrogenation can give us more unsaturated products, such as
dihydro-methylnaphthalene and methylnaphthalene.
4)
Generation Dependent Ultrafast Charge Transfer Dynamics in PyreneViologen Dendrons
Zheng Gong*1, Jianhua Bao1, Takehiro Kawauchi2 and Piotr Piotrowiak1
1
Department of Chemistry, 2Tokyo Institute of Technology, Department of Chemistry and
Materials Science, Tokyo Institute of Technology
Charge-transfer processes in a series of pyrene-viologen dendrons were studied using
femtosecond pump-probe spectroscopy. The transient absorption spectra show the
generation of pyrene radical cations at 465 nm and methyl viologen radical cations at 600
nm, therefore, the time-dependent absorbance change was recorded at these two
wavelengths. The fitting results indicate a fast charge separation and geminate
recombination between pyrene and the attached methyl viologen within τ1= 3 ps, as well
as a slower decay τ2= 5-20 ps which is associated with electron hopping between adjacent
methyl viologens. Furthermore, the solvent effect on charge-transfer reaction was
investigated by measuring the decay in acetonitrile and propionitrile. The polarity
dependence of τ1 and τ2 has been interpreted with the help of Marcus theory.
5)
HafSOx Radiation Mechanistic Study with Low Energy Electrons Exposure
Feixiang Luo*1, Boris Yakshinskiy2, Alexei Ermakov1 and Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, 2Department of Physics and Astronomy
and Laboratory for Surface Modification
There is a strong need for new lithographic resists sensitive to EUV radiation that can
produce higher resolution features than current organic ones. HafSOx is a new inorganic
resist that has attracted much attention. Unfortunately the radiation chemistry associated
with HafSOx development is still not fully understood. Since the secondary electrons
(SEs) originating from EUV photons are thought to be the key species changing the film
chemistry, we developed a low energy e-beam system to examine resist performance with
electrons.
* = Student Presenter
17
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
6)
Characterization of LiFePO4 Cathode Nanocrystals by STEM/EELS
Analysis
Joseph Schneider-Haefner*1, Yuxuan Wang2, Jiye Fang2, Natasha Chernova2, Doug Su3
and Frederic Cosandey1
1
Department of Materials Science and Engineering, 2Materials Science Department,
Binghamton University, 3CFN, Brookhaven National Laboratory
LiFePO4 is currently in use as cathode material for rechargeable Li-Ion batteries because
of its safety, low cost and high charge-discharge rate capabilities. In this study, we have
investigated the delithiation patterns within individual particles. The Fe L3/L2 ratio and O
Pre-K/K ratio were mapped on the EELS Spectrum Images to distinguish delithiated and
lithiated LiFePO4.
7)
Helium Atom Diffraction of Cyclooctatetraene on Cu (001)
John L. Wieczorek*, Erkan Z. Ciftlikli and B.J. Hinch
Department of Chemistry and Chemical Biology
Cyclooctatetraene (C8H8, COT) adsorbs readily on a copper (001) surface at room
temperature at coverages below one monolayer. Helium atom scattering exhibits
diffraction from COT coverage-dependent high-order-commensurate phases. We see the
first evidence of ordering below 0.05% of a monolayer. Thermal annealing can be used
to increase long range order, or possible molecular desorption. Complete desorption is
apparent above 190oC. Thermally induced disordering is observed at temperatures above
150oC. The possible influence of molecular COT conformational changes will also be
addressed.
8)
Nanoscale Synthesis of Nickel Phosphides as Novel HER Electrocatalysts
Ajay R. Kashi*, Anders B. Laursen, Bin Liu, Mariana J. Whitaker, Martha Greenblatt
and G. Charles Dismukes
Department of Chemistry and Chemical Biology
Producing renewable hydrogen (H2) is an imposing challenge for developing sustainable
energy systems. Low stoichiometric ratios of nickel phosphides, such as Ni5P4, have
been shown to be catalytically active for the hydrogen evolution reaction (HER) achieved
by the splitting of water. Ni5P4 demonstrates exceptional efficiency and stability in both
acidic and alkaline electrolytes with Tafel slope and turnover frequency (TOF) close to
that of standard noble metal catalysts as Pt. Synthesis of the nanoparticles is carried out
by high-temperature solid-state, hydrothermal, and solvothermal methods.
