August 2014 - Che-courtesy-list

Amir Gharachorlou dissertation defense is Tuesday, 8/19, at 10:00 a.m. in B124
by Field, Catherine A 17 Aug '14

17 Aug '14

This e-mail is to announce that Amir Gharachorlou will be defending his dissertation, Surface Science Approach To Atomic Layer Deposition Chemistry, on Tuesday, August 19th, at 10:00 a.m. in FRNY B124. The dissertation is being directed by Dr. Ribeiro, and the abstract is attached. All are welcome to attend. Catherine Field, Ph.D. Graduate Program Administrator School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette, IN 47906 E-mail: field2(a)purdue.edu<mailto:field2@purdue.edu> Phone: 765-494-4057 Fax: 765-494-0805 www.engineering.purdue.edu/ChE<http://www.engineering.purdue.edu/ChE>

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School Calendar and Updated School Service Assignments 2014-15
by Murray, Chris L 15 Aug '14

15 Aug '14

The school calendar and an updated list of school service assignments are attached (the only change is an addition to the international programs committee). I'll send a revised school calendar when the graduate, graduate recruiting, and undergraduate committee meeting schedules are finalized. Please let me know if any changes need to be made. Thanks, Chris

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Anuj Verma Dissertation Defense is Tuesday, 8/19, at 2:00 p.m. in B124
by Field, Catherine A 13 Aug '14

13 Aug '14

This e-mail is to announce that Anuj Verma will be defending his dissertation, Fundamental Studies on Copper Zeolites for Catalytic NOx Abatement, on Tuesday, August 19th, at 2:00p.m. in FRNY B124. The dissertation is being co-directed by Dr. Ribeiro and Dr. Delgass, and the abstract is below. All are welcome to attend. Abstract: Stringent regulations in mobile NOx emissions have resulted in the development of Standard Selective Catalytic Reduction (SCR) as the dominant NOx abatement technology in lean burn diesel engines. Standard SCR is a reaction of nitric oxide (NO) with ammonia (NH3), in the presence of oxygen (O2) to form nitrogen (N2) and water (H2O). Copper containing zeolites show commercially viable SCR performance. Cu-SSZ-13 (CHA framework), a member of this family, is a preferred catalyst for SCR applications because it shows exceptional hydrothermal stability in addition to commercially viable SCR performance. Our work focuses on 1) determination of the active sites, and 2) elucidation of the dominant reaction steps on active sites, for standard SCR (at 473 K) and catalytic oxidation of NO (at 550 K), over Cu-SSZ-13. A series of Cu-SSZ-13 catalysts (Si:Al = 4.5) tested for standard SCR kinetics exhibited a linear increase in the rate of nitrogen production (per gram catalyst) with Cu:Al ratio till Cu:Al = 0.2. Separate catalyst characterization tools like Ultra-Violet-Visible-Near Infra-red (UV-Vis-NIR) spectroscopy under ambient conditions, X-ray Absorption Near Edge structure (XANES) of Cu ions during standard SCR, Density Functional Theory (DFT) calculations, and titration of residual acid sites with amine titrants on this series of catalysts established isolated Cu ions ion exchanged at the framework Al sites in six member rings of SSZ-13 as the dominant Cu ion configuration below Cu:Al = 0.2, which we assign as the dominant active sites for low temperature standard SCR (T = 473 K). Above Cu:Al = 0.2, Cu ion clusters (CuxOy) were formed, which stabilized on framework Al sites at favorable distances, in the eight member cage of SSZ-13. CuxOy was active in catalyzing dry NO oxidation to NO2 via oxygen activation mediated by local Cu-Oy-Cu bonds. The density of local Cu-Oy-Cu bonds was quantified from in-situ XANES under NO oxidation and correlated linearly with the rate of NO oxidation, thereby establishing CuxOy as the active sites for NO oxidation. NO oxidation was also explored on catalysts prepared to contain exclusively isolated Cu(II) ions and the Gibbs free energy of reaction intermediates was shown to be higher than the free energy of similar intermediates formed from local Cu-Oy-Cu bonds, consistent with the experimental observation of experimentally undetectable rate of NO oxidation on isolated Cu(II) ions in the six member rings of SSZ-13. As a result, dry NO oxidation is proposed as a probe reaction to detect Cu ion clustering in Cu-SSZ-13 formulations. Operando XANES during standard SCR also implicated isolated Cu ions (in the six member SSZ-13 ring) as the active site; however, the +2 oxidation state of Cu is not preserved. Experimental XANES analysis during appropriate reactant cutoff from steady state standard SCR and DFT calculated Gibbs free energy analysis of adsorbates under reaction conditions point toward a Cu ion redox between Cu(I) and Cu(II) to mediate standard SCR. The isolated Cu(II) ion reduction is achieved by both NO and NH3 to make nitrogen, isolated Cu(I) ions, and experimentally detectable proximal Brønsted acidic sites. These proximal acid sites can stabilize ammonium ions during standard SCR catalysis, while NO and O2 oxidize the Cu(I) back to Cu(II) via nitrite (NO2-) intermediate formation, as predicted by DFT. The close proximity between nitrites (on Cu) and ammonium ions (on proximal Brønsted acid sites) enable the formation of nitrogen and water via an intermediate which resembles ammonium nitrite, thereby completing the catalytic cycle. These findings highlight the bi-functional nature of Cu-SSZ-13 displayed by a close proximity of Bronsted acidic sites and redox metal ion centers which work in concert to catalyze the selective reduction of NO with NH3 in the presence of oxygen, to form nitrogen and water. Catherine Field, Ph.D. Graduate Program Administrator School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette, IN 47906 E-mail: field2(a)purdue.edu<mailto:field2@purdue.edu> Phone: 765-494-4057 Fax: 765-494-0805 www.engineering.purdue.edu/ChE<http://www.engineering.purdue.edu/ChE>

