Zn Mod­i­fi­ca­tion of Pt(111) for the Hydrodeoxy­gena­tion of Aldoses

2014 Spring Symposium

 
Jesse R. McManus, Eddie Martono, & John M. Vohs
Uni­ver­si­ty of Penn­syl­va­nia
 
Abstract — The high oxy­gen con­tent and mul­ti­ple func­tion­al groups in bio­mass-derived plat­form mol­e­cules like glu­cose pose an inter­est­ing reac­tion engi­neer­ing chal­lenge for the con­ver­sion of bio­mass to val­ue-added fuels and chem­i­cals. The key to under­stand­ing the reac­tion path­ways nec­es­sary for these con­ver­sions lies in elu­ci­dat­ing reac­tion active sites on cat­alyt­i­cal­ly rel­e­vant sur­faces and iden­ti­fy­ing the role of each func­tion­al­i­ty exhib­it­ed by the feed mol­e­cule in the reac­tion mech­a­nism. In this study, tem­per­a­ture pro­grammed des­orp­tion (TPD) and high res­o­lu­tion elec­tron ener­gy loss (HREEL) spec­troscopy are uti­lized to probe the reac­tion path­way of the bio­mass-rel­e­vant glu­cose mol­e­cule, as well as mod­el aldos­es glyc­er­alde­hyde and gly­co­lalde­hyde, and sim­ple alde­hyde acetalde­hyde on a Pt cat­a­lyst sur­face. The effects of mod­i­fi­ca­tion of the Pt(111) sur­face with oxyphilic Zn adatoms are explored with regard to hydrodeoxy­gena­tion chem­istry, and reac­tion mech­a­nisms are pro­posed. With all mol­e­cules stud­ied, it was found that Zn addi­tion to Pt(111) result­ed in an increase in the bar­ri­er for C-H and C-C scis­sion, as well as notable activ­i­ty for deoxy­gena­tion at the alde­hyde oxy­gen as a func­tion of polyal­co­hol con­tent. These results help elu­ci­date the role of mul­ti­ple alco­hol func­tion­al­i­ties in bio­mass-derived oxy­genates and high­light the poten­tial of using alloy effects to mod­i­fy cat­alyt­ic chem­istry.
 
Jess_R_McManusBiog­ra­phy — Dr. Jesse R. McManus recent­ly com­plet­ed his PhD research in Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Penn­syl­va­nia under the tute­lage of Prof. John M. Vohs, suc­cess­ful­ly defend­ing his the­sis “Reac­tion Char­ac­ter­i­za­tion of Bio­mass-Derived Oxy­genates on Noble Met­al Cat­a­lysts”. In 2009, he received his BSE in Chem­i­cal Engi­neer­ing at Tulane Uni­ver­si­ty, grad­u­at­ing Sum­ma Cum Laude with an Hon­ors dis­tinc­tion. Dur­ing his stud­ies, Dr. McManus has received sev­er­al awards for his aca­d­e­m­ic accom­plish­ments, includ­ing the Tulane-Richards Schol­ar­ship for Aca­d­e­m­ic Excel­lence, The R.C. Reed Schol­ar Award for aca­d­e­m­ic achieve­ment and promise for the future, and the Doc­tor­al Franklin Schol­ar Award for stu­dents with high promise to suc­ceed in cre­ative research at the cut­ting edge of their dis­ci­pline. In the spring, Dr. McManus plans to depart from aca­d­e­m­ic research and pur­sue a career in the ener­gy sec­tor with a major ener­gy com­pa­ny.

