2010 Spring Symposium

 
Paul J. Dauen­hauer
Uni­ver­si­ty of Mass­a­chu­setts, Amherst


Abstract — Par­ti­cles of micro­crys­talline cel­lu­lose approx­i­mate­ly 300 µm in diam­e­ter ther­mal­ly decom­pose on high tem­per­a­ture (700 °C) inor­gan­ic sur­faces coat­ed with Rh-based reform­ing cat­a­lyst to an inter­me­di­ate liq­uid. The inter­me­di­ate liq­uid main­tains con­tact with the sur­face per­mit­ting high heat trans­fer which results in an inter­nal ther­mal gra­di­ent with­in the par­ti­cle. Con­ver­sion from sol­id to liq­uid occurs along the inter­nal ther­mal gra­di­ent final­ly result­ing in a ful­ly liq­uid droplet which com­plete­ly boils to vapors.

Speaker’s Biog­ra­phy — Paul Dauen­hauer is an assis­tant pro­fes­sor of Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Mass­a­chu­setts, Amherst. His research cur­rent­ly exam­ines the chem­istry of bio­mass pyrol­y­sis in the pres­ence of reform­ing and com­bus­tion cat­a­lysts. He was for­mer­ly a Senior Research Engi­neer with the Dow Chem­i­cal Com­pa­ny in Mid­land, MI, and Freeport, TX, as part of both Core R&D – Reac­tion Engi­neer­ing and Chem­istry and Catal­y­sis, as well as the Hydro­car­bons and Ener­gy R&D divi­sion. He was the co-inven­tor of the process Reac­tive Flash Volatiliza­tion for the con­ver­sion of bio­mass to syn­the­sis gas at mil­lisec­ond res­i­dence times, and he cur­rent­ly is a co-author of four patent appli­ca­tions relat­ed to cat­alyt­ic bio­mass pro­cess­ing. For­mer employ­ment includ­ed Cargill, Inc. at Gainesville, GA, as part of the Grain & Oilseeds Divi­sion as well as Wah­peton, ND, as part of the Sweet­en­ers divi­sion for the wet milling of maize.

2010 Spring Symposium

 
Dustin W. Fick­el and Raul F. Lobo
*Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy
Depart­ment of Chem­i­cal Engi­neer­ing
Uni­ver­si­ty of Delaware
Newark, Delaware 19716

Abstract — Nitro­gen oxides (NOx) are a major atmos­pher­ic pol­lu­tant pro­duced through the com­bus­tion of fos­sil fuels in inter­nal com­bus­tion engines. Cop­per-exchanged zeo­lites are promis­ing as selec­tive cat­alyt­ic reduc­tion cat­a­lysts for the direct con­ver­sion of NO into N₂ and O₂, and recent reports have shown the enhanced per­for­mance of Cu-CHA cat­a­lysts over oth­er zeo­lite frame­works in the NO decom­po­si­tion of exhaust gas streams.

In the present study, Rietveld refine­ment of vari­able-tem­per­a­ture XRD syn­chro­tron data obtained for Cu-SSZ-13 and Cu-SSZ-16 is used to inves­ti­gate the loca­tion of cop­per cations in the zeo­lite pores and the effect of tem­per­a­ture on these sites and on frame­work sta­bil­i­ty. The XRD pat­terns show that the ther­mal sta­bil­i­ty of SSZ-13 is increased sig­nif­i­cant­ly when cop­per is exchanged into the frame­work com­pared with the acid form of the zeo­lite, H-SSZ-13. Cu-SSZ-13 is also more ther­mal­ly sta­ble than Cu-SSZ-16. From the refined dif­frac­tion pat­terns, the atom­ic posi­tions of atoms, cop­per loca­tions and occu­pan­cies, and ther­mal dis­place­ment para­me­ters were deter­mined as a func­tion of tem­per­a­ture for both zeo­lites. Cop­per is found in the cages coor­di­nat­ed to three oxy­gen atoms of the six-mem­bered rings. This study also shows the enhanced per­for­mance of cop­per exchanged small-pore zeo­lites towards the selec­tive cat­alyt­ic reduc­tion of nitric oxide com­pared to Cu-ZSM-5 after hydrother­mal­ly treat­ing the zeo­lites.