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Re: [ChE-Courtesy-list] Active Shooter Presentation-today at 11 am
by Nagy, Gabriela 13 Aug '14

13 Aug '14

Hello Everyone, This is a reminder that the "Active Shooter" presentation is scheduled for TODAY at 11 am in FRNY G140. I encourage everyone to attend! Sincerely, Gabriela On behalf of the ChE Safety Committee From: Nagy, Gabriela Sent: Tuesday, August 12, 2014 2:27 PM To: 'chme(a)ecn.purdue.edu'; 'chmegrad(a)ecn.purdue.edu' Subject: Active Shooter Presentation Importance: High Hello Everyone, This is a reminder that Lt. Keene Red-Elk from the Purdue Police Department will present for our School on how to deal in case of an active shooter on campus. His presentation is scheduled for tomorrow, Wednesday, August 13 from 11 am in FRNY G140. I encourage everyone to attend. Sincerely, Gabriela On behalf of the ChE Safety Committee ________ Gabriela Nagy, PhD Industrial Education Director ChE Safety Committee Chair School of Chemical Engineering Room FRNY G051 Purdue University Tel: (765)-496-1710 E-mail: nagyg(a)purdue.edu<mailto:nagyg@purdue.edu> From: Nagy, Gabriela Sent: Thursday, August 07, 2014 2:51 PM To: 'chme(a)ecn.purdue.edu'; 'chmegrad(a)ecn.purdue.edu' Cc: Red Elk, Keene L Subject: Active Shooter Presentation Importance: High Hello Everyone, This is just a gentle reminder that Lt. Keene Red-Elk from the Purdue Police Department will present for our School on how to deal in case of an active shooter on campus. His presentation is scheduled for next week on Wednesday, August 13, from 11 am in FRNY G140. Please attend. Sincerely, Gabriela On behalf of the ChE Safety Committee ________ Gabriela Nagy, PhD Industrial Education Director ChE Safety Committee Chair School of Chemical Engineering Room FRNY G051 Purdue University Tel: (765)-496-1710 E-mail: nagyg(a)purdue.edu<mailto:nagyg@purdue.edu> From: Nagy, Gabriela Sent: Wednesday, June 18, 2014 4:59 PM To: chme(a)ecn.purdue.edu<mailto:chme@ecn.purdue.edu>; chmegrad(a)ecn.purdue.edu<mailto:chmegrad@ecn.purdue.edu> Cc: Red Elk, Keene L Subject: Save the date - Active Shooter Presentation Hello Everyone, Lt. Keene Red-Elk from the Purdue Police Department agreed to present exclusively for us on how to deal in case of an active shooter on campus. This presentation is scheduled for Wednesday, August 13, from 11 am in FRNY G140. More details nearer the time, but for now please save the date! Sincerely, Gabriela On behalf of the ChE Safety Committee ________ Gabriela Nagy, PhD Industrial Education Director ChE Safety Committee Chair School of Chemical Engineering Room FRNY G051 Purdue University Tel: (765)-496-1710 E-mail: nagyg(a)purdue.edu<mailto:nagyg@purdue.edu>

