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AIChE Annual Meeting
November 14, 2006
Part 2 of 3 Parts
Program Director Catalysis and Biocatalysis Directorate for Engineering National Science Foundation
S. Ted Oyama
Catalytic oxidation using ozone is a promising technology for the lowtemperature destruction of volatile organic compounds, such as acetone. A silicasupported manganese oxide (MnO2/SiO2) was used because of its strong oxidizing ability. EXAFS showed that a 3 wt % sample had isolated octahedral Mn atoms while a 10 wt % sample had clusters resembling fragments of Mn3O4. The rate was higher on the clusters, indicating that multiple adjacent Mn centers facilitated the reaction.
CH3COCH3 + 8 O3
3 CO2 + 3 H2O + 8 O2
O Mn O O O O O O O Si O Si Mn O Si O Si
O Mn Si O O
Raman spectroscopy at reaction conditions showed the presence of two surface intermediates, a peroxide species derived from ozone, with a band at 890 cm-1, and an adsorbed species with intact C-H bonds derived from acetone, with a band at 2930 cm-1. Simultaneous measurements of rate and coverage showed that the adsorbed acetone intermediate reacted with atomically adsorbed oxygen species to form complete oxidation products.
C. Ted Lee, Jr.
University of Southern California
CBET-0554115 One of our overarching goals has been to investigate how photo-reversible control of protein structure with light-responsive surfactants could be used to control enzyme activity. We soon realized that while in vitro conformations from small-angle neutron scattering (SANS) provide unique insight into catalytic processes, enzyme dynamics can have considerable influence on activity. Both native and partially-folded lysozyme display similar active sites, however, neutron spin echo (NSE) detects nanosecond/nanometer domain motions in the partially-folded form. This increased molecular flexibility leads to 5 × superactivity relative to the native state. Five students (two graduate, two undergraduate, and one high-school), all of whom are young female scientists, have been involved in this NSF-sponsored work.
Photo-control of lysozyme form, dynamics, and function
active site SANS X-ray cryst. UV visible
native state: • rigid, no detectible ns/nm motions
partially-folded state: • flexible, ns/nm domain motions • 5× superactivity vs. the native state
Nitrogen Doped TiO2 Nanoparticles
S. Ismat Shah (PI):
We have previously reported the results of doping TiO2 with N to change the absorbed wavelengths from UV to visible which allows the degradation of the environmental pollutants with the more abundant visible part of the sun light. Figure 1 shows the effect of optimization of N concentration in TiO2 on the removal of a chemical pollutant from water.
Michael P. Harold
University of Houston
A team at UH is developing new types of composite Pd/ceramic hollow fiber membranes to extract and purify hydrogen at high temperatures and pressures. Pd and Pd alloy films are deposited on or between nanoporous alumina layers or grown in the pores of alumina through sequential electroless plating and sol-gel processing steps. “Pd Nanopore” hollow fiber membranes exhibit excellent flux and hydrogen permselectivity, improved durability with use, and have high surface to volume. The membranes have been used to produce a high purity hydrogen stream during hydrogen generating reactions such as methanol autothermal reforming and ammonia decomposition.
Porous α -Al2O3 hollow fibers are coated with micron-thick layers of Pd alloys and γ -Al2O3
Methanol + Steam Air Pd Membrane
Hydrogen Permeate Retentate
A “dual membrane reactor” utilizes porous membranes for air supply to mitigate hot spots and Pd composite hollow fibers for H2 removal and purification.