* Fick­el, D.W., Lobo, R.F., Cop­per Loca­tion Study of Cu-SSZ-13 and Cu-SSZ-16 Vari­able Tem­per­a­ture XRD Riet­feld Refine­ment, J. Phys. Chem. C, DOI: 10.1021/jp9105025.

2010 Spring Symposium

 
Ray­mond J. Gorte
Chem­i­cal & Bio­mol­e­c­u­lar Engi­neer­ing
Uni­ver­si­ty of Penn­syl­va­nia
Philadel­phia, PA 19104 USA
gorte@​seas.​upenn.​edu

Abstract — SOFC and SOE are based on elec­trolytes that are oxy­gen-ion con­duc­tors. SOFC can there­fore oper­ate on a wide range of fuels, includ­ing methane and oth­er hydro­car­bons. Like­wise, elec­trol­y­sis of CO₂ is fea­si­ble in an SOE. How­ev­er, to allow sta­ble oper­a­tion with a wider range of feeds to the elec­trodes, new elec­trode mate­ri­als must be devel­oped. This talk will describe the meth­ods being devel­oped at Penn that allow the elec­trode com­po­si­tion and struc­ture to be var­ied eas­i­ly. Results for both fuel- and air-side elec­trodes will be dis­cussed.

Speaker’s Biog­ra­phy — Dr. Ray­mond J. Gorte joined the fac­ul­ty at the Uni­ver­si­ty of Penn­syl­va­nia in 1981 after receiv­ing his PhD in Chem­i­cal Engi­neer­ing from the Uni­ver­si­ty of Min­neso­ta. He is cur­rent­ly the Rus­sell Pearce and Eliz­a­beth Crim­i­an Heuer Pro­fes­sor of Chem­i­cal & Bio­mol­e­c­u­lar Engi­neer­ing, with a sec­ondary appoint­ment in Mate­ri­als Sci­ence & Engi­neer­ing. Since join­ing Penn, Dr. Gorte has served as Chair­man of Chem­i­cal Engi­neer­ing from 1995 to 2000 and was the Carl V. S. Pat­ter­son Pro­fes­sor of Chem­i­cal Engi­neer­ing from 1996 through 2001. He received the 1997 Par­ra­vano Award of the Michi­gan Catal­y­sis Soci­ety, the 1998 Philadel­phia Catal­y­sis Club Award, the 1999 Paul Emmett Award of the North Amer­i­can Catal­y­sis Soci­ety, the 2001 Penn Engi­neer­ing Dis­tin­guished Research Award, and the 2009 AIChE Wil­helm Award. He has served as Chair­man of the Gor­don Con­fer­ence on Catal­y­sis (1998) and Pro­gram Chair­man of the 12th Inter­na­tion­al Zeo­lite Con­fer­ence (1998). His present research inter­ests are focused on elec­trodes for sol­id-oxide fuel cells and on ther­mo­dy­nam­ic stud­ies of redox prop­er­ties with oxi­da­tion cat­a­lysts. He is also known for his research on zeo­lite acid­i­ty and for met­al-sup­port effects, espe­cial­ly with ceria-sup­port­ed pre­cious met­als, used in auto­mo­tive emis­sions con­trol.

2010 Spring Symposium

 
Jing­guang G. Chen
Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy
Depart­ment of Chem­i­cal Engi­neer­ing
Uni­ver­si­ty of Delaware
Newark, DE 19716

Abstract — Met­al car­bides [1–3] and bimetal­lic alloys [4–7] often show nov­el cat­alyt­ic and elec­tro­cat­alyt­ic prop­er­ties. How­ev­er, it is dif­fi­cult to know a pri­ori how the chem­i­cal prop­er­ties of par­tic­u­lar car­bide and bimetal­lic sys­tems will be mod­i­fied rel­a­tive to the par­ent met­als. In the past few years our research group has inves­ti­gat­ed the nov­el cat­alyt­ic prop­er­ties of var­i­ous car­bide and bimetal­lic sys­tems, using a com­bi­na­tion of Den­si­ty Func­tion­al The­o­ry (DFT) cal­cu­la­tions, sur­face sci­ence stud­ies on sin­gle crys­tal sur­faces, and reac­tor and fuel cell stud­ies of sup­port­ed cat­a­lysts. The gen­er­al trends from the exper­i­men­tal and the­o­ret­i­cal stud­ies of car­bide [1] and bimetal­lic sur­faces [4] have been sum­ma­rized in recent reviews.