Characterization of these methods will allow better understanding of how to scale up
production of phase-pure Ni2P and Ni5P4 nanoparticles for high-surface area HER
electrodes with cheaper, earth-abundant materials.
* = Student Presenter
18
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
9)
Ultrasmall Palladium Nanoparticles Supported on Amine-Functionalized
SBA-15 as Efficient Catalysts for Hydrogen Evolution from Formic Acid
Katherine Koh*1, Jung-Eun Seo3, Jin Hee Lee3, Anandarup Goswami1,2, Chang Won
Yoon3 and Tewodros Asefa1,2
1
Department of Chemistry and Chemical Biology, 2Department of Chemical and
Biochemical Engineering, 3Fuel Cell Research Center, Korea Institute of Science and
Technology
The success of the so-called “hydrogen economy” for large-scale applications will
ultimately depend on efficient and sustainable production, storage and distribution of
hydrogen. Owing to its low toxicity, high volumetric H2 storage capacity and
availability both from renewable resources (e.g., biomass) as well as nonrenewable
resources (e.g., fossil fuel feedstocks), formic acid is one of the most favorable
chemical hydrogen storage media for large-scale energy storage applications. However,
for FA to become a viable hydrogen storage medium, efficient catalysts that enable it to
release H2 at low cost are necessary. Herein we show a facile synthetic route to aminefunctionalized nanoporous silica-supported ultrasmall Pd nanoparticles (SBA-15Amine/Pd) that were highly active catalysts for formic acid dehydrogenation,
producing hydrogen at ambient temperature with a high turn-over-frequency (TOF) of
293 h-1—which was among the highest TOFs ever reported for the reaction by a
heterogeneous catalyst. We also show that the material is easily recyclable multiple
times, without losing its catalytic activity. So, the catalyst we developed might
contribute to some of the solutions of our sustainability challenges.
10)
The Effect of Fe-Doping on the Electronic Structure and Activity of Nickel
Phosphide, Ni2P a Catalyst for H2 Evolution from Water
Kelly R. Patraju*1, Anders B. Laursen1, Martha Greenblatt1 and G. Charles Dismukes1
1
Department of Chemistry and Chemical Biology
Nickel-phosphide Ni5P4 is an excellent catalyst comparable to the typical platinum (Pt)
catalyst for hydrogen (H2) evolution. The catalyst Ni2P shows structural similarities and
H2 evolution activity similar to that of Ni5P4. This study shows the tuning of the electron
density of the active site of Ni2P by isostructural substitutional doping of iron (Fe)
resulting in FexNi2-xP in the full range 0 < x < 2. The structure is investigated by PXRD
and the electronegativity difference between Fe and Ni used to explain the changes in
electronegativity on the active Ni site.
* = Student Presenter
19
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
11)
Title Ni5P4 a Game Changing H2 Evolution Catalyst
Anders B. Laursen1, Kelly R. Patraju1, Mariana J. Whitaker1, Tapati Sarkar2, Nan Yao3,
Kandalam V. Ramanujachary4, Martha Greenblatt1 and G. Charles Dismukes1
1
Department of Chemistry and Chemical Biology, 2Uppsala University, Sweden, 3PRISM
Imaging and Analysis Center, Princeton University, 4Department of Chemistry, Rowan
University
Hydrogen produced from fossil-free resources, e.g. electrocatalytic water-splitting,
could not only introduce “the hydrogen economy” but is also an industrially relevant
bulk chemical with a current ~108 ton annual production from natural gas. In
electrochemical water-splitting platinum and nickel (or alloys thereof) are the
electrocatalysts of choice for the hydrogen evolution reaction (HER) in acid and alkali,
respectively. The scarcity of platinum, and the low efficiency of nickel, have greatly
restricted the development of renewable hydrogen. Molecular nickel organophosphine
complexes and more recently the crystalline solid Ni2P have proven highly active HER
catalysts but both decompose during operation. Here we report, that the Ni5P4,
outperforms Ni2P and is comparable to platinum in its electrical efficiency for HER
(kinetics and intrinsic overpotential). Unlike for Ni2P, Ni5P4 is corrosion resistant in
both strong acid and alkali during electrocatalysis. We will present a structural basis for
the unusually high catalytic activity and corrosion resistance.
