Author Archives: Carl Menning

In Silico Prediction of Materials for Energy Applications

Meeting Program – September 2016

Dion Vlachos
Dion Vlachos
Elizabeth Inez Kelley Professor of Chemical
& Biomolecular Engineering and Professor of Physics,
University of Delaware

Abstract – In this talk, the need for new materials in various energy domains will be discussed. Multiscale simulation will then briefly be introduced as an enabling technology to address diverse engineering topics. A specific application of multiscale simulation is the prediction of macroscopic behavior from first principles. A more impactful avenue of research is how one could use multiscale modeling in reverse engineering for predicting new materials for production of energy and chemicals and energy storage. We will demonstrate how descriptor-based modeling can enable such a search of novel materials with emergent behavior and assess this framework with experiments. An outstanding question is how reliable and robust are model predictions in comparing to data and our quest for searching new materials. We will demonstrate this methodology for the specific example of ammonia decomposition for hydrogen production for fuel cells and briefly touch upon renewable chemicals and fuels from lignocellulosic biomass.
Biography – Dionisios (Dion) G. Vlachos is the Elizabeth Inez Kelley Professor of Chemical & Biomolecular Engineering and Professor of Physics at the University of Delaware and the Director of the Catalysis Center for Energy Innovation (CCEI), an Energy Frontier Research Center (EFRC) funded by the Department of Energy (DOE). He obtained a five-year diploma in Chemical Engineering from the National Technical University of Athens, Greece in 1987, his M.S. and Ph.D. from the University of Minnesota in 1990 and 1992 respectively, and spent a postdoctoral year at the Army High Performance Computing Research Center in Minnesota. After that, Dr. Vlachos joined the University of Massachusetts as an assistant professor, was promoted to an associate professor in 1998 and joined the University of Delaware in 2000. He was a visiting fellow at Princeton University in the spring of 2000, a visiting faculty member at Thomas Jefferson University and Hospital in the spring of 2007 and the George Pierce Distinguished Professor of Chemical Engineering and Materials Science at the University of Minnesota in the fall of 2007.

Professor Vlachos is the recipient of the R. H. Wilhelm Award in Chemical Reaction Engineering from AIChE and is an AAAS Fellow. He also received a NSF Career Award and an Office of Naval Research Young Investigator Award. He is a member of AIChE, ACS, the Combustion Institute, MRS, the North American Catalysis Society (NACS) and the Society for Industrial and Applied Mathematics (SIAM).

Dr. Vlachos’ main research thrust is multiscale modeling and simulation along with their application to catalysis, crystal growth, portable microchemical devices for power generation, production of renewable fuels and chemicals, catalyst informatics, detailed and reduced kinetic model development and process intensification. He is the corresponding author of more than 340 refereed publications with nearly 10,000 citations and has given over 200 plenary lectures, keynote lectures and other invited talks. Professor Vlachos has served as an executive editor of the Chemical Engineering Science journal and also served or currently serves on the editorial advisory board of ACS Catalysis, Reaction Chemistry & Engineering, Industrial and Engineering Chemistry Research, Applied Catalysis A: General, Proceedings of the Combustion Institute, the Open Energy and Fuels Journal, the Journal of Nano Energy and Power Research and the Journal of Chemical Engineering & Process Technology.

Prof. Dion Vlachos is the Winner of the 2016 Catalysis Club of Philadelphia Award

Dion VlachosThe Catalysis Club of Philadelphia is pleased to announce Prof. Dion Vlachos as the recipient of the 2016 Catalysis Club of Philadelphia Award, in recognition of his long-standing creative technical contributions, both theoretical and experimental; advancing the understanding of the molecular basis of heterogeneous catalysis of complex systems; and his leadership role at the Catalysis Center for Energy Innovation and Center for Catalytic Science and Technology.

Prof. Vlachos received his PhD form the Chemical Engineering and Materials Science Department, University of Minnesota, where he studied the structures and dynamics of adsorbed phases and crystal surfaces. He joined the Chemical Engineering Department at the University of Massachusetts in 1993 as an Assistant Professor and in 1998 became an Associate Professor at the department. In 2000, Dion joined the Department of Engineering at the University of Delaware, where he currently holds a position as Elizabeth Inez Kelley Professor of Chemical Engineering.

Dion has pioneered the work on development of multi-scale modeling and applying this approach to technologically important problems in energy, catalysis, biomass conversion, nanotechnology and cellular engineering. His research has been adopted by chemical industry in companies, such as ConocoPhillips, Praxair, and Rohm and Haas, for chemical processes design and emissions reduction.

