Author Archives: Carl Menning

Structure Activity Relationships in Homogeneous Catalysis

Meeting Program – September 2017

Thomas Colacot
Thomas Colacot
Technical Fellow & Global R & D Manager
Johnson Matthey

 

Abstract – Homogeneous catalysis is a molecular phenomenon, where the structure of the catalyst plays a significant role on the activity and selectivity of a catalytic reaction. Three cases studies will be discussed during the talk to explain the phenomena. The topics are

  1. High purity palladium acetate vs commercial in organic synthesis
  2. Ir pre catalysts for C-H activated borylation
  3. Generation of L1Pd(0) catalysts for advanced cross coupling.

References:

  • Book: New Trends in Cross Coupling: Theory and Applications, ed. Thomas J. Colacot, Royal Society of Chemistry, Cambridge, UK, 2015. ISBN: 978-1-84973-896-5
  • Carin C. C. Johansson Seechurn, Thomas Sperger, Theresa. G. Scrase, Franziska. Schoenebeck and Thomas. J. Colacot*, J. Am. Chem. Soc., 2017 (DOI: 10.1021/jacs.7b01110). This work was featured in the April 5 th issue of C & EN. Please see: http://acsmeetings.cenmag.org/chemists-get-better-acquainted-with-palladium-catalysts/
  • William A. Carole and Thomas J. Colacot* Chem. Eur. J, 2016, 22, 7686 (with journal cover graphics – this work was featured in C & EN. page 20, May 2 nd, 2016)
  • Peter G. Gildner, Andrew DeAngelis, and Thomas J. Colacot*, Org. Lett., 2016, 18 (6), 1442–1445 DOI: 10.1021/acs.orglett.6b0037
  • William A. Carole, Jonathan Bradley, Misbah Sarwar and Thomas J. Colacot* Org. Lett., 2015, 17 (21), 5472–5475. DOI: 10.1021/acs.orglett. 5b02835
  • Thomas. J. Colacot, Angew Chem. Int. Ed. 2016, 54, 15611-15612.
  • Peter G. Gildner and Thomas J. Colacot* Organometallics, 2015, 34 (23), 5497–5508. DOI: 10.1021/acs.organomet.5b00567
  • Andrew J. DeAngelis , Peter G. Gildner , Ruishan Chow , and Thomas J. Colacot* J. Org. Chem., 2015, 80 (13), pp 6794–6813, DOI: 10.1021/acs.joc.5b01005
  • Carin C. C. Johansson Seechurn, Vilvanathan Sivakumar, Deepak Satoskar and Thomas J. Colacot*, Organometallics, 2014, 33, 3514−3522.

Biography – Dr. Thomas J. Colacot received his Ph.D. in Chemistry from IIT Madras in 1989, following a B.Sc. and M.Sc. in Chemistry from the University of Kerala in 1981 and 1983, respectively. After his doctoral and post-doctoral studies in the US, Dr. Colacot went on to pursue an education in management, acquiring an MBA from Pennsylvania State University in 2005, while working at Johnson Matthey. Before joining Johnson Matthey in 1995, Dr. Colacot had also worked as a Research Associate Southern Methodist University (TX, USA) on a project funded by Advanced Technology Program, as an Assistant Professor at Florida A&M University, and as a Post-Doctoral/Teaching Fellow at University of Alabama. Having climbed up the ranks from Development Associate (bench chemist), Dr. Colacot is currently the Technical Fellow at Johnson Matthey, USA, the highest technical rank for a scientist with reports from different parts of the world.

As a researcher, Dr. Colacot has focused on many areas of homogenous catalysis, particularly becoming proficient in palladium-catalyzed cross-coupling. He also has extensive experience in organometallic and organic syntheses, and in process chemistry. His work is reflected in several patents to his name, more than one hundred peer-reviewed publications, and numerous invited lectures and seminars spanning India, USA, China, and Europe. His recently edited book: New Trends in Cross Coupling: Theory and Applications by the Royal Society of Chemistry is widely used in academia and industry. Through his work, Dr. Colacot is credited with being a leading influence in developing exceptional catalytic systems for the advancement of metal-catalyzed synthetic organic chemistry for real world applications such as drug development, OLED’s/liquid crystals and agriculture. His emphasis in designing catalysts and catalytic processes has been on their applicability in industrial settings, particularly pertaining to agriculture, electronics and medicine. He is the finest example of a link between academia and industry.