Daniel E. Resasco
University of Oklahoma (CTS-0308619)
Our group investigate the growth of well structured arrays of single-walled carbon nanotubes on flat surfaces (e.g. silicon wafer). The goal of the project is to produce catalyst supports with controlled structure on which Pt clusters can be deposited for applications in fuel cells and gas sensors. We have demonstrated that the density and distribution on the flat surface of the catalyst moieties responsible for the nanotube growth (Co-Mo catalyst) is crucial to determine whether the nanotubes grow in vertically oriented fashion (“forest”) or a random network parallel to the surface (“grass”). We found that different forms of SWNT arrays can be reproducibly obtained on flat silicon substrates when the Co-Mo catalyst particles have the appropriate distribution, which can be readily controlled by simply varying the concentration of catalyst solution. Also, the CoMo catalyst can be patterned and the resulting nanotube forest copies the catalyst pattern. In a subsequent step, to effect the selective deposition of Pt precursors on the nanotube forest, we choose the charge of the precursor (e.g. anionic) and the pH of the solution (e.g. lower than the point of zero charge) to generate on the nanotube an opposite charge to that of the Pt precursor and take advantage of the Coulombic attraction
Structured Pt/SWNT catalyst electrically connected to a Si wafer
Pt Si wafer
University of Cincinnati (UC)
NSF-CTS # 0403897 This interdisciplinary team (Biocatalytic Membrane Nanosystems) is investigating the effects of surface curvature and confined nanoscale environment on biocatalytic activity of Burkholderia cepacia lipase and cytochrome P450 BM3 immobilized on dense colloidal silica sphere array and ordered mesoporous SBA-15 silica possessing 5.5-24 nm pores. This NIRT team is comprised of four researchers at two institutions: Vadim Guliants (UC biocatalysis), Neville Pinto (UC - enzymesurface interactions), Jerry Lin (Arizona State – membrane reaction engineering) and Carol Caperelli (UC – protein expression)
University of South Carolina
60 EpB Conversion (%) 50 40 30
Conventional methods for preparing bimetallic catalysts provide little regulation over metal placement. An alternative method is Electroless Deposition (ED) wherein a metal salt is deposited from solution by a controlled chemical reaction that is catalyzed by the preexisting metal or by the metal which is being deposited. Experimental results show that ED derived catalyst provide more targeted metal placement than their incipient wetness counterparts. Catalytic evaluation for the hydrogenation of 3,4-Epoxy-1-butene (EpB) revealed a significant improvement in both activity and selectivity to butylene oxide with the addition of small amounts of Ag to Pt/SiO2 catalysts. Higher Ag loadings resulted in the expected catalyst poisoning.
60 Selectivity to Butylene Oxide (%) 50 40 30 crotonaldehyde H2 H2
20 10 0 0 EpB 0.05
0 H2 crotonaldehyde H2 H2 0.1 0.15 0.2 0.25 OH Silver Loading (wt%) OH n-Bu H2 H2 3-Bu-1-ol OH isomerization
H2 OH H2
EpB = 3,4 n-butanal = n-butyraldehy FT-IR results epoxy-1-butene indicate that crotonaldehyde = 2-buten-1-al Pt(111) sites n-BuOH = n-butanol crotyl alcohol = 2-buten-1-ol BO = butylene oxide Hby Ag, suggesting (epo are selectively 3-buten-1-ol 3-Bu-1-ol = covered BO that Ag-induced ensemble modifications are responsible = 3,4 epoxy-1-butene EpB for the enhanced catalytic = n-buty n-butanal crotonaldehyde = 2-buten-1-al n-BuOH = n-butan properties shown above. crotyl alcohol = 2-buten-1-ol BO = butylene ox
3-Bu-1-ol = 3-buten-1-ol
Louisiana Tech University
CAREER Award # CTS-0449046
Schematic representation of methanol oxidation by bacteria Methanol Dehydrogenase (MDH) in fuel cell anode (right).
Bacterial Methanol Dehydrogenase/ Mediator Products Methanol
The nature of the ion in the active site of MDH modifies the binding and orientation of methanol, facilitating the methanol oxidation reaction as the highlighted hydrogen-oxygen distance decreases (left). Learning kits and “in vivo” demonstrations of computational research activities distributed to students during 2006 Engineer’s Day at LA Tech (right). Mainly, these educational activities have a direct impact on K-12, high school, and prospective students from small rural and small town schools around Louisiana Tech’s region.
