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.

CO2 Conversion via Catalysis and Electrocatalysis

Meeting Program — January 2016

Jingguang Chen
Jing­guang Chen
Thay­er Lind­s­ley Pro­fes­sor of Chem­i­cal Engi­neer­ing
Colum­bia Uni­ver­si­ty

Abstract — Ocean acid­i­fi­ca­tion and cli­mate change are expect­ed to be two of the most dif­fi­cult sci­en­tif­ic chal­lenges of the 21st cen­tu­ry. Con­vert­ing CO2 into valu­able chem­i­cals and fuels is one of the most prac­ti­cal routes for reduc­ing CO2 emis­sions while fos­sil fuels con­tin­ue to dom­i­nate the ener­gy sec­tor. The cat­alyt­ic reduc­tion of CO2 by H2 can lead to the for­ma­tion of three types of prod­ucts: CO through the reverse water-gas shift (RWGS) reac­tion, methanol via selec­tive hydro­gena­tion, and hydro­car­bons through com­bi­na­tion of CO2 reduc­tion with Fis­ch­er-Trop­sch (FT) reac­tions. In the cur­rent talk we will dis­cuss some of our recent results in CO2 con­ver­sion via both het­ero­gen­er­ous catal­y­sis and elec­tro­catal­y­sis. Our research approach­es involve the com­bi­na­tion of DFT cal­cu­la­tions and sur­face sci­ence stud­ies over sin­gle crys­tal sur­faces, eval­u­a­tions over sup­port­ed cat­a­lysts, and in-situ char­ac­ter­i­za­tion under reac­tion con­di­tions. We will also dis­cuss chal­lenges and oppor­tu­ni­ties in this impor­tant research field.
Biog­ra­phy — Jing­guang Chen is the Thay­er Lind­s­ley Pro­fes­sor of chem­i­cal engi­neer­ing at Colum­bia Uni­ver­si­ty. He received his PhD degree from the Uni­ver­si­ty of Pitts­burgh and then car­ried out his Hum­boldt post­doc­tor­al research in Ger­many. After spend­ing sev­er­al years as a staff sci­en­tist at Exxon Cor­po­rate Research he start­ed his aca­d­e­m­ic career at the Uni­ver­si­ty of Delaware in 1998, and then took the roles as the direc­tor of the Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy and the Claire LeClaire Pro­fes­sor of chem­i­cal engi­neer­ing. He moved to Colum­bia Uni­ver­si­ty in 2012. He is the co-author of 20 US patents and over 300 jour­nal arti­cles with over 12,000 cita­tions. He received many awards, includ­ing the awards from the catal­y­sis clubs of Philadel­phia (2004), New York (2008), Chica­go (2011) and Michi­gan (2015). He recent­ly won the 2015 George Olah award from the Amer­i­can Chem­i­cal Soci­ety.

Engineering Molecular Transformations over Supported Metal Catalysts for the Sustainable Conversion of Biomass-Derived Intermediates to Chemicals and Fuels

Meeting Program — October 2015

Matt Neurock
Matt Neu­rock
Shell Pro­fes­sor of Chem­i­cal Engi­neer­ing and Mate­ri­als Sci­ence
Uni­ver­si­ty of Min­neso­ta