Alkene Metathe­sis for Propy­lene Pro­duc­tion over W-based Cat­a­lysts: Insights from Multi-Functional Cat­a­lysts and Met­al­la­cy­clobu­tanes

2014 Spring Symposium

 
Christo­pher P. Nicholas

 
Abstract — Tung­sten oxide sup­port­ed on sil­i­ca is an effi­cient cat­a­lyst for olefin metathe­sis used in indus­tri­al process­es since the 1960s. Sev­er­al ele­ments point to iso­lat­ed met­al cen­ters as the active sites, and from the Chau­vin mech­a­nism, it is rea­son­able to expect that car­bene species are involved, pos­si­bly bear­ing an oxide lig­and in the metal’s lig­and sphere. Owing to the strate­gic impor­tance of olefins as build­ing blocks for the world chem­i­cal indus­try, devel­op­ment of effi­cient process­es is of utmost rel­e­vance. More specif­i­cal­ly, tai­lored het­ero­ge­neous cat­a­lysts with known structure–activity rela­tion­ships may improve life­times and have high­er num­bers of active sites.

With our col­lab­o­ra­tors, we have been study­ing tung­sten hydride sup­port­ed on alu­mi­na pre­pared by the sur­face organometal­lic chem­istry method as an active pre­cur­sor for metathe­sis process­es at low tem­per­a­ture and pres­sure. Taoufik, et​.al. showed that eth­yl­ene can be con­vert­ed to propy­lene at very high selec­tiv­i­ties of 99% via a tri-func­tion­al mech­a­nism involv­ing dimer­iza­tion, iso­mer­iza­tion and cross-metathe­sis of eth­yl­ene and the pro­duced 2-butene. Recent­ly, via a con­tact time study we revealed that the dimer­iza­tion of eth­yl­ene to 1-butene is the pri­ma­ry and also the rate lim­it­ing step in this reac­tion and results in deac­ti­va­tion of the cat­a­lyst due to a side reac­tion like olefin poly­mer­iza­tion pro­duc­ing car­bona­ceous deposits on the cat­a­lyst.

With that knowl­edge, we have also inves­ti­gat­ed per­for­mance of the cat­a­lyst in the pres­ence of eth­yl­ene and butenes. At low tem­per­a­ture (120 °C) in the cross-metathe­sis of eth­yl­ene and 2-butene, the cat­a­lyst deac­ti­vates notably with time on stream. How­ev­er, at 150 °C, the cat­a­lyst was sta­ble with time and there­by gave a high pro­duc­tiv­i­ty in propy­lene. The ratio of eth­yl­ene to trans-2-butene was also stud­ied, and the W-H/Al2O3 cat­a­lyst is sta­ble and high­ly selec­tive to propy­lene even at sub-sto­i­chio­met­ric eth­yl­ene ratios.

Sur­pris­ing­ly, we have also been able to obtain propy­lene in high yields from butene only feeds. 1-butene and 2-butene are both able to be con­vert­ed into propy­lene at high­er selec­tiv­i­ty than expect­ed due to iso­mer­iza­tion and metathe­sis occur­ring simul­ta­ne­ous­ly. Then, by study­ing isobutene / 2-butene cross-metathe­sis, we observed that the cat­alyt­ic cycle involv­ing the less ster­i­cal­ly hin­dered tungsta­cy­clobu­tane inter­me­di­ate gov­erns the con­ver­sion rate of the cross-metathe­sis reac­tion for propy­lene pro­duc­tion from butenes and/or eth­yl­ene.
 