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Dhairya Mehta Dissertation Defense on Friday 8/15 at 1:00 p.m.
by Field, Catherine A 13 Aug '14

13 Aug '14

Hello Everyone, There was an error in my earlier announcement of Dhairya Mehta's upcoming defense. His dissertation is being co-directed by both Dr. Ribeiro and Dr. Agrawal. I apologize for the error, and please see the corrected announcement below. Thank you. Best, Katie This e-mail is to announce that Dhairya Mehta will be defending his dissertation, Kinetic Studies of Model Reactions to Transform Biomass into Fuels, on Friday, August 15th, at 1:00p.m. in FRNY G124. The dissertation is being co-directed by Dr. Ribeiro and Dr. Agrawal, and the abstract is below. All are welcome to attend. Abstract: Second-generation biofuels utilizing lignocellulosic biomass are considered to be a promising alternative to fossil-based fuels. Lignocellulosic biomass is structurally diverse and therefore requires detailed understanding of the thermal depolymerization and catalytic hydrodeoxygenation reactions to optimize the overall process. This dissertation describes experimental work using model compounds to elucidate the role of bimetallic catalysts and control of the reaction operating parameters such as temperature and hydrogen pressure to maximize energy recovery in the liquid product from biomass resources. Fast-hydropyrolysis of biomass followed by in-line catalytic hydrodeoxygenation has been shown to have the potential to produce hydrocarbon fuels using hydrogen as a co-feed. The objective of the research project was to identify and quantify the primary products of fast hydropyrolysis as well as to establish the effect of temperature on the overall product distribution. A torch igniter, typically used in rocket engines, was modified to design a reactor that is able to continuously feed biomass at a gram per minute scale and complete the entire process from fast hydropyrolysis to condensation of bio-oil in less than about 70 ms at 3.6 MPa hydrogen pressure. The identification and quantification of products with molecular weight higher than the monomer (levoglucosan) at 70 ms residence time compared to their absence in reactors with residence time of 2-3 s indicate that levoglucosan is not the sole primary product of cellulose pyrolysis. Thus a portion of levoglucosan is a result of dimer (cellobiosan) and trimer (cellotriosan) degradation. Catalytic hydrodeoxygenation is used to selectively remove oxygen as water and thus transform the oxygenated organic compounds to fungible hydrocarbon fuels. Furfural and dihydroeugenol were the chosen model compounds to represent the cellulose and lignin fractions of biomass. Discerning the role of catalyst descriptors and hydrogen pressure were the main goals of this study. A bimetallic catalyst system comprising platinum as a hydrogenation function and molybdenum as an oxophilic promoter supported on multi-walled carbon nanotubes (MWCNT) was used to achieve 100% hydrodeoxygenation of dihydroeugenol resulting in >96% yield of C9 aromatic and saturated hydrocarbons. At 0.1 MPa hydrogen pressure, direct deoxygenation of the phenolic hydroxyl group to produce propylbenzene was the dominant pathway, whereas at higher hydrogen pressures (0.7 and 2.4 MPa), aromatic ring hydrogenation followed by dehydration took precedence yielding propylcyclohexane as the major product. In the case of furfural, increasing the hydrogen pressure from 0.1 to 1.9 MPa resulted in an increase of C5 product selectivity from ~25% to ~80% at a conversion of 18%. Scanning transmission electron microscopy combined with electron energy loss spectroscopic analysis on the 5%Pt-2.5%Mo/MWCNT revealed that 77% of nanoparticles were bimetallic Pt-Mo. X-ray absorption spectroscopy also confirmed the presence of Pt-Mo alloy and that Mo was partially reduced with an average oxidation state between 0 and +4. Combination of results from catalyst characterization and kinetic studies over a series of Pt-Mo catalysts suggest that the overall site time yield was proportional to Pt loading, whereas the selectivity toward C-O scission products increased as the relative Mo to Pt ratio increased. Catherine Field, Ph.D. Graduate Program Administrator School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette, IN 47906 E-mail: field2(a)purdue.edu<mailto:field2@purdue.edu> Phone: 765-494-4057 Fax: 765-494-0805 www.engineering.purdue.edu/ChE<http://www.engineering.purdue.edu/ChE>

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Updated Guide to Graduate Studies on ChE Website
by Field, Catherine A 12 Aug '14