C. Buddie Mullins
University of Texas at Austin
Our group is investigating the growth of thin films of porous titania nanocolumns in ultra-high vacuum. These films have high surface area and a high concentration of ‘defect’ sites, providing an opportunity to study materials resembling those used in classical catalysis with the techniques of surface science (electron, photon, and temperature desorption based spectroscopies). Study of physisorption and chemisorption processes on these films may provide a link between chemi-physical properties of single crystal surfaces typically used in UHV studies and more complex structures employed in industrial catalysis. Because TiO2 is widely used in catalytic and photocatalytic applications, we are exploring the activity of these films for promoting relevant chemical reactions and how reactivity changes with modification of the films’ composition and structure. The C. Buddie Mullins research group at UT-Austin is working in close collaboration with investigators Bruce D. Kay and Zdenek Dohnalek at Pacific Northwest National Laboratory.
SEM images of high surface area film
TEM of single column from film showing porosity
Kathryn E. Parent
ACS Green Chemistry Institute
The 10th Annual Green Chemistry & Engineering Conference, held June 26-30, 2006, in Washington, D.C., provided a forum for discussing the role of green chemistry and engineering in “Designing for a Sustainable Future”. The conference technical program focused on the areas of energy, agriculture, renewable feedstocks, toxicity reduction, and health & medicine. NSF funding provided travel support to 49 undergraduate, graduate and post-doctoral students. Twenty-seven (55%) of the sponsored students gave oral presentations. The conference attracted over 420 attendees from academia, industry, government, and non-governmental organizations, representing 26 different countries and 203 unique institutions. Over 100 undergraduate, graduate and post-doctoral students participated in the conference.
See www.GCandE.org for 2007 Conference info.
University of North Carolina at Chapel Hill
The Lin group is designing practically useful heterogeneous asymmetric catalysts based on metal-organic frameworks. The crystalline nature of the present system allows the engineering of perfectly uniform catalytic sites and thus provides a platform for detailed interrogation of the factors important to catalytic activity and stereoselectivity. The students engaged in this research are trained with invaluable skills in synthetic chemistry, solid-state chemistry, and asymmetric catalysis.
Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940-8941.
University of North Carolina at Chapel Hill
The Lin group is designing practically useful heterogeneous asymmetric catalysts by combining synthetic chemistry with nanotechnology. Readily recyclable and reusable catalysts were for example obtained by immobilizing functionalized molecular catalysts on superparamagnetic magnetite nanoparticles. The students engaged in this research are trained with not only invaluable skills in synthetic chemistry and catalysis but also practical experience with nanomaterial characterization.
OH H2 R Up to 98.0% ee Used for 14 times
(BINAP)Ru(DPEN)Cl2 O P O
Hu, A.; Yee, G.T.; Lin, W. J. Am. Chem. Soc. 2005, 127, 12486 (highlighted in 2 September 2005 issue of Science).
James F. Rusling
University of Connecticut
A team including Peterson Guto, C. V. Kumar, and James Rusling showed that crosslinked films of enzymes and poly-Llysine (PLL) on surfaces are capable of biocatalysis at 90 oC. Peroxidases in these films were stable for up to 9 hr at 90 oC, compared to <20 min in solution. The biocatalytic films can be made on flat electrodes or 0.5 µ carboxyl-silica beads, and catalyzed butyl hydroperoxide reduction and phenol oxidation at much higher rates at 90 oC than at 25 oC. These novel biocatalytic films hold great promise for future high temperature chiral synthesis.
University of California at Riverside
CTS0404376 Low-dielectric constant (low-k) materials are urgently needed to replace dense silica (k ≈ 4) for the production of future generation faster and cheaper microprocessors. We have been studying a new class of low-k materials - pure-silica-zeolites (PSZs) whose unique crystalline nature provides them with high mechanical strength, uniform micropores (<2 nm), and high heat conductivity, properties that are lacking in other low-k candidates (i.e., polymer, sol-gel silica and surfactant templated mesoporous silica). Our most recent experimental results (see Figure) provide definitive evidence that PSZs offer a significantly superior elastic modulus to amorphous silicas at any given k or porosity. Moreover, our theoretical calculations (see Figure) of PSZ single crystals validate our experimental results and further suggest that there is much room for improving both k and E of PSZ low-k films. Four investigators are funded through this collaborative research: Yushan Yan (UCR), Mark E. Davis (Caltech), Michael Deem (Rice) and Piotr Zelenay (LANL).