Abstract — Future strate­gies for ener­gy pro­duc­tion will undoubt­ed­ly require process­es and mate­ri­als that can effi­cient­ly con­vert sus­tain­able resources such as bio­mass into fuels and chem­i­cals. While nature’s enzymes ele­gant­ly inte­grate high­ly active cen­ters togeth­er with adap­tive nanoscale envi­ron­ments to con­trol the cat­alyt­ic trans­for­ma­tion of mol­e­cules to spe­cif­ic prod­ucts, they are dif­fi­cult to incor­po­rate into large scale indus­tri­al process­es and lim­it­ed in terms of their sta­bil­i­ty. The design of more robust het­ero­ge­neous cat­alyt­ic mate­ri­als that can mim­ic enzyme behav­ior, how­ev­er, has been hin­dered by our lim­it­ed under­stand­ing of how such mol­e­c­u­lar trans­for­ma­tions pro­ceed over inor­gan­ic mate­ri­als. The tremen­dous advances in ab ini­tio the­o­ret­i­cal meth­ods, mol­e­c­u­lar sim­u­la­tions and high per­for­mance com­put­ing that have occurred over the past two decades pro­vide unprece­dent­ed abil­i­ty to track these trans­for­ma­tions and how they pro­ceed at spe­cif­ic sites and with­in par­tic­u­lar envi­ron­ments. This infor­ma­tion togeth­er with the unique abil­i­ties to fol­low such trans­for­ma­tions spec­tro­scop­i­cal­ly is enabling the design of unique atom­ic sur­face ensem­bles and nanoscale reac­tion envi­ron­ment that can effi­cient­ly cat­alyze spe­cif­ic mol­e­c­u­lar trans­for­ma­tions. This talk dis­cuss­es recent advances in com­pu­ta­tion­al catal­y­sis and their appli­ca­tion to engi­neer­ing mol­e­c­u­lar trans­for­ma­tions for the con­ver­sion of bio­mass into chem­i­cals and fuels. We will dis­cuss the active sites, mech­a­nisms and nanoscale reac­tion envi­ron­ments involved in spe­cif­ic bond mak­ing and break­ing reac­tions impor­tant in the con­ver­sion of bio­mass-derived inter­me­di­ates into chem­i­cals and fuels and the design of 3D envi­ron­ments nec­es­sary to car­ry out such trans­for­ma­tions.
Biog­ra­phy — Matt Neu­rock is the Shell Pro­fes­sor of Chem­i­cal Engi­neer­ing and Mate­ri­als Sci­ence at the Uni­ver­si­ty of Min­neso­ta. He received his B.S. degree in Chem­i­cal Engi­neer­ing from Michi­gan State Uni­ver­si­ty and his Ph.D. from the Uni­ver­si­ty of Delaware in 1992. He worked as a Post­doc­tor­al Fel­low at the Eind­hoven Uni­ver­si­ty of Tech­nol­o­gy in the Nether­lands from 1992–1993 and sub­se­quent­ly as Vis­it­ing Sci­en­tist in the Cor­po­rate Catal­y­sis Cen­ter at DuPont from 1993–1994. He joined the fac­ul­ty in Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Vir­ginia in 1995 where he held joint appoint­ments in Chem­i­cal Engi­neer­ing and Chem­istry. In 2014 he moved to the Uni­ver­si­ty of Min­neso­ta and is cur­rent­ly on the fac­ul­ty in Chem­i­cal Engi­neer­ing and Mate­ri­als Sci­ence. He has made sem­i­nal advances to devel­op­ment and appli­ca­tion of com­pu­ta­tion­al meth­ods toward under­stand­ing cat­alyt­ic and elec­tro­cat­alyt­ic reac­tion mech­a­nisms, and the sites and envi­ron­ments that car­ry out reac­tions under work­ing con­di­tions. He has received var­i­ous awards for his research in com­pu­ta­tion­al catal­y­sis and mol­e­c­u­lar reac­tion engi­neer­ing includ­ing the Robert Bur­well Lec­ture­ship from the North Amer­i­can Catal­y­sis Soci­ety, R.H. Wil­helm Award in Chem­i­cal Reac­tion Engi­neer­ing from the Amer­i­can Insti­tute of Chem­i­cal Engi­neers, Paul H. Emmett Award in Fun­da­men­tal Catal­y­sis from the North Amer­i­can Catal­y­sis Soci­ety, Dis­tin­guished Vis­it­ing Pro­fes­sor of Uni­ver­si­ty of Mont­pel­li­er, East­man Chem­i­cal Lec­tur­er at the Uni­ver­si­ty of Cal­i­for­nia Berke­ley, Richard S. H. Mah Lec­tur­er at North­west­ern Uni­ver­si­ty, Johansen-Cros­by Lec­tur­er at Michi­gan State Uni­ver­si­ty, NSF Career Devel­op­ment Award, DuPont Young Inves­ti­ga­tor Award, Ford Young Fac­ul­ty Award. He has co-authored over 240 papers, two patents and two books. He is an edi­tor for the Jour­nal of Catal­y­sis and serves on numer­ous oth­er edi­to­r­i­al and advi­so­ry boards.