In this talk we will describe the uti­liza­tion of tung­sten car­bides as poten­tial anode elec­tro­cat­a­lysts for Direct Methanol Fuel Cells (DMFC). Cur­rent­ly, the anode elec­tro­cat­a­lysts for DMFC are Pt and Pt/Ru, which are dis­ad­van­ta­geous in terms of the pro­hib­i­tive­ly high costs and their sus­cep­ti­bil­i­ty to be poi­soned by CO. We will describe how to con­trol the decom­po­si­tion path­ways of methanol on sin­gle crys­tal sur­faces of tung­sten car­bides under well-con­trolled ultra­high vac­u­um (UHV) con­di­tions. We will also dis­cuss the syn­the­sis of phase pure tung­sten car­bide elec­trodes using Phys­i­cal Vapor Depo­si­tion (PVD) to bridge the “mate­ri­als gap” between sin­gle crys­tal sur­faces and poly­crys­talline films. We will then present our results of the elec­tro­chem­i­cal eval­u­a­tion of the tung­sten car­bide elec­trodes to bridge the “pres­sure gap” between UHV envi­ron­ment and elec­tro­chem­i­cal con­di­tions. We will also briefly dis­cuss the ther­mo­dy­nam­ic sta­bil­i­ty and kinet­ic mea­sure­ments regard­ing the bimetal­lic sur­faces in the pres­ence of oxy­gen under both UHV [8] and atmos­pher­ic [9] con­di­tions, which should help iden­ti­fy active and sta­ble bimetal­lic cath­ode elec­tro­cat­a­lysts in the Oxy­gen Reduc­tion Reac­tion (ORR) in fuel cells.

[1] Hwu & Chen, Chem­i­cal Reviews, 105 (2005) 185–212.
[2] Na, Zhang, Zheng, Wang & Chen, Angew. Chem. Int. Ed. 47 (2008) 8510.
[3] Weigert, Stot­tle­my­er, Zell­ner & Chen, J. Phys. Chem. C, 111 (2007) 14617.
[4] Chen, Men­ning & Zell­ner, Sur­face Sci­ence Reports, 63 (2008) 201–254.
[5] Hwu, Eng & Chen, J. Am. Chem. Soc. 124 (2002) 702.
[6] Kitchin, Norskov, Barteau & Chen, Phys. Rev. Lett. 93 (2004) 156801.
[7] Muril­lo, Goda & Chen, J. Am. Chem. Soc. 129 (2007) 7101.
[8] Men­ning & Chen, J. Chem. Phys. 130 (2009) 174709.
[9] Men­ning & Chen, J. Pow­er Sources, 195 (2010) 3140.

Speaker’s Biog­ra­phy — Jing­guang Chen is the Claire D. LeClaire Pro­fes­sor of chem­i­cal engi­neer­ing. He also holds the posi­tions of the Inter­im Direc­tor of the Uni­ver­si­ty of Delaware Ener­gy Insti­tute and Co-Direc­tor of the Ener­gy Fron­tier Research Cen­ter at the Uni­ver­si­ty of Delaware. He received his Ph.D. degree from the Uni­ver­si­ty of Pitts­burgh 1988. He spent one year in Ger­many as a Hum­boldt Post­doc­tor­al Fel­low before start­ing his career at the Exxon Cor­po­rate Research Lab­o­ra­to­ries. In 1998 he accept­ed a fac­ul­ty posi­tion at the Uni­ver­si­ty of Delaware and served as the Direc­tor of the Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy (CCST) from 2000–2007. He has 200 jour­nal pub­li­ca­tions and 17 US patents. He is very active in serv­ing the sur­face sci­ence and catal­y­sis com­mu­ni­ties, includ­ing respon­si­bil­i­ties as the Chair for the Gor­don Research Con­fer­ence on Catal­y­sis in 2002, the Chair of the Philadel­phia Catal­y­sis Club in 2004, the Catal­y­sis Sec­re­tari­at of the Amer­i­can Chem­i­cal Soci­ety in 2007, and the Board of Direc­tors for the North Amer­i­can Catal­y­sis Soci­ety. He is also the co-founder and team leader of the first Syn­chro­tron Catal­y­sis Con­sor­tium in the US for the Depart­ment of Ener­gy.