References

  1. (a) J. C. Mol, J. Mol. Catal. 2004, 213, 39; (b) L. F. Heck­els­berg, R. L. Banks and G. C. Bai­ley, Ind. Eng. Chem. Prod. Res. Dev. 1968, 7, 29.
  2. A. Spamer, T. I. Dube, D. J. Mood­ley, C. van Schalk­wyk and J. M. Botha, Appl.Catal.A 2003, 255, 153.
  3. Y. Chau­vin, Angew. Chem., Int. Ed. 2006, 45, 3740.
  4. Taoufik, M.; Le Roux, E.; Thivolle-Cazat, J.; Bas­set, J.-M. Angew. Chem. Int. Ed. 2007, 46, 7202 –7205.
  5. Mazoy­er, E.; Sze­to, K.C.; Mer­le, N.; Thivolle-Cazat, J.; Boy­ron, O.; Bas­set, J.-M.; Nicholas, C.P.; Taoufik, M. J. Mol. Catal. A, 2014, in press.
  6. Mazoy­er E.; Sze­to K. C.; Mer­le, N.; Nor­sic, S.; Boy­ron, O.; Bas­set J.-M.; Taoufik, M.; Nicholas, C. P. J. Catal. 2013, 301, 1–7.
  7. Mazoy­er, E.; Sze­to, K. C.; Nor­sic, S.; Gar­ron, A.; Bas­set, J.-M.; Nicholas, C. P.; Taoufik, M. ACS Catal­y­sis, 2011, 1, 1643–6.
  8. Mazoy­er E.; Sze­to K. C; Bas­set J.-M.; Nicholas, C. P; Taoufik, M. Chem. Com­mun. 2012, 48, 3611–13.
  9. Sze­to, K.C.; Mazoy­er, E.; Mer­le, N.; Nor­sic, S.; Bas­set, J.-M.; Nicholas, C.P.; Taoufik, M. ACS Catal­y­sis 2013, 3, 2162–8.

 
Christopher_P_NicholasBiog­ra­phy — Chris joined UOP in 2006 after earn­ing a Ph.D. from North­west­ern Uni­ver­si­ty and work­ing in the Hard Mate­ri­als Cen­ter of Excel­lence at Sig­ma-Aldrich. He has worked in the Catal­y­sis and Explorato­ry Research depart­ments and is cur­rent­ly focused on New Mate­ri­als Research. Chris is an inven­tor or co-inven­tor on 30+ US and for­eign patents and coau­thor of 13 peer reviewed jour­nal arti­cles and a book chap­ter. He has been involved with the Chica­go Catal­y­sis Club since grad­u­ate stu­dent days and is cur­rent­ly serv­ing as the Pro­gram Chair for the Chica­go Catal­y­sis Club. Chris’ research inter­ests encom­pass the gamut of inor­gan­ic and cat­alyt­ic tech­nolo­gies rang­ing from mate­ri­als syn­the­sis to char­ac­ter­i­za­tion to cat­a­lyst and process devel­op­ment. He has par­tic­u­lar­ly enjoyed under­stand­ing the rela­tion­ship between homo­ge­neous and het­ero­ge­neous cat­a­lysts.

Analy­sis of the Mech­a­nism of Elec­tro­chem­i­cal Oxy­gen Reduc­tion and Devel­op­ment of Ag– and Pt-alloy Cat­a­lysts for Low Tem­per­a­ture Fuel Cells

2014 Spring Symposium

 
Suljo Lin­ic

 
Abstract — The oxy­gen reduc­tion reac­tion (ORR) is the major source of over­po­ten­tial loss in low-tem­per­a­ture fuel cells. Expen­sive, Pt-based mate­ri­als have been found to be the most effec­tive cat­a­lysts, but explo­ration of alter­na­tives has been ham­pered by sta­bil­i­ty con­straints at the typ­i­cal oper­at­ing con­di­tions of low pH and high poten­tial.

I will dis­cuss how we stud­ied ele­men­tary mech­a­nism of ORR on var­i­ous met­al elec­trodes using kinet­ic and micro-kinet­ic analy­sis of reac­tion path­ways and quan­tum chem­i­cal cal­cu­la­tions. These stud­ies allowed us to iden­ti­fy the ele­men­tary steps and mol­e­c­u­lar descrip­tors that gov­ern the rate of ORR. Using these per­for­mance descrip­tors we have been able to iden­ti­fy fam­i­lies of Pt and Ag-based alloys that exhib­it supe­ri­or ORR per­for­mance is acid and base respec­tive­ly.