12 Aug '14

Hello Everyone, This is just a note to let you know that Dr. Morgan and I updated the Guide to Graduate Studies, and the updated Guide is now on our website (see link below). https://engineering.purdue.edu/ChE/Academics/Graduate/index.html Grad Students: For those of you planning to take your Quals or Prelims, please review the relevant sections in the Guide since we extensively updated those sections to make exam procedures and requirements more clear. I will also send general e-mail reminders to those of you taking exams this semester (Quals, Prelims, and Finals), and of course, please contact me if you have any questions. Thank you. Best, Katie Catherine Field, Ph.D. Graduate Program Administrator School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette, IN 47906 E-mail: field2(a)purdue.edu<mailto:field2@purdue.edu> Phone: 765-494-4057 Fax: 765-494-0805 www.engineering.purdue.edu/ChE<http://www.engineering.purdue.edu/ChE>

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Dhairya Mehta Dissertation Defense on Friday, August 15th, at 1:00 p.m. in G124
by Field, Catherine A 12 Aug '14

12 Aug '14

This e-mail is to announce that Dhairya Mehta will be defending his dissertation, Kinetic Studies of Model Reactions to Transform Biomass into Fuels, on Friday, August 15th, at 1:00p.m. in FRNY G124. The dissertation is being directed by Dr. Ribeiro, and the abstract is below. All are welcome to attend. Abstract: Second-generation biofuels utilizing lignocellulosic biomass are considered to be a promising alternative to fossil-based fuels. Lignocellulosic biomass is structurally diverse and therefore requires detailed understanding of the thermal depolymerization and catalytic hydrodeoxygenation reactions to optimize the overall process. This dissertation describes experimental work using model compounds to elucidate the role of bimetallic catalysts and control of the reaction operating parameters such as temperature and hydrogen pressure to maximize energy recovery in the liquid product from biomass resources. Fast-hydropyrolysis of biomass followed by in-line catalytic hydrodeoxygenation has been shown to have the potential to produce hydrocarbon fuels using hydrogen as a co-feed. The objective of the research project was to identify and quantify the primary products of fast hydropyrolysis as well as to establish the effect of temperature on the overall product distribution. A torch igniter, typically used in rocket engines, was modified to design a reactor that is able to continuously feed biomass at a gram per minute scale and complete the entire process from fast hydropyrolysis to condensation of bio-oil in less than about 70 ms at 3.6 MPa hydrogen pressure. The identification and quantification of products with molecular weight higher than the monomer (levoglucosan) at 70 ms residence time compared to their absence in reactors with residence time of 2-3 s indicate that levoglucosan is not the sole primary product of cellulose pyrolysis. Thus a portion of levoglucosan is a result of dimer (cellobiosan) and trimer (cellotriosan) degradation. Catalytic hydrodeoxygenation is used to selectively remove oxygen as water and thus transform the oxygenated organic compounds to fungible hydrocarbon fuels. Furfural and dihydroeugenol were the chosen model compounds to represent the cellulose and lignin fractions of biomass. Discerning the role of catalyst descriptors and hydrogen pressure were the main goals of this study. A bimetallic catalyst system comprising platinum as a hydrogenation function and molybdenum as an oxophilic promoter supported on multi-walled carbon nanotubes (MWCNT) was used to achieve 100% hydrodeoxygenation of dihydroeugenol resulting in >96% yield of C9 aromatic and saturated hydrocarbons. At 0.1 MPa hydrogen pressure, direct deoxygenation of the phenolic hydroxyl group to produce propylbenzene was the dominant pathway, whereas at higher hydrogen pressures (0.7 and 2.4 MPa), aromatic ring hydrogenation followed by dehydration took precedence yielding propylcyclohexane as the major product. In the case of furfural, increasing the hydrogen pressure from 0.1 to 1.9 MPa resulted in an increase of C5 product selectivity from ~25% to ~80% at a conversion of 18%. Scanning transmission electron microscopy combined with electron energy loss spectroscopic analysis on the 5%Pt-2.5%Mo/MWCNT revealed that 77% of nanoparticles were bimetallic Pt-Mo. X-ray absorption spectroscopy also confirmed the presence of Pt-Mo alloy and that Mo was partially reduced with an average oxidation state between 0 and +4. Combination of results from catalyst characterization and kinetic studies over a series of Pt-Mo catalysts suggest that the overall site time yield was proportional to Pt loading, whereas the selectivity toward C-O scission products increased as the relative Mo to Pt ratio increased.