100 90 80 70
Amorphous silica exp. Amorphous silica exp. data fitted line MFI spin-on film MFI porogen spin-on film MEL spin-on films MFI in-situ film MFI seeded growth film PSZ single crystal exp. PSZ single crystal cal.
60 50 40 30 20 10 0 4.0
MFI BEA CHA
Figure. Elastic modulus (E) versus dielectric constant (k) for amorphous silicas and PSZs. The open circles and solid data fitted line are experimental data from Xu et al. Squares are experimental data for polycrystalline PSZ MFI films. Triangles are experimental data for spin-on PSZ MFI and MEL films. Diamonds are from calculations of PSZ single crystals. The star is experimental data for FER single crystal. From Angewandte Chemie. 118(2006)6477
Arizona State University
Award # CTS-0508434 and 0625340 Applications of carbon nanotubes (CNTs) are dependent on their structure, morphology and properties. CNTs are often synthesized by catalytic decomposition of hydrocarbons. We are exploring the effect of temperature and synthesis conditions on catalysts by patterning individual catalyst particles of controlled size (top left) by electron beam induced decomposition of organometallic precursors (e.g.ferrocene) and observing growth process of CNTs, in situ, from these particles using a specially modified transmission electron microscope (top right). These observations are used to obtain growth mechanisms and kinetics (bottom left) and control the morphology and structure of CNTs formed (bottom right). The interpretation of in situ observations are modeled (M.M.J. Treacy) and supported by theoretical modeling (Peter Rez).
Controlled growth of catalyst particles for CNT synthesis
Growth of Carbon nantubes at 477C
200 Length (nm) 150 100 50 0 0 1 2 3 Time (Sec) 4 5 6 tube D=6.36nm Tube2 D=4.95nm Tube3 D=4.76nm Tube1 D=3.84nm Tube4 D=6.38nm
Statistics of nanotubes around 1mTorr
650C 600C 550C 500C 450C
Percent of total tubes
0.6 0.4 0.2 0 1 2 3 4 5
No. of walls
Michael W. Deem
A combined theoretical and experimental effort at Rice, Caltech, and UCI is seeking zeolite-type materials suitable for low-k dielectric microelectronics aplications.
Angew Chem. Int. Ed. 45 (2006) 6329
Richard C. Alkire & Richard D. Braatz
University of Illinois at Urbana-Champaign
A multiscale model has been developed for the electrodeposition of copper onto surfaces and trenches in the presence of additives. The process is widely used to make various nanostructures including on-chip interconnects in microelectronic devices. The predictions of the model agree well with experimental data over the range of additive concentrations used for fabricating interconnects (see graph). The next step is to use the model to design improved additives that increase the geometric uniformity of electrodeposited nanostructures.
PEG concentration (g/L)
1 0.8 0.6 0.4 0.2 00 20
Voids & defects occasionally occur inside the trenches Voids & defects increase. No good filling for small trenches.
Chloride concentration (ppm) Comparison of experimental data with numerical simulations of the regions of additive concentrations that reliably fill, occasionally fill, and do not fill trenches such as used for on-chip wiring.
Robert J. Davis
University of Virginia
Increased US production of biodiesel fuel from vegetable oil will lead to excess supplies of the byproduct glycerol. Using gold catalysts supported on carbon, glycerol can be selectively transformed at high rates to value-added products, which can be used within both the pharmaceutical and specialty chemicals industries. Proper catalyst design and reaction conditions must be applied in order to minimize formation of unwanted products during the reaction.
OH OH OH
O glyceric acid
Gold nanoparticles on a carbon support
Robert J. Davis
University of Virginia
OH HO OH O OH OH
Plant-derived biomass is considered to be the most feasible alternative to petroleum feedstocks for the production of commodity chemicals and materials. In one processing scheme, biomass can first be broken down into its sugar monomers. These sugars can then be converted to intermediates like sorbitol and glycerol. Our research group is focusing on conversion of polyols to commodity oxygenated chemicals over various transition metal-based catalysts such as Pt and Ru.
OH HO OH
Ethylene glycol CH4
Propylene glycol + CO2
Moles of carbon in product / Sum (moles of carbon in all products)
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