We have syn­the­sized these alloys to demon­strate the supe­ri­or ORR activ­i­ty with rotat­ing disk elec­trode exper­i­ments. We have also per­formed thor­ough struc­tur­al char­ac­ter­i­za­tion of the bulk and sur­face prop­er­ties with a com­bi­na­tion of cyclic voltam­me­try, x-ray dif­frac­tion, and elec­tron microscopy with spa­tial­ly resolved ener­gy-dis­per­sive x-ray spec­troscopy and elec­tron ener­gy loss spec­troscopy.
 

Reference

  1. Holewin­s­ki and Lin­ic. J. Elec­trochem. Soc. 159, (2012).

 
Suljo_LinicBiog­ra­phy — Prof. Lin­ic obtained his PhD degree, spe­cial­iz­ing in sur­face and col­loidal chem­istry and het­ero­ge­neous catal­y­sis, at the Uni­ver­si­ty of Delaware in 2003 under the super­vi­sion of Prof. Mark Barteau after receiv­ing his BS degree in Physics with minors in Math­e­mat­ics and Chem­istry from West Chester Uni­ver­si­ty in West Chester (PA). He was a Max Planck post­doc­tor­al fel­low with Prof. Dr. Matthias Schef­fler at the Fritz Haber Insti­tute of Max Planck Soci­ety in Berlin (Ger­many), work­ing on first prin­ci­ples stud­ies of sur­face chem­istry. He start­ed his inde­pen­dent fac­ul­ty career in 2004 at the Depart­ment of Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Michi­gan in Ann Arbor where he is cur­rent­ly the Class of 1983 Fac­ul­ty Schol­ar Pro­fes­sor of chem­i­cal engi­neer­ing.

Prof. Linic’s research has been rec­og­nized through mul­ti­ple awards includ­ing the 2014 ACS (Amer­i­can Chem­i­cal Soci­ety) Catal­y­sis Lec­ture­ship for the Advance­ment of Cat­alyt­ic Sci­ence, award­ed annu­al­ly by the ACS Catal­y­sis jour­nal and Catal­y­sis Sci­ence and Tech­nol­o­gy Divi­sion of ACS, the 2011 Nanoscale Sci­ence and Engi­neer­ing Forum Young Inves­ti­ga­tor Award, award­ed by Amer­i­can Insti­tute of Chem­i­cal Engi­neers, the 2009 ACS Unilever Award award­ed by the Col­loids and Sur­face Sci­ence Divi­sion of ACS, the 2009 Camille Drey­fus Teacher-Schol­ar Award award­ed by the Drey­fus Foun­da­tion, the 2008 DuPont Young Pro­fes­sor Award, and a 2006 NSF Career Award. Prof. Lin­ic has pre­sent­ed more than 100 invit­ed and keynote lec­tures and pub­lished more than 50 peer reviewed arti­cles in lead­ing jour­nals in the fields of gen­er­al sci­ence, Physics, Chem­istry, and Chem­i­cal Engi­neer­ing.

Wel­come to HEL – Bet­ter Chem­istry – Faster

2014 Spring Symposium

 


 
HEL is a lead­ing equip­ment provider for cat­alyt­ic process­es in chem­i­cal, petro­chem­i­cal and phar­ma­ceu­ti­cal Indus­try. Stirred and fixed-bed reac­tors for cat­alyt­ic & ther­mal con­ver­sions (hydro­gena­tion reac­tor, poly­mer­iza­tion, hydro­c­rack­ing, bio-fuel syn­the­sis etc.) are sup­plied to a range of indus­tries. Often at ele­vat­ed tem­per­a­ture & pres­sure, HEL spe­cial­izes in research scale, mul­ti-reac­tor and high pres­sure reac­tors pro­cess­ing, test­ing, equip­ment and sys­tems. Cus­tom designs to client flow sheets are also sup­plied includ­ing pilot scale process­es.