12)
Investigation of Propene and Pentene Dimerization by Acid Zeolites
Longfei Chao* and Fuat E. Celik
Department of Chemical and Biochemical Engineering
C5 hydrocarbons, with limited commercial applications, are major byproducts of a
number of commercially important processes. In the present study, multiple zeolites and
reaction conditions are investigated to transform C5 olefins to C10 olefins that are more
commercially valuable. Propene is studied as a common secondary product as well.
13)
Biased Photoemission and Ab-Initio Studies of Metal-InsulatorSemiconductor Structures
Malathi Kalyanikar*1, Sylvie Rangan2, Junxi Duan2, Gang Liu3, Stephen Weitzner4,
Robert Bartynski2, Eva Andrei2, Leonard Feldman3, Ismaila Dabo4 and Eric Garfunkel1
1
Department of Chemistry and Chemical Biology, 2Department of Physics and Astronomy
and Laboratory for Surface Modification, 3Institute for Advanced Materials, Devices and
Nanotechnology, 4Department of Material Science and Engineering, Penn State
University
Electrostatic potential changes across thin films is of great importance for understanding
properties of multilayer structures and devices. Studies of potential changes across metalinsulator-semiconductor systems can be performed using XPS with an external bias
placed perpendicular to the surface. The shift in photoemission binding energies across
graphene-SiO2-Si structures as a function of external bias is studied in this work.
Complementary DFT calculations of metal/graphene systems are conducted to help
understand the underlying electronic structure and potential profile.
* = Student Presenter
20
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
14)
Surface Phonons in the Superlattice of the Topological Insulator Bi2Se3
Maryam Salehi*1, H.-H. Kung2, N. Koirala2, M. Brahlek2, S. Oh2 and G. Blumberg2
1
Department of Material Science and Engineering, 2Department of Physics and
Astronomy and Laboratory for Surface Modification
The Dirac surface states of the topological insulator Bi2Si3 has attracted a lot of interest
since its recent discovery. However, very few attention has been given to their
interaction with the surface phonon. We use polarization resolved Raman spectroscopy
to study the symmetries of the low energy excitations in MBE grown Bi2Se3 thin films.
By increasing the surface to volume ratio of Bi2Se3 through Bi2Se3-In2Se3 superlattice
structure, we were able to detect two weak surface phonon modes. The energies are
consistent with theoretical calculations incorporating electron-phonon interactions of
the surface states.
15)
The Rutgers UltraSTEM
Maureen Joel Lagos and Philip E. Batson
Institute for Advanced Materials, Devices and Nanotechnology, Department of Materials
Science and Engineering, Department of Physics and Astronomy and Laboratory for
Surface Modification
Recently, Rutgers University has become the house of one of the most advanced scanning
transmission electron microscope (STEM) in the world. The RUTGERS UltraSTEM
instrument is equipped with both aberration corrector and energy monochromator, which
allows the physical exploration of phenomena over a wide energy range with both high
spatial and energy resolution. Currently, our instrument has achieved angstrom resolution
(~ 1 Å) and 10 meV of energy resolution at 60 KV. With this outstanding performance,
we can perform studies of vibrational, plasmonic, interband transition and core-shell
spectroscopy with atomic resolution. The remarkable capabilities of the new RUTGERS
UltraSTEM are illustrated through a large variety of experimental results from ongoing
collaborations with both internal and external researchers.
16)
Capture and Release of Plasmonic Electrons in Ag@hexaniobate
Nanopeapod Assemblies
Mengdi Liu1, John B. Wiley2 and Piotr Piotrowiak1
1
Department of Chemistry, 2Department of Chemistry, University of New Orleans
Photoinduced charge transfer in Ag@hexaniobate nanopeapod assemblies was studied
using ultrafast pump-probe spectroscopy. The “nanopods” consist of thin potassium
hexaniobate sheets tightly wound around linear arrays of metallic silver nanoparticles.