Dr. Colacot’s contributions to the field have resulted in many awards and accolades, amongst them the recent prestigious IIT Madras 2016 Distinguished Alumnus Award for Technology Innovations and Chemical Research Society of India (2016 CRSI) Medal for outstanding contributions in Organometallics and Homogeneous Catalysis. He is the first Indian to be awarded the American Chemical Society (ACS) National Award in Industrial Chemistry in 2015. He also received the 2015 IPMI Henry Alfred Award (2015) from the International Precious Metal Institute, sponsored by the BASF. In 2014 he received the Indian American Kerala Culture and Civic Center Award for his outstanding contributions in Applied Sciences. In addition, he received Royal Society of Chemistry 2012 Applied Catalysis Award and Medal. He is also a Fellow of the Royal Society of Chemistry, UK.

2017 Spring Symposium

8:00 AMRegistration / Breakfast
8:55 AMOpening Remarks
9:00 AMEmerging Challenges In Catalysis For Sustainable Production Of Transport Fuels: An Industrial View
Dr. John Shabaker, BP Products North America
Abstract »
9:40 AMScience And Technology Of Framework Metal-Containing Molecular Sieves Catalysts
Prof. Laszlo Nemeth, University of Nevada, Las Vegas
Abstract »
10:20 AMCoffee Break
10:40 AMSynthesis Of Zincosilicate Catalysts For The Oligomerization Of Propylene
Dr. Mark Deimund, ExxonMobil Research and Engineering Company
Abstract »
11:20 AMZeolite Catalysis With A Focus on Downstream Refining Applications
Dr. C.Y. Chen, Chevron Energy Technology Company
Abstract »
12:00 PMLunch
1:20 PMContinuous Reactors For Homogeneous Catalysis In Pharmaceutical Manufacturing
Dr. Martin Johnson, Eli Lilly and Company
Abstract »
2:00 PMMechanisms And Materials For Alkaline Hydrogen Electrocatalysis
Prof. Maureen Tang, Drexel University
Abstract »
2:40 PM Award Announcement
2:55 PMCoffee Break
3:15 PMProduction Of para-Methylstyrene And para-Divinylbenzene From Furanic Compounds
Maura Koehle, University of Delaware (Student Poster Award Speaker)
Abstract »
3:35 PMDesign Of Complex Metal/Metal-oxide Heterogeneous Catalytic Materials For Energy And Chemical Conversion
Prof. Eranda Nikolla, Wayne State University
Abstract »
4:15 PMThe Mechanism Of CO2 Reduction Over Pd/Al2O3: A Combined Steady State Isotope Transient Kinetic Analysis (SSITKA) And Operando FTIR Investigation
Dr. János Szanyi, Pacific Northwest National Laboratory
Abstract »
4:55 PMClosing Remarks
5:00 PMConference Adjourns

2016 Spring Symposium

8:00 AMRegistration / Breakfast
8:50 AMOpening Remarks
9:00 AMScience and Serendipity in Heterogeneous Catalysis Research
Ive Hermans, University of Wisconsin - Madison
9:40 AMHydrogen Spillover to Carbon Supports: Bridging the Gap Between Experiment and Theory
Angela Lueking, Pennsylvania State University
10:20 AMCoffee Break
10:40 AMDesign and Synthesis of Nanostructured Carbide and Nitride Based Catalysts
Levi Thompson, University of Michigan - Ann Arbor
11:20 AMMicrolith Coated Mesh Substrates for Process Intensification
Jeffrey Weissman, Precision Combustion
12:00 PMLunch
1:20 PMCatalytic Conversion of Sour Natural Gas into Value Added Fuels and Chemicals
Jonas Baltrusaitis, Lehigh University
2:00 PMSerendipitous Discovery of a Nano-structured Yttrium Oxychloride Catalyst for the Selective Dehydration of Phenol
David Barton, Dow Chemical Co.
2:40 PMCoffee Break
3:00 PM Award Announcement
3:20 PMStabilization of Metastable Oxides via Surface Modification
Daniel Gregory, Lehigh University
3:40 PMControlling the Al Distribution and Cu Speciation and Proximity in Cu-SSZ-13 Zeolites: Consequences for NOx SCR Catalysis
Raj Gounder, Purdue University
4:20 PMClosing Remarks
4:30 PMConference Adjourns

2016-2017 Meeting Program

Thursday, Sept. 15th, 2016Dion VlachosIn Silico Prediction of Materials for Energy Applications
Dion Vlachos, University of Delaware - 2016 CCP Award Winner
Abstract » | Announcement »