Dion’s research of biomass conversion, specifically catalytic transformation of sugars into fuels and chemicals, helped to advance the understanding of sugar chemistry. His work on the elucidation of active species in HCl/CrCl3 involved in sugar transformations resulted in a high impact publication with a record number of citations. His theoretical study of Sn-Beta catalyst for glucose isomerization has found the active form of tin in the zeolite and revealed the importance of neighboring silanol groups for the selectivity of the isomerization reaction. Dion’s theoretical work was later confirmed experimentally by Davis group in Caltech.

As the founder and director of the Catalysis Center for Energy Innovation (CCEI), Dion has shown an outstanding leadership and obtained $29.5M in funding over nine years. Through CCEI, he helped to nurture collaborations between research groups from leading academic institutions. CCEI focuses on the development of new catalysis and processes for biomass conversion to fuel and chemicals.

Dion has published over 340 scientific papers, which collectively have over 9400 citations. In the past few years, he has been publishing over 30 research papers per year, which makes Dion one of the most productive catalysis researchers.

Please join us in congratulating Dion on receiving the 2016 Catalysis Club of Philadelphia award.

Past Recipients of the Award

1968 Adalbert Farkas
1969 Charles J. Plank
1970 Paul H. Emmett
1971 G. Alex Mills
1972 Alfred E. Hirschler
1973 Paul B. Weisz
1974 Roland C. Hansford
1975 Paul Venuto
1976 Heinz Heinemann
1977 G.C.A. Schuit
1978 George W. Parshall
1979 Alvin B. Stiles
1980 Abraham Schneider
1981 James F. Roth
1982 Robert Eischens
1983 Edward Rosinski
1984 James R. Katzer
1985 N.Y. Chen
1986 Bruce C. Gates
1987 James E. Lyons
1988 George Kokotailo
1989 Maurice Mitchell, Jr.
1990 Werner O. Haag
1991 John A. Sofranko
1992 Fran Waller
1993 George Kerr
1994 Theodore A. Koch
1995 John N. Armor
1996 Mae Rubin
1997 Leo E. Manzer
1998 Ray Gorte
1999 Anne M. Gaffney
2000 Henry C. Foley
2001 Mark Barteau
2002 Steven D. Ittel
2003 Frank E. Herkes
2004 Jingguang Chen
2005 Israel Wachs
2006 James Dumesic
2007 John Vohs
2008 David Olson
2009 Ted Oyama
2010 Chuck Coe
2011 Chunshan Song
2012 Rostam Madon
2013 Daniel Resasco
2014 Haiying Chen
2015 Sourav Sengupta
2016 Dion Vlachos
2017 Thomas Colacot

2015–2016 Meet­ing Program

Thursday, Sept. 17th, 2015Sourav SenguptaCatalysis – An Indispensable Tool
Sourav Sengupta, DuPont - 2015 CCP Award Winner
Abstract » | Announcement »

Thursday, Oct. 15th, 2015Matt NeurockEngineering Molecular Transformations over Supported Metal Catalysts for the Sustainable Conversion of Biomass-Derived Intermediates to Chemicals and Fuels
Matt Neurock, University of Minnesota
Abstract » | Announcement »

Brian MurphyStudent Speaker
Selectivity Control in the Catalytic Dehydration of Methyl Lactate over Alkali-Metal Zeolites

Brian Murphy, University of Delaware |  Abstract »
Thursday, Nov. 19th, 2015John HolladayCatalysis for renewable fuels and chemicals: Challenges today and a look into where we are going
John Holladay, PNNL
Abstract » | Announcement »
Graduate Student Poster Session
Thursday, Jan. 28th, 2016Jingguang ChenCO2 Conversion via Catalysis and Electrocatalysis
Jingguang Chen, Columbia University
Abstract » | Announcement »

Student Speaker
Methanol reactivity on nanocrystalline anatase TiO2 thin films

David Bennett, University of Pennsylvania  |  Abstract »
Thursday, Feb. 18th, 2016Susannah ScottActivation and Self-Initiation in the Phillips Ethylene Polymerization Catalyst
Susannah Scott, UCSB
Abstract » | Announcement »

Student Speaker
Ethylene Polymerization by Supported CrOx/SiO2 Catalysts:
Active Sites, Surface Intermediates and Structure-Activity Relationship

Anisha Chakrabarti, Lehigh University  |  Abstract »
Officer Nominations
Thursday, Mar. 24th, 2016Bingjun XuIdentification of Active Sites for Methyl Lactate Dehydration on Faujasites
Bingjun Xu, UD
Abstract » | Announcement »
Officer Nominations
Thursday, Apr. 21st, 2016TBA
Rob Rioux, PSU
Officer Elections
Thursday, May 12th, 2016Spring Symposium
Online Dinner Reservation » | Directions to Double Tree Hotel »