Transient absorption spectra and decay dynamics were measured. The result show a very
rapid hot-electron relaxation from above Fermi level of silver and a competing process of
hot-electron injection into the conduction band of the hexaniobate scroll followed by
slower charge recombination in the picosecond time domain. Direct capture of plasmonic
electrons is of great interest in the fields of solar energy conversion, photocatalysis and
optoelectronics.
* = Student Presenter
21
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
17)
Metallic 1T Phase MoS2 Nanosheets as Supercapacitor Electrode Materials
Muharrem Acerce*, Damien Voiry and Manish Chhowalla
Material Science and Engineering
We show that chemically exfoliated nanosheets of metallic 1T phase MoS2 can
electrochemically intercalate ions (H+, Li+, Na+ and K+) with high capacitance values up
to ~700 F cm−3 in a variety of aqueous electrolytes. We also demonstrate that this
material is suitable for in non-aqueous organic electrolytes, showing prime volumetric
energy and power density values with high stability over 5,000 cycles. High
electrochemical performance is mainly a result of their high electrical conductivity,
hydrophillicity and the ability of dynamic expansion of layers via ion intercalation
according to XRD analysis.
18)
Increasing Visible-Light Photocatalytic Activity via Modification of TiO2
Photocatalysts
Ashley M. Pennington*, Katelyn A. Dagnall, Deniz A. Dindi and Fuat E. Celik
Department of Chemical and Biochemical Engineering
Titanium Dioxide (TiO2), a metal oxide semiconductor, has high photocatalytic activity
under ultraviolet illumination and is stable under catalytic conditions. We aim to modify
the band gap, increasing activity under visible-light. Modified TiO2 is active for
photocatalytic reforming of methanol, a model for biomass, producing hydrogen gas, a
zero-emission fuel.
19)
Understanding Electron Energy Loss Mechanisms in EUV Resists Using
REELS and First-Principles Calculations
Sylvie Rangan1, Robert A. Bartynski1, Amrit Narasimhan2 and Robert Brainard2
1
Department of Physics and Astronomy and Laboratory for Surface Modifications,
2
College of Nanoscale Science and Engineering University, Albany
X-ray and UV photoemission spectroscopies have been performed on materials relevant
to EUV resist materials and interpreted using ground states properties calculated for
simple molecular models using ab-initio techniques. Additionally, the origin of energy
loss mechanisms for low energy electrons (30 eV to 110 eV) in these materials has been
investigated by comparing experimental reflection electron energy spectroscopy spectra
to calculated absorption spectra.
20)
A Click Approach to “STAR” Ruthenium-Sensitizer
Runkun Sun*, Hao Fan and Elena Galoppini
Department of Chemistry, Rutgers, Newark
2, 2′-Bipyridine (bpy) derivatives has been widely used for the synthesis of Ruthenium
complex using in Dye-sensitized solar cell (DSSC). The synthesis of several bpy
derivatives involves several step low yield and tedious reactions. We proposed a new
strategy with fewer steps and higher yields, which will promote the applications of 2, 2′bipyridine derivatives. With these derivatives, we started the synthesis of a Ruthenium
complex, which will be used for the DSSCs.
* = Student Presenter
22
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
21)
Selective Electrochemical Deposition of LiCoO2 and Its Properties as an
Electrocatalyst for Water Oxidation/Oxygen Evolution
Shinjae Hwang*, Graeme Gardner, Eric Garfunkel and G. Charles Dismukes
Department of Chemistry and Chemical Biology, Institute for Advanced Materials,
Devices and Nanotechnology
The electrolytic splitting of water into hydrogen and oxygen is one strategy being
explored for large-scale electrical energy storage/conversion from solar and wind energy
sources. Nanoparticles of the cubic polymorph of LiCoO2 prepared by sol-gel methods
were previously demonstrated to exhibit high activity for oxygen evolution reaction
(OER), two orders of magnitude higher than the layered polymorph of LiCoO2 1. Here,
we have developed an electrochemical method to selectively deposit cubic spinel
LixCoO2 (0≤x≤1) as a film onto conducting substrates. The deposited film shows a low
overpotential for the OER and exhibits long-term stability at 10 mA/cm2 current density
in alkaline electrolyte (1 M NaOH).