Life Cycle of Cat­alytic Diesel Emis­sion Con­trol Sys­tems

2014 Spring Symposium

 
Alek­sey Yez­erets, Neal Cur­ri­er, Krish­na Kamasamu­dram, Jun­hui Li, Hong­mei An, Ashok Kumar, Jiny­ong Luo, Saurabh Joshi


 
Abstract — A diverse spec­trum of high­ly capa­ble diesel cat­alyt­ic emis­sion con­trol sys­tems has emerged in the recent years, in response to strin­gent envi­ron­men­tal reg­u­la­tions in sev­er­al lead­ing world mar­kets. By tak­ing the brunt of the emis­sion reduc­tion, these high­ly effec­tive sys­tems allowed the engines to be designed and tuned for max­i­mum fuel effi­cien­cy and min­i­mum CO2 emis­sions.

Unlike their gaso­line emis­sion con­trol pre­de­ces­sors, diesel sys­tems include mul­ti­ple cat­a­lysts with dis­tinct func­tions, along with a vari­ety of sen­sors and actu­a­tors, thus rep­re­sent­ing ver­i­ta­ble chem­i­cal plants. For exam­ple, the emis­sion con­trol sys­tem com­mer­cial­ized in Cum­mins-pow­ered 2010 heavy-duty diesel vehi­cles includes four dis­tinct cat­alyt­ic devices, a diesel oxi­da­tion cat­a­lyst (DOC), cat­alyzed diesel par­tic­u­late fil­ter (DPF), selec­tive cat­alyt­ic reduc­tion (SCR) cat­a­lyst, and an ammo­nia slip selec­tive oxi­da­tion cat­a­lyst (ASC). The sys­tem fur­ther includes eight sen­sors, and two flu­id injec­tors, along with the respec­tive con­trols and diag­nos­tic algo­rithms. Anoth­er sys­tem, com­mer­cial­ized by Cum­mins in 2007 and 2010 Dodge Ram pick­ups, is based on a NOx adsor­ber cat­a­lyst and rep­re­sents sim­i­lar lev­el of sophis­ti­ca­tion. Under­ly­ing the sys­tem-lev­el com­plex­i­ty is the intri­ca­cy of the indi­vid­ual cat­alyt­ic ele­ments, some of which include mul­ti­ple dis­tinct chem­i­cal func­tions and com­plex topol­o­gy.

Pre­dictably, life­cy­cles of such sys­tems are shaped by the behav­iors of the indi­vid­ual cat­alyt­ic ele­ments and their inter­ac­tions. These often fea­ture a vari­ety of reversible process­es, in response to depo­si­tion and removal of var­i­ous poi­sons and mask­ing agents, reversible chem­i­cal and mor­pho­log­i­cal changes, along with irre­versible degra­da­tion, often referred to as aging.

In this pre­sen­ta­tion, we will review sev­er­al exam­ples of inter­ac­tions between cat­a­lysts in the con­text of the above diesel emis­sion con­trol sys­tems, empha­siz­ing how the recent advances in their prac­ti­cal appli­ca­tion were under­pinned by the devel­op­ments in the broad­er field of het­ero­ge­neous catal­y­sis and reac­tion engi­neer­ing.
 