2010 Spring Symposium

 
George J. Antos
Direc­tor, Catal­y­sis and Bio­catal­y­sis Pro­gram
Direc­torate for Engi­neer­ing
Nation­al Sci­ence Foun­da­tion


Abstract — Catal­y­sis played an impor­tant role in the devel­op­ment of the petro­le­um-derived fuel indus­try into the key part of the world­wide indus­tri­al pic­ture that it is today. For var­i­ous strate­gic rea­sons, a new fuel plat­form based on bio­mass is desired to sup­ple­ment and replace the petro­le­um of today. Corn-derived ethanol from fer­men­ta­tion was the first move­ment. Addi­tion­al tech­nol­o­gy is seen to be nec­es­sary how­ev­er. Where can we seek the tools nec­es­sary to achieve ambi­tious petro­le­um-replace­ment goals? Recent advances in catal­y­sis and bio­catal­y­sis hold great promise for new path­ways to the mass pro­duc­tion of next gen­er­a­tion hydro­car­bon bio­fu­els: green gaso­line, diesel and jet fuel from switch­grass, for­est waste, and agri­cul­tur­al residue. The poten­tial advan­tages of hydro­car­bon pro­duc­tion from lig­no­cel­lu­losic feed­stocks will be dis­cussed, and the newest process path­ways and catal­y­sis impacts will be out­lined. Com­mer­cial­iza­tion efforts will be dis­cussed. Yet gaps in knowl­edge still exist. Fed­er­al fund­ing oppor­tu­ni­ties in hydro­car­bon bio­fu­els will be touched on.

Speaker’s Biog­ra­phy — Dr. George J. Antos is cur­rent­ly the Direc­tor of the Catal­y­sis and Bio­catal­y­sis Pro­gram in the Engi­neer­ing Direc­torate at the Nation­al Sci­ence Foun­da­tion. This pro­gram receives 150–200 pro­pos­als for uni­ver­si­ty research fund­ing in fun­da­men­tal catal­y­sis, bio­catal­y­sis, bio­mass con­ver­sion, elec­tro­catal­y­sis and pho­to­catal­y­sis each year with mil­lions of dol­lars award­ed annu­al­ly. George joined NSF after a 33+ year career in indus­try with UOP LLC. This expe­ri­ence encom­passed the research, devel­op­ment and com­mer­cial­iza­tion of process, cat­a­lyst and mate­r­i­al tech­nolo­gies for the petro­le­um refin­ing and petro­chem­i­cal indus­tries. George has authored and co-authored over 160 US patents, and has develped a large num­ber of pre­sen­ta­tions and papers in the area. George is also an Adjunct Pro­fes­sor with the Chem­i­cal and Bio­log­i­cal Engi­neer­ing Depart­ment at the Uni­ver­si­ty of Wis­con­sin, Madi­son and is CEO of Cat­a­lyst Real­iza­tions, Inc., a con­sult­ing com­pa­ny. His edu­ca­tion includes a B.S. in Chem­istry from Iowa State Uni­ver­si­ty, and M.S. and Ph.D. degrees in Chem­istry from North­west­ern Uni­ver­si­ty.

2010 Spring Symposium

 
Alessan­dro Fal­di
Exxon­Mo­bil Research & Engi­neer­ing Com­pa­ny
1545 Route 22 East
Annan­dale, NJ 08801
Alessandro.​Faldi@​ExxonMobil.​com


The pre­sen­ta­tion first high­lights ExxonMobil’s Out­look for Ener­gy, which reflects an assess­ment of glob­al sup­ply and demand through 2030 based on the under­ly­ing fac­tors that are shap­ing impor­tant ener­gy chal­lenges around the world. As always, the Out­look for Ener­gy focus­es on sev­er­al key areas of inter­est, which this year will include grow­ing trans­porta­tion and pow­er gen­er­a­tion demands as well as the out­look for ener­gy-relat­ed CO₂ emis­sions.