References: 1. Gardner, G. P.; Go, Y. B.; Robinson, D. M.; Smith, P. F.; Hadermann, J.;
Abakumov, A.; Greenblatt, M.; Dismukes, G. C. Angew. Chem. Int. Ed. 2012, 51, 1616
22)
Characterization of Catalysts Using Helium Ion Microscopy and
Temperature Programmed Desorption
Viacheslav Manichev*1, Can Xu1, Hao Wang1, Wenhua Chen1, Leonard Feldman1,2,
Torgny Gustafsson1 and Robert A. Bartynski1
1
Department of Physics and Astronomy and Laboratory for Surface Modification,
2
Institute for Advanced Materials Devices and Nanotechnology
Using our newly established helium ion microscopy (HIM), we have obtained highresolution images of industrial catalysts prepared by various methods. HIM, has also been
used to characterize the morphology of adsorbate-covered faceted Re(12-31) with results
consistent with reciprocal space measurement by low energy electron diffraction (LEED)
performed under UHV condition. Our results demonstrate that HIM is a powerful
technique to quickly image the morphology of both industrial catalysts and model
catalysts.
Temperature programmed desorption (TPD) was used to characterize reactivity and
selectivity in ammonia oxidation of model Ir catalysts of planar Ir(210) and faceted
Ir(210) exposing three-sided pyramids. Evidence has been found for the formation of
N2O from both surfaces, which is the first observation of N2O production in catalytic
ammonia oxidation under UHV conditions (<1×10-9 Torr).
This work was supported by Rutgers Institute for Advanced Materials, Devices and
Nanotechnology, NSF grant DMR-1126468, and DOE grant DE-FG02-93ER14331.
* = Student Presenter
23
TWENTY-NINTH ANNUAL SYMPOSIUM
LABORATORY FOR SURFACE MODIFICATION
23)
Yeast Cells-Derived Hollow Heteroatom-Doped Carbon Microparticles for
Sustainable Electrocatalysis and Renewable Energy Applications
Xiaoxi Huang*1 and Tewodros Asefa1,2
1
Department of Chemistry and Chemical Biology, 2 Department of Chemical and
Biochemical Engineering
The use of renewable resources to make various synthetic materials is increasing in
order to meet some of our sustainability challenges. We show that yeast cells can be
thermally transformed into hollow, core-shell heteroatom-doped carbon microparticles
that can effectively electrocatalyze the oxygen reduction and hydrazine oxidation
reactions, reactions that are highly pertinent to fuel cells or renewable energy
applications. We also show that yeast cell walls, which can be separated from the cells,
can produce carbon materials with electrocatalytic activity for both reactions, albeit
with lower activity compared with former one. The results reveal that the intracellular
components of the yeast cells are indirectly responsible for the latter's higher
electrocatalytic activity, by providing it with more heteroatom dopants. The synthetic
method we report here can serve as a general route for the synthesis of (electro)
catalysts using microorganisms as raw materials.
24)
Functionalization of Rubrene Single Crystal with Self Assembled Monolayers
Yuan Chen*1, Sylvie Rangan2, H.T.Yi2, Elena Galoppini1, Robert Bartynski2 and Vitaly
Podzorov2
1
Department of Chemistry, Rutgers, Newark, 2Department of Physics and Astronomy and
Laboratory for Surface Modification
Organic semiconductors such as polyaromatic hydrocarbons are widely applied in new
types of sensors, OLED, OFET and other electronic devices. Rubrene single crystal is a
p-type semiconductor that has the highest field-effect hole mobility as large as 20 cm2V1 -1
s . Such electronic properties that depend on the surface properties of the semiconductor
can be tuned by effective surface functionalization. We report the use of self-assembled
molecules such as (3-bromopropyl) trichlorosilane and 4-bromobenzenediazonium
tetrafluoroborate to functionalize rubrene single crystal through the forming of permanent
strong covalent bond. The functionalized rubrene single crystal showed improved
electronic properties.
* = Student Presenter
24