Thursday, Oct. 27th, 2016Keiichi TomishigeDevelopment of heterogeneous catalysts for the production of biomass-derived chemicals by selective C-O hydrogenolysis and deoxydehydration
Keiichi Tomishige, Tohoku University
Abstract » | Announcement »


Student Speaker
Thursday, Nov. 10th, 2016Ravindra DattaUnraveling Catalytic Mechanisms and Kinetics: Lessons from Electrical Networks
TBA
Ravindra Datta, Worcester Polytechnic Institute
Abstract » | Announcement »
 
Graduate Student Poster Session
Thursday, Jan. 19th, 2017Ahmad MoiniCiapetta Award Lecture:
Novel Zeolite Catalysts for Diesel Emission Applications

Ahmad Moini, BASF
Abstract » | Announcement »



Student Speaker
Thursday, Feb. 16th, 2017Raul LoboBiomass and Natural Gas Valorization by Zeolite Catalysis
Raul Lobo, University of Delaware
Abstract »

Student Speaker
 
Officer Nominations
Thursday, Mar. 16th, 2017Manuela SerbanParallel between UOP’s Reforming and Dehydrogenation Technologies and Catalysts
Manuela Serban, Honeywell (UOP)
Abstract »
 
Officer Nominations
Thursday, Apr. 20th, 2017Avelino CormaSolid Catalysts Design: From Fundamental Knowledge To Catalytic Application
Avelino Corma, Instituto de Tecnología Química
Abstract »  |  Announcement »
 
Officer Elections
May 2017Spring Symposium
Online Dinner Reservation » | Directions to Double Tree Hotel »

2016-2017 Officers

2016-2017 Officers

 

Chair
Anton Petushkov
Zeolyst Inter­na­tional
anton.​petushkov@​pqcorp.​com
Past Chair
Torren Carlson
DuPont
torren.r.carlson@dupont.com
Chair-Elect
Josh Pacheco
Zeolyst Inter­na­tional
josh.pacheco@​pqcorp.​com
Treasurer
Lifeng Wang
Zeolyst International
lifeng.wang@pqcorp.com
Secretary
Dan Slanac
DuPont
daniel.a.slanac@dupont.com
Program Chair
Istvan Halasz
Zeolyst International
istvan.halasz@pqcorp.com
Arrangements Chair
Tzia Ming
University of Pennsylvania
tonn@seas.upenn.edu
Director Membership
Jacob Dickinson
DuPont
jacob.g.dickinson@dupont.com
Director Poster Session
Eric Sacia
DuPont
eric.r.sacia@dupont.com
Director Sponsorship
Thomas Yeh
Johnson Matthey
thomas.yeh@jmusa.com
Webmaster
Carl Menning
Sentry Data Systems
amenning@sentryds.com
Representative to NACS
Dion Vlachos
University of Delaware
vlachos@udel.edu

Production of para-methylstyrene and para-divinylbenzene from furanic compounds

2017 Spring Symposium

Molly Koehle and Raul Lobo, Chemical and Biomolecular Engineering, University of Delaware, Newark, DE

Abstract – Of the three isomers of methylstyrene, para-methylstyrene is highly desirable because it yields polymers with superior properties over polystyrene and mixed poly-methylstyrene [1]. However, controlling the substitution of methylstyrene via direct acylation or alkylation of toluene is difficult because even though the para isomer is favored, meta and ortho isomers are also formed [1, 2], and separation of the isomer mixture is very difficult due to their nearly identical properties.

The Diels-Alder cycloaddition and dehydration of substituted furans with ethylene is a plausible route to p-methylstyrene since it is inherently selective to para aromatic species. We have successfully developed a three-step catalytic route to p-methylstyrene from methylfuran (Scheme 1) at high yield and very high isomer selectivity. The process uses Friedel-Crafts acylation, selective reductions with hydrogen and Diels-Alder cycloaddition with ethylene. The raw materials—furans, ethylene and acetic acid—can all be derived from biomass [3,4], thus allowing ‘green’ styrene production from renewable carbon sources. This approach has also been extended to the production of p-divinylbenzene. As the acylation step is known to be catalyzed by Lewis acids, recent work has focused on studying this step on Brønsted and Lewis acid zeolites and will be presented as well.

Scheme 1: Production of para-methylstyrene from methylfuran

References:
[1] W.W. Kaeding and G.C. Barile, in: B.M. Culbertson and C.U. Pittman, Jr. (Eds.), New Monomers and Polymers, Plenum Press, New York, NY, 1984, pp. 223-241.
[2]“Aromatic Substitution Reactions.” http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/benzrx1.htm
[3] A.A. Rosatella; S.P. Simeonov; R.F.M. Frade, R.F.M..; C.A.M. Afonso, Green Chem., 13 (2011) 754.
[4] C.H. Christensen; J. Rass-Hansen; C.C. Marsden; E. Taarning; K. Egeblad, ChemSusChem, 1 (2008) 283.