Catalysis for renewable fuels and chemicals: Challenges today and a look into where we are going

Meeting Program — November 2015

John Holladay
John Hol­la­day
Bio­mass Sec­tor Man­ag­er, and Asso­ciate Direc­tor of the Insti­tute for Inte­grat­ed Catal­y­sis
Pacif­ic North­west Nation­al Lab­o­ra­to­ry

Abstract — Renew­able car­bon sources, such as bio­mass and sug­ars, offer alter­na­tive start­ing mate­ri­als for pro­duc­ing fuels and chem­i­cals. How­ev­er, catal­y­sis of high­ly oxy­genat­ed mate­ri­als, often oper­at­ing in the con­densed phase, present sub­stan­tial chal­lenges with cat­a­lyst deac­ti­va­tion due to poi­son­ing and reac­tor bed/support sta­bil­i­ty. In essence, the cat­a­lysts devel­oped with­in the petro­chem­i­cal indus­try are often not suit­able and new solu­tions are need­ed if we are to match the effi­cien­cy that has been born from near­ly 90 years of sci­ence and tech­nol­o­gy aimed at hydro­car­bon pro­cess­ing.
In cov­er­ing chal­lenges today we will sur­vey two fam­i­lies of cat­alyt­ic tech­nolo­gies that pro­duce fuels—with an empha­sis on dis­til­lates and mid-dis­til­lates and chem­i­cal prod­ucts. These tech­nolo­gies will cov­er (i) upgrad­ing of oxy­genates (from alco­hols to com­plex bio-oils) and (ii) catal­y­sis of fer­men­ta­tion derived mol­e­cules that have been min­i­mal­ly processed. The pri­ma­ry focus will be on prob­lems and spe­cif­ic solu­tions that allowed long term, sta­ble and effi­cient oper­a­tion under con­tin­u­ous reac­tion con­di­tions suit­able for indus­try.
In part 2 of the lec­ture we will take a for­ward look toward where we would like to move the state of cat­a­lyst tech­nol­o­gy to allow pro­cess­ing of a broad­er range of car­bon from waste resources at the (small) size of the point source while keep­ing cap­i­tal and oper­at­ing cost low. Such feed­stocks include gaseous streams, such as CO-rich off gas; wet streams from food pro­cess­ing and waste water sludges; as well as dry streams from agri­cul­ture and for­est residues or munic­i­pal sol­id waste.
Biog­ra­phy — John Hol­la­day joined the Pacif­ic North­west Nation­al Lab­o­ra­to­ry (PNNL) in 2001 after work­ing for five years at Union Car­bide in South Charleston, WV. John cur­rent­ly serves as the Bio­mass Sec­tor Man­ag­er at PNNL, where he is respon­si­ble for shap­ing PNNL’s strat­e­gy and vision for renew­able fuels and chem­i­cals. The pro­gram focus­es on mul­ti­ple areas includ­ing: devel­op­ing cost-effec­tive cat­a­lysts for renew­able car­bon con­ver­sion, learn­ing from the effi­cien­cy that fun­gi offers for nat­u­ral­ly pro­cess­ing bio­mass, and under­stand­ing alter­na­tive means for pro­duc­ing bio­mass in waste streams that are wet/dry or gaseous. He facil­i­tates PNNL’s col­lab­o­ra­tion with oth­ers in acad­e­mia, indus­try and gov­ern­ment to advance the nation’s bio­fu­els research. He served as Chief Sci­en­tif­ic Offi­cer for the Nation­al Advanced Bio­fu­els Con­sor­tium, Chief Oper­a­tions Offi­cer for the Nation­al Alliance for Bio­fu­els and Bio­prod­ucts and is cur­rent­ly an Asso­ciate Direc­tor of the Insti­tute for Inte­grat­ed Catal­y­sis at PNNL.