Eco­nom­ic progress and grow­ing pop­u­la­tions, espe­cial­ly in devel­op­ing coun­tries, will dri­ve ener­gy demand approx­i­mate­ly 35% high­er in 2030 ver­sus 2005. This demand increase is antic­i­pat­ed despite sub­stan­tial effi­cien­cy gains, which are expect­ed to accel­er­ate as new tech­nolo­gies are devel­oped and deployed.

Ris­ing trans­porta­tion needs will increase relat­ed ener­gy require­ments approx­i­mate­ly 40% by 2030, even as light-duty vehi­cles with much bet­ter fuel econ­o­my pen­e­trate the mar­ket. The rise in trans­porta­tion demand will be met pri­mar­i­ly by oil, which will pro­vide close to 95 per­cent of all trans­porta­tion fuels in 2030.

As economies grow, glob­al demand for elec­tric­i­ty is pro­ject­ed to increase 75 per­cent by 2030. Con­sis­tent with this pro­jec­tion, ener­gy for pow­er gen­er­a­tion is expect­ed to remain the largest and fastest grow­ing seg­ment of glob­al demand, dri­ven in large part by increas­es in Asia Pacif­ic. Meet­ing the expect­ed world­wide growth in pow­er demand will require a diverse set of ener­gy sources. Today coal is dom­i­nant and will retain the largest share glob­al­ly through 2030; how­ev­er, nat­ur­al gas, nuclear, and renew­ables will all gain mar­ket share.

In the sec­ond part of my talk, I’ll describe that meet­ing this ener­gy demand requires an inte­grat­ed set of solu­tions, includ­ing expand­ing all types of sup­ply, improv­ing effi­cien­cy, and mit­i­gat­ing green­house gas emis­sions. I’ll touch on exam­ples of how tech­nol­o­gy will play a crit­i­cal role in meet­ing these chal­lenges, and dis­cuss ExxonMobil’s alliance with a lead­ing biotech com­pa­ny, Syn­thet­ic Genomics Inc., to research and devel­op next gen­er­a­tion bio­fu­els from pho­to­syn­thet­ic algae.

Speaker’s Biog­ra­phy Alessan­dro Fal­di — Alessan­dro has a Lau­rea in Chem­i­cal Engi­neer­ing from the Poly­tech­nic of Milan, Italy, and a Ph. D. in Chem­i­cal Engi­neer­ing from the Uni­ver­si­ty of Min­neso­ta. He joined Exxon Chem­i­cal Com­pa­ny in 1994 as a research engi­neer at the Bay­town Poly­mers Cen­ter, Exxon Chem­i­cal Tech­nol­o­gy, where he held tech­ni­cal posi­tions in mate­ri­als char­ac­ter­i­za­tion, advanced char­ac­ter­i­za­tion and prod­uct devel­op­ment.

In 2000, Alessan­dro moved to Exxon­Mo­bil Chemical’s head­quar­ters in Hous­ton, Texas where he held mar­ket plan­ner and mar­ket devel­op­ment posi­tions in the Polypropy­lene busi­ness.

In 2005, Alessan­dro returned to Chemical’s Tech­nol­o­gy in Bay­town, Texas to become Pro­gram Leader of a break­through team that devel­oped advan­taged tech­nol­o­gy for Exxon­Mo­bil Chemical’s spe­cial­ty busi­ness.

In 2007, he was appoint­ed Cor­po­rate Pro­grams Port­fo­lio Man­ag­er in Cor­po­rate Strate­gic Research, Exxon­Mo­bil Research and Engi­neer­ing Com­pa­ny and is respon­si­ble for man­ag­ing emerg­ing-oppor­tu­ni­ty pro­grams that sup­port the Corporation’s gen­er­al inter­est.