Biography – Molly obtained her B.S. in Chemical Engineering from the University of Pittsburgh and her M.S. in Chemical Engineering from the University of Connecticut. She has worked at the Catalysis Center for Energy Innovation in Prof. Raul Lobo’s group since 2013. Her work focuses on transformations of biomass to fuels and chemicals with Bronsted and Lewis acid zeolites.

The mechanism of CO2 reduction over Pd/Al2O3: a combined steady state isotope transient kinetic analysis (SSITKA) and operando FTIR investigation

2017 Spring Symposium

Xiang Wang, Hui Shi and János Szanyi, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA

Abstract – Understanding the critical steps involved in the heterogeneous catalytic CO2 reduction has attracted a lot of attention recently. In order to fully understand the mechanism of this reaction the determination of both the rate-determining steps and reaction intermediates are vital. Steady-State Isotopic Transient Kinetic Analysis (SSITKA) is one of the most powerful techniques used to investigate the elementary steps under steady-state reaction conditions. This technique provides valuable information on mean resident lifetime of surface intermediates, surface concentrations of adsorbed reactant species and an upper bound of the turnover frequency. Coupling SSITKA with operando-FTIR spectroscopy allows us to discriminate between active and spectator species present on the catalytic surface under steady state reaction conditions.  In the present work operando SSITKA experiments coupled with transmission FTIR, mass spectrometry (MS) and gas chromatography (GC) were performed to probe both the chemical nature and kinetics of reactive intermediates over a Pd-Al2O3 catalysts and provide a clear mechanistic picture of the CO2 hydrogenation reaction by revealing the rate-determining steps for CH4 and CO production.

Figure 1 shows normalized real-time signals for the decay and increase of methane (a) and carbon-monoxide (b) in the effluent at 533 K reaction temperature after the feed gas was switched at 0 s from CO2/H2/Ar mixture to 13CO2/H2 mixture.  With increasing temperature, the decay of CH4 and CO get faster.  By integration under the decay curves , the mean surface-residence times CH4 and  CO), the abundance of adsorbed surface intermediates leading to CH4 and CO products  CH4 and  CO) at 533-573 K were calculated. At low temperature, CO2 methanation is slower than the reverse water-gas shift reaction, but became faster as the temperature was increased over 563 K.  The similar apparent activation energies obtained for the hydrogenation of adsorbed CO and for the formation of CH4 indicates that the hydrogenation of CO is the rate-determining step during the CO2 methanation reaction. Moreover, the similar apparent activation energies estimated for the consumption of adsorbed formates (FTIR) and for the formation of CO (MS), indicates that the H-assisted decomposition of formates is the rate determining step in the reverse water gas shift reaction.  The rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivities to CH4 and CO. We applied this knowledge to design catalysts and achieved high selectivities to desired products. 


Figure 1. Normalized response of (a) CH4 and 13CH4 products and (b) CO and 13CO products as functions of time.

Biography – Dr. Szanyi`s research is focused on surface science, spectroscopy and kinetic studies on heterogeneous catalytic reaction systems aimed at understanding structure-reactivity relationships. In particular, he is interested in understanding the mechanistic consequences of very high (atomic) metal dispersion on different support materials. Using a series of ensemble averaged spectroscopy methods he investigates the fundamental properties of metal atoms and small metal clusters prepared under well controlled UHV conditions. These results provide information on the energetics of the interactions between highly dispersed metals and selected probe molecules. Applying in situ RAIR spectroscopy they study the binding configurations of adsorbates to metals, and identify surface species present on the metal and support materials under elevated reactant pressures. Simultaneously, they are conducting detailed kinetics and operando spectroscopy measurements on model high surface area supported metal catalysts using flow reactors and SSITKA/FTIR/MS techniques. These measurements provide detailed kinetic information together with surface speciation that allow them to greatly enhance our mechanistic understanding of heterogeneous catalytic systems, in particular the reduction of CO2. Dr Szanyi is also involved in research related to the fundamental understanding of automotive emission control catalysis, conducting research in selective catalytic reduction of NOx on zeolite-based catalysts, low temperature NO and CO oxidation on metal oxides, and low temperatures NOx and HC storage in zeolites.