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Active Shooter Presentation
by Nagy, Gabriela 12 Aug '14

12 Aug '14

Hello Everyone, This is just a gentle reminder that Lt. Keene Red-Elk from the Purdue Police Department will present for our School on how to deal in case of an active shooter on campus. His presentation is scheduled for next week on Wednesday, August 13, from 11 am in FRNY G140. Please attend. Sincerely, Gabriela On behalf of the ChE Safety Committee ________ Gabriela Nagy, PhD Industrial Education Director ChE Safety Committee Chair School of Chemical Engineering Room FRNY G051 Purdue University Tel: (765)-496-1710 E-mail: nagyg(a)purdue.edu<mailto:nagyg@purdue.edu> From: Nagy, Gabriela Sent: Wednesday, June 18, 2014 4:59 PM To: chme(a)ecn.purdue.edu; chmegrad(a)ecn.purdue.edu Cc: Red Elk, Keene L Subject: Save the date - Active Shooter Presentation Hello Everyone, Lt. Keene Red-Elk from the Purdue Police Department agreed to present exclusively for us on how to deal in case of an active shooter on campus. This presentation is scheduled for Wednesday, August 13, from 11 am in FRNY G140. More details nearer the time, but for now please save the date! Sincerely, Gabriela On behalf of the ChE Safety Committee ________ Gabriela Nagy, PhD Industrial Education Director ChE Safety Committee Chair School of Chemical Engineering Room FRNY G051 Purdue University Tel: (765)-496-1710 E-mail: nagyg(a)purdue.edu<mailto:nagyg@purdue.edu>

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Phone List
by Akers, Christa N 12 Aug '14

12 Aug '14

Hello, Here is an up to date phone list attached. Thank you The Sky is the limit just reach for it and see how far you can go! Christa N. Akers Secretary room 1060 Forney Hall of Chemical Engineering 408 Stadium Mall Dr. West Lafayette, IN 47907 765-494-4050 cakers(a)purdue.edu

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Jeff Switzer's defense is Thursday, August 14th, at 2:00 p.m. in 3062A
by Field, Catherine A 11 Aug '14

11 Aug '14

This e-mail is to announce that Jeffrey Switzer will be defending his dissertation, Quantitative Kinetic Analysis of Olefin Polymerization by Single-Site Group IV Amine Bis-Phenolate Catalysts, on Thursday, August 14th , at 2:00PM in FRNY 3062A. The dissertation is being directed by Dr. Caruthers and Dr. Thomson, and the abstract is below. All are welcome to attend. Abstract: Polymerization by homogeneous single-site catalysts is a recent and growing area of research. While single-site catalysts are typically not as fast as heterogeneous ones, their major advantage is that the kinetic rate constants may be manipulated through precise changes to the catalyst structure and reaction conditions. Such a process yields tailored polymers not generally available through heterogeneous catalysis. Two breakthroughs are needed in this field in order to achieve this goal: (i) reliable rate constants must come from experimental data, and (ii) correlations between rate constants and chemical structure must be discovered. At present, the majority of new single-site catalysts are reported without detailed kinetic parameters, in part due to the complexity of simultaneously modeling all polymerization data. The purpose of this body of work is in part to discuss the complex process of kinetic modeling in the context of single-site polymerization in order to promote this activity by other researchers. To this end, kinetic modeling has been performed for a number of single-site catalyst systems. The Group IV amine bisphenolate catalysts studied are all similar in structure except for the metal (Zr or Hf) and the pendant donor arm (THF, pyridine, NMe2, furan, or SMe). The similar systems were chosen in order to probe how these small changes affect the kinetic rate constants. It was found that the donor arm has a large effect on the rate of chain transfer of the polymer, changing the rate by 1-2 orders of magnitude depending on the system. Meanwhile, the metal has a large effect on the propagation rate constant, with the rate constants in Zr faster than those in Hf by an order of magnitude. The temperature dependence of the rate constants was also examined for selected catalysts (Zr metal with THF, NMe2, and SMe pendants). The key findings were: (i) lower temperatures were discovered to prefer monomer dependent chain transfer while higher temperatures prefer monomer independent chain transfer, and (ii) reactions with sterically bulky active sites have high entropies but low enthalpies of activation, while less sterically hindered active sites have low entropies but high enthalpies of activation. These results allow for the possibility to manipulate the kinetic mechanism and can direct future catalyst and experiment design in order to engineer desired polymer products.

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