2015-2016 Officers

2015-2016 Officers


Torren Carlson
Past Chair
Vladimiros Nikolakis
W.L. Gore & Associates, Inc.
Anton Petushkov
Zeolyst Inter­na­tional
Stephen Harris
Dan Slanac
Program Chair
Alan Allgeier
Arrangements Chair
Alex Mironenko
University of Delaware
Director Membership
Eric Sacia
Director Poster Session
Bingjun Xu
University of Delaware
Director Sponsorship
Pranit Metkar
Carl Menning
Representative to NACS
Dion Vlachos
University of Delaware

Insight into Supported Metal Catalyst Stability by Quantifying Thermodynamic Interactions at the Solid-liquid Interface

Meeting Program – April 2016

Robert Rioux
Robert Rioux
Friedrich G. Helfferich Associate Professor of Chemical Engineering
Pennsylvania State University

Abstract – Industrial applications of supported late transition metal catalysts demand economic and scalable synthesis of these catalysts and current synthetic methods lack precision in terms of size, shape and compositional control. Moreover, supported metal catalysts suffer from poor stability, manifested in the form of sintering (i.e., particle growth) during reaction. The proper selection of the oxide support is of great importance to ensure high dispersion, activity and selectivity of the nanoparticles. The ability of these supports to enhance the dispersion of the active metal on their surface and control their morphology and sintering kinetics is fundamentally related to the nature and strength of the metal–metal oxide interaction at the time of adsorption. In this work, we have utilized isothermal titration calorimetry (ITC), a technique capable of quantifying the thermodynamic description (ΔG, ΔH, ΔS, n (stoichiometry)) of transition metal association with a support material in a single experiment. After providing a brief introduction to ITC and methods of catalyst synthesis, we will discuss our results to quantify the electrostatic interactions between solvated transition metal ions and charged amphoteric metal oxide surface. Within this interaction-type, we have studied both refractory and reducible metal oxides. With a reducible metal oxide, ceria, we demonstrate a potentially new mechanism of adsorption, which may describe the successful stabilization of noble metals enabling maintenance of small sized nanoparticles compared to other oxide supports. In addition to ITC, bulk uptake studies have aided in quantifying the amount of metal precursor adsorbed on the support surface and equilibrium isotherms describe the uptake behavior and may provide insight for predicting long term stability of the nanoparticles. In the second half of the talk, we discuss the adsorption of transition metal oxide and hydroxide nanoparticles in the galleries of of Nb-based perovskites. ITC was used to quantitatively rank the strength of adsorption between the metal nanoparticle and their propensity to sinter, as assessed by in-situ, high-temperature transmission electron microscopy. In both examples, we will emphasize this initial interaction at the solid-liquid interface is important and conveys a history effect to the catalyst that is evident during post-processing (drying, calcination and reduction). The estimated thermodynamic parameters are expected to quantify the type of bonding at the interface, shed light on the binding mechanism and the growth and sintering kinetics of supported catalysts.
Biography – Robert (Rob) M Rioux is the Friedrich G. Helfferich Associate Professor of Chemical Engineering at the Pennsylvania State University. Prior to joining the Pennsylvania State University in 2008, he was a National Institutes of Health Postdoctoral Fellow at Harvard University in the Department of Chemistry and Chemical Biology working with Professor George Whitesides. He received his Ph.D. in physical chemistry from the University of California, Berkeley in 2006 working for Professor Gabor Somorjai. He holds a B.S. and M.S. degree in chemical engineering from Worcester Polytechnic Institute and the Pennsylvania State University, respectively. Since joining the Penn. State faculty, he has received a number of awards, including a DARPA Young Faculty Award, an Air Force Office of Scientific Research Young Investigator Program Award, a NSF CAREER Award and a 3M Non-Tenured Faculty Award. Research in his laboratory is currently sponsored by NSF, DOE-BES, DARPA, AFOSR, AFRL, ACS-PRF and industry. His group’s current research focus is on the development of spatially- and temporally-resolved spectroscopic techniques for imaging catalytic chemistry, single molecule methods to understand single molecule/particle catalytic kinetics and dynamics, elucidating reaction mechanisms in nanoscale systems, including catalyst synthesis, development of solution calorimetric techniques to understand catalytic processes at the solid-liquid interface and the development of base-metal catalysts for chemoselective chemical transformations, including biomass to chemicals conversion.