Catalysis – An Indispensable Tool

Meeting Program — September 2015

Sourav Sengupta
Sourav Sen­gup­ta
Mol­e­c­u­lar Sci­ences, CR&D
E. I. DuPont de Nemours & Co
Wilm­ing­ton, DE

Abstract — In the past three decades, there has been a con­cert­ed effort in the chem­i­cal, agro­chem­i­cal, phar­ma­ceu­ti­cal, nutraceu­ti­cal, and petro­le­um indus­tries to design cost-advan­taged, inher­ent­ly safer, sus­tain­able, and envi­ron­men­tal­ly-friend­ly process­es. Catal­y­sis plays a cru­cial role in improv­ing process effi­cien­cies and process inten­si­fi­ca­tion lead­ing to increased atom uti­liza­tion, reduced by-prod­uct for­ma­tion, cheap­er process, and low­er cap­i­tal invest­ment. Also, there is an increas­ing inter­est in using renew­ably-sourced feed­stocks for the pro­duc­tion of fuels, chem­i­cals, and advanced mate­ri­als due to fluc­tu­a­tions in petro­le­um prices, lim­it­ed avail­abil­i­ty of petro­le­um resources, and increas­ing con­sumer con­scious­ness about sus­tain­able process­es.
Although catal­y­sis is a major tour-de-force in dri­ving this effi­ca­cious and green chem­istry rev­o­lu­tion, the role of reac­tion engi­neer­ing, reac­tor design, process devel­op­ment, and opti­mum oper­at­ing con­di­tions can­not be under­es­ti­mat­ed. Some of the fun­da­men­tal con­cepts of catal­y­sis will be dis­cussed and linked to chem­i­cal process­es of indus­tri­al rel­e­vance. Specif­i­cal­ly, the role of sci­ence and engi­neer­ing in indus­tri­al catal­y­sis will be illus­trat­ed with par­tic­u­lar empha­sis on cat­a­lyst eval­u­a­tion, process opti­miza­tion, cat­a­lyst deac­ti­va­tion, and reac­tor design asso­ci­at­ed with indus­tri­al process­es. Case stud­ies will include hydro­gena­tion reac­tions using sup­port­ed base met­al and pre­cious met­al cat­a­lysts and sol­id acid cat­alyzed reac­tions, includ­ing the hydro­gena­tion of hexa­flu­o­roace­tone and cat­mint oil, and dehy­dra­tion of xylose.
Biog­ra­phy — Dr. Sourav K. Sen­gup­ta is a Research Fel­low in the Mol­e­c­u­lar Sci­ences Divi­sion (Cen­tral Research & Devel­op­ment Depart­ment) of E. I. DuPont de Nemours & Co. He received his PhD degree in Chem­i­cal Engi­neer­ing from the Uni­ver­si­ty of Delaware in 1991. Imme­di­ate­ly after com­plet­ing his PhD, Dr. Sen­gup­ta joined the DuPont Com­pa­ny and was placed on loan to Cono­co where he devel­oped nov­el path­ways for the oxida­tive desul­fu­r­iza­tion of gaso­line and qual­i­fied new hydrodesul­fu­r­iza­tion and FCC cat­a­lysts. Short­ly after­wards, he was trans­ferred to the Cor­po­rate Catal­y­sis Cen­ter (CR&D). At CR&D, he worked on sol­id acid, sol­id base, and hydro­gena­tion catal­y­sis pro­grams and made impor­tant con­tri­bu­tions to a num­ber of Strate­gic Busi­ness Unit (SBUs).
Dr. Sen­gup­ta spent sev­er­al years at DuPont’s Nylon busi­ness unit, where he worked on a num­ber of com­mer­cial process­es and research pro­grams, includ­ing low-pres­sure and high-pres­sure ADN hydro­gena­tion, hydro­gen cyanide syn­the­sis by Andrus­sow and induc­tion-heat­ing process­es, and nitrous oxide destruc­tion cat­a­lyst tech­nol­o­gy.
When DuPont sold their Nylon, poly­ester, and Lycra busi­ness­es to Koch Indus­tries, Dr. Sen­gup­ta joined Invista, a whol­ly-owned sub­sidiary of Koch Indus­tries, where his work involved inves­ti­gat­ing the tech­ni­cal and eco­nom­ic fea­si­bil­i­ty of capro­lac­tam com­mer­cial­iza­tion.
After a short stint at Invista, Dr. Sen­gup­ta came back to DuPont, and joined their Chem­i­cal Solu­tions Enter­prise (DCSE) as a man­u­fac­tur­ing tech­ni­cal chemist at Cham­bers Works in New Jer­sey. His respon­si­bil­i­ty cov­ered 42 dif­fer­ent spe­cial­ty chem­i­cals. There he worked with a team of experts to design, devel­op, and com­mer­cial­ize a nov­el hydro­gena­tion process for the pro­duc­tion of hexa­flu­o­roiso­propanol (HFIP) and hexa­flu­o­roace­tone (HFA) recov­ery process. He was also involved in the com­mer­cial­iza­tion of a num­ber of Cap­stone prod­ucts. In 2009, he start­ed up a Process Devel­op­ment Cen­ter for DCSE at the Exper­i­men­tal Sta­tion. In 2011, he moved back to CR&D and has been work­ing on a num­ber of R&D pro­grams on using renew­able feed­stock to man­u­fac­ture chem­i­cals and mate­ri­als and new cat­a­lyst devel­op­ment.
Dr. Sengupta’s exper­tise is in the area of catal­y­sis, reac­tion engi­neer­ing and reac­tor analy­sis, and process devel­op­ment. He has over 65 US patents, pub­li­ca­tions, and pre­sen­ta­tions to his cred­it.

The Design of New Catalysts for Biomass Conversion with Atomic Layer Deposition

Meeting Program — April 2015

George Huber
Depart­ment of Chem­i­cal and Bio­log­i­cal Engi­neer­ing
Uni­ver­si­ty of Wis­con­sin, Madi­son, WI

The objec­tive of the Huber research group is to devel­op new cat­alyt­ic process­es and cat­alyt­ic mate­ri­als for the pro­duc­tion of renew­able fuels and chem­i­cals from bio­mass, solar ener­gy, and nat­ur­al gas resources. We use a wide range of mod­ern chem­i­cal engi­neer­ing tools to design and opti­mize these clean tech­nolo­gies includ­ing: het­ero­ge­neous catal­y­sis, kinet­ic mod­el­ing, reac­tion engi­neer­ing, spec­troscopy, ana­lyt­i­cal chem­istry, nan­otech­nol­o­gy, cat­a­lyst syn­the­sis, con­cep­tu­al process design, and the­o­ret­i­cal chem­istry. In this pre­sen­ta­tion we will first dis­cuss the hydrodeoxy­gena­tion of bio­mass into dif­fer­ent fuels and chem­i­cals. In addi­tion we can use HDO to eas­i­ly pro­duce new class­es mol­e­cules that are not cur­rent­ly pro­duced from petro­le­um feed­stocks. Hydrodeoxy­gena­tion (HDO) is a plat­form tech­nol­o­gy used to con­vert liq­uid bio­mass feed­stocks (includ­ing aque­ous car­bo­hy­drates, pyrol­y­sis oils, and aque­ous enzy­mat­ic prod­ucts) into alka­nes, alco­hols and poly­ols. In this process the bio­mass feed reacts with hydro­gen to pro­duce water and a deoxy­genat­ed prod­uct using a bifunc­tion­al cat­a­lyst that con­tains both met­al and acid sites. The chal­lenge with HDO is to selec­tive­ly pro­duce tar­get­ed prod­ucts that can be used as fuel blend­stocks or chem­i­cals and to decrease the hydro­gen con­sump­tion. We will dis­cuss how dif­fer­ent bio­mass based feed­stocks can be con­vert­ed into fuels or chem­i­cals by HDO. We will out­line the fun­da­men­tal cat­alyt­ic chem­istry and the sci­en­tif­ic chal­lenges. We will then dis­cuss how ALD can be used to design improved cat­alyt­ic mate­ri­als.

Atom­ic lay­er depo­si­tion (ALD) has emerged as a tool for the atom­i­cal­ly pre­cise design and syn­the­sis of cat­alyt­ic mate­ri­als. We dis­cuss exam­ples where