Aleksey_YezeretsBiog­ra­phy — At Cum­mins, the world’s largest inde­pen­dent man­u­fac­tur­er of diesel engines and relat­ed equip­ment, Dr. Yez­erets leads an R&D team respon­si­ble for guid­ance and sup­port of emis­sion con­trol prod­ucts at all stages of their life­cy­cle, and coor­di­nates a port­fo­lio of col­lab­o­ra­tive research pro­grams with Nation­al Labs, uni­ver­si­ties and indus­tri­al part­ners. Dr. Yez­erets serves on the Edi­to­r­i­al Board of the Jour­nal of Applied Catal­y­sis B: Envi­ron­men­tal, has act­ed as a guest edi­tor of three issues of the Catal­y­sis Today Jour­nal, and orga­nized a num­ber of envi­ron­men­tal catal­y­sis ses­sions in indus­tri­al and aca­d­e­m­ic meet­ings. He has received 11 US patents, pub­lished over 50 peer-reviewed arti­cles, as well as pre­sent­ed numer­ous invit­ed, keynote, and award lec­tures. Dr. Yez­erets has a spe­cial appoint­ment to the Grad­u­ate Fac­ul­ty of Chem­i­cal Engi­neer­ing at Pur­due Uni­ver­si­ty. His con­tri­bu­tions to the field of cat­alyt­ic emis­sion con­trol were rec­og­nized by the Her­man Pines Award in Catal­y­sis, R&D 100 Award, nation­al awards by the Amer­i­can Chem­i­cal Soci­ety, Amer­i­can Insti­tute of Chem­i­cal Engi­neers, and Soci­ety Auto­mo­tive Engi­neer­ing, as well as Julius Perr Award for Inno­va­tion by Cum­mins.

Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride

Meeting Program — January 2014

 
Eyas Mah­moud†, Don­ald A. Wat­son‡ and Raul F. Lobo†
†Catal­y­sis Cen­ter for Ener­gy Inno­va­tion
Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing
Uni­ver­si­ty of Delaware
Newark, DE 19716 USA
 
‡Depart­ment of Chem­istry and Bio­chem­istry
Uni­ver­si­ty of Delaware
Newark, DE 19716 USA

 
Abstract — A route to renew­able phthal­ic anhy­dride (2-benzofuran-1,3-dione) from bio­mass-derived furan and male­ic anhy­dride (furan-2,5-dione) is inves­ti­gat­ed. Furan and male­ic anhy­dride were con­vert­ed to phthal­ic anhy­dride in two reac­tion steps: Diels Alder cycload­di­tion fol­lowed by dehy­dra­tion. Excel­lent yields for the Diels-Alder reac­tion between furan and male­ic-anhy­dride were obtained at room tem­per­a­ture and sol­vent-free con­di­tions (SFC) yield­ing 96% exo-4,10-Dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione (oxanor­bornene dicar­boxylic anhy­dride) after 4 hrs of reac­tion. It is shown that this reac­tion is resis­tant to ther­mal run­away because its reversibil­i­ty and exother­mic­i­ty. The dehy­dra­tion of the oxanor­bornene was inves­ti­gat­ed using mixed-sul­fon­ic car­boxylic anhy­drides in methane­sul­fon­ic acid (MSA). An 80% selec­tiv­i­ty to phthal­ic anhy­dride (87% selec­tiv­i­ty to phthal­ic anhy­dride and phthal­ic acid) was obtained after run­ning the reac­tion for 2 hrs at 298 K to form a sta­ble inter­me­di­ate fol­lowed by 4 hrs at 353 K to dri­ve the reac­tion to com­ple­tion. The struc­ture of the inter­me­di­ate was deter­mined. This result is much bet­ter than the 11% selec­tiv­i­ty obtained in neat MSA using sim­i­lar reac­tion con­di­tions.
 
Biog­ra­phy — Eyas Mah­moud, recip­i­ent of the AIChE SCI Schol­ar award, grad­u­at­ed sum­ma cum laude from from the Uni­ver­si­ty of Penn­syl­va­nia with a B.S.E.in Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing in 2011. Since then he received the NSF Grad­u­ate Research Fel­low­ship (GRFP) and went on to pur­sue a Ph.D. in the Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing from the Uni­ver­si­ty of Delaware, under the super­vi­sion of Pro­fes­sor Raul F. Lobo. His the­sis work focus­es on the renew­able pro­duc­tion of aro­mat­ics from bio­mass-feed­stocks. Recent­ly, he has pub­lished work on the renew­able pro­duc­tion of phthal­ic anhy­dride from furan and male­ic anhy­dride by using mixed sul­fon­ic-car­boxylic anhy­drides.