Identification of Active Sites for Methyl Lactate Dehydration on Faujasites

Meeting Program – March 2016

Bingjun Xu
Bingjun Xu
Chemical and Biomolecular Engineering
University of Delaware

Abstract – The dwindling reserve of crude oil and surge in natural gas production is rapidly changing the mix of the carbon source pool for the production of fuels and chemical feedstocks, and in turn creating shortages of several key commodity chemicals, e.g., propylene and butadiene. The shortage of certain commodity chemicals, such as propylene, drives up their prices, which in turn raises the cost of the downstream chemicals, such as acrylic acid. In this regard, lignocellulosic biomass derived feedstocks, e.g., lactic acid and its esters, can potentially bridge the gap. Currently, the commercial fermentation process using biomass-derived sugars can achieve a lactic acid (or its esters) yield of up to 90%. The absence of efficient and selective catalyst for lactic acid dehydration is the main missing link in the production of renewable acrylic acid. The primary roadblock for the rational design of catalysts for lactic acid dehydration is the lack of the mechanistic understanding of the nature of active sites and mechanistic steps leading to the selective removal of the α-hydroxyl group by dehydration. Through kinetic and in-situ spectroscopic investigations, we identify the dehydration reaction proceeds through dissociative adsorption, acid-mediated dehydration, and associative desorption steps. These mechanistic insights will guide the design of selective catalysts for this reaction.
Biography – Bingjun Xu is currently an Assistant Professor in the Department of Chemical and Biomolecular Engineering at University of Delaware. Dr. Xu received his Ph.D. in Physical Chemistry, advised by Prof. Friend, from Harvard University in 2011. His thesis established a mechanistic framework for oxidative coupling reactions on Au surface through surface science studies. Dr. Xu worked with Prof. Davis at Caltech on the development of a low temperature, manganese oxide based thermochemical cycle for water splitting. Upon finishing his postdoc, he joined University of Delaware in the fall of 2013. The current research interest of the Xu lab spans heterogeneous catalysis, electrocatalysis and in-situ spectroscopy.

Activation and Self-Initiation in the Phillips Ethylene Polymerization Catalyst

Meeting Program – February 2016

Susannah Scott
Susannah Scott
Duncan and Suzanne Mellichamp Chair in Sustainable Catalysis
Chemical Engineering and Chemistry & Biochemistry
University of California, Santa Barbara

Abstract – The mechanism of spontaneous activation of the Phillips (Cr/SiO2) ethylene polymerization catalyst in the absence of an alkylating co-catalyst is one of the longest-standing problems in heterogeneous catalysis. Experimental and computational evidence has long pointed to organochromium(III) active sites, and the preparation of grafted (SiO)2CrCH(SiMe3)2 sites by the reaction of Cr[CH(SiMe3)2]3 with partially dehydroxylated silica supports this conclusion. However, a plausible mechanism for their formation from the interaction of chromate and ethylene alone remains to be found. A key issue is the incommensurate nature of the required redox reactions, since Cr(VI) must be reduced by an odd number of electrons (three), while only closed-shell organic oxidation products are detected. For the CO-reduced catalyst, Cr K-edge XANES, EPR and UV-vis spectroscopies are consistent with initial step-wise reduction of Cr(VI) in two-electron steps, first to Cr(IV), and ultimately to Cr(II). According to Cr K-edge EXAFS and UV-vis spectroscopy, the Cr(II) sites have a coordination number higher than two, most likely through interaction with neighboring siloxane oxygens. After removal of adsorbed CO, the Cr(II) sites react with ethylene in an overall one-electron redox reaction to generate organochromium(III) sites and organic radicals.
Biography – Scott received her B.Sc. in Chemistry from the University of Alberta (Canada) in 1987, and her Ph.D. in Inorganic Chemistry from Iowa State University in 1991, where she worked with J. Espenson and A. Bakac on the activation of O2 and organic oxidation mechanisms. She was a NATO Postdoctoral Fellow with Jean-Marie Basset at the Institut de recherches sur la catalyse (CNRS) in Lyon, France, before joining the faculty of the University of Ottawa (Canada) in 1994 as an Assistant Professor of Chemistry. She held an NSERC Women’s Faculty Award, a Cottrell Scholar Award, a Union Carbide Innovation Award and was named a Canada Research Chair in 2001. She moved to the University of California, Santa Barbara in 2003, where she is currently holds the Duncan and Suzanne Mellichamp Chair in Sustainable Catalysis, with joint faculty appointments in both Chemical Engineering and Chemistry & Biochemistry. She directs the NSF-sponsored Partnership for International Research and Education in Electron Chemistry and Catalysis at Interfaces, a collaborative research program involving UCSB and several prominent catalysis research groups in China. Her research interests include surface organometallic chemistry, olefin polymerization, nanomaterials, biomass conversion, environmental catalysis and the development of new kinetic and spectroscopic methods to probe reaction mechanisms at surfaces. In 2013, Scott became an Associate Editor for the journal ACS Catalysis.