2009 Spring Symposium

 
Jochen Lauter­bach
Depart­ment of Chem­i­cal Engi­neer­ing
Uni­ver­si­ty of Delaware
Newark, DE

Abstract — We have been using high-through­put (HT) approach­es based on rapid-scan FTIR hyper­spec­tral imag­ing in the mid-infrared to screen cat­a­lyst for­mu­la­tions for the dis­cov­ery and opti­miza­tion of new and improved mate­ri­als. In com­bi­na­tion with HT meth­ods, we also employ a vari­ety of more tra­di­tion­al spec­tro­scop­ic meth­ods to under­stand the under­ly­ing fun­da­men­tal sci­ence.

Two exam­ples will be used to illus­trate this research approach: de-NOx for auto­mo­tive exhaust after-treat­ment and ammo­nia decom­po­si­tion cat­a­lysts for CO free hydro­gen generation.While HT screen­ing is a macro­scop­ic analy­sis tech­nique, we are also inter­est­ed in observ­ing non-lin­ear phe­nom­e­na on work­ing cat­a­lysts in situ on the microscale using spec­tro­scop­ic imag­ing based on ellip­som­e­try. The col­lec­tive, glob­al behav­iour of a cat­alyt­ic sys­tem depends on the effec­tive com­mu­ni­ca­tion of local reac­tiv­i­ty vari­a­tions to dis­tant points in the sys­tem. One mode of com­mu­ni­ca­tion occurs via par­tial pres­sure fluc­tu­a­tions in the gas-phase above the cat­alyt­i­cal­ly active sur­face. This gas-phase cou­pling mode is con­sid­ered to be most effec­tive under vac­u­um con­di­tions, where the mean free path between mol­e­c­u­lar col­li­sions is large. We take advan­tage of a spa­tial­ly dis­trib­uted sys­tem of iso­lat­ed chem­i­cal oscil­la­tors to inves­ti­gate the details of gas-phase com­mu­ni­ca­tion in the 10–3 Torr range. Char­ac­ter­i­za­tion of local gas-phase vari­a­tions, in con­junc­tion with local kinet­ic activ­i­ty on the sur­face, shows that sur­face/­gas-phase inter­ac­tion might dif­fer from the con­ven­tion­al assump­tion of a gra­di­ent free, mol­e­c­u­lar flow envi­ron­ment near the sur­face. This analy­sis pro­vides a quan­ti­ta­tive esti­mate of the effec­tive gas-phase cou­pling length in a het­ero­ge­neous sys­tem. This cou­pling length was found to be in agree­ment with sur­face imag­ing results which qual­i­ta­tive­ly showed cou­pling between oscil­la­tors.

Speaker’s Biog­ra­phy — Jochen Lauter­bach received his Diplo­ma in Physics at the Uni­ver­si­ty of Bayreuth, Ger­many under Prof. J. Küp­pers and his Doc­tor­ate in Phys­i­cal Chem­istry at the Fritz-Haber Insti­tute of the Max-Planck-Soci­ety, Berlin, Ger­many under Pro­fes­sor G. Ertl. He came to the US in 1994 with a Feodor-Lynen-Fel­low­ship of the Alexan­der von Hum­boldt-Foun­da­tion and per­formed his post-doc­tor­al work at the Uni­ver­si­ty of Cal­i­for­nia at San­ta Bar­bara under Prof. W.H. Wein­berg. He joined the fac­ul­ty at Pur­due in 1996 and, in 2002, moved to the Uni­ver­si­ty of Delaware, where he cur­rent­ly is a Pro­fes­sor in the Chem­i­cal Engi­neer­ing Depart­ment. His research inter­ests include the design of cat­alyt­ic mate­ri­als using high-through­put screen­ing method­olo­gies and in situ spec­tro­scop­ic tech­niques, devel­op­ment of cat­a­lyst syn­the­sis method­olo­gies based on microemul­sions, nano-engi­neered poly­mer films from renew­able feed­stock, and non-lin­ear dynam­ics of chem­i­cal reac­tions, in par­tic­u­lar exter­nal spa­tiotem­po­ral forc­ing. Pro­fes­sor Lauter­bach has pub­lished close to 100 papers/book chap­ters and has giv­en over 150 invit­ed pre­sen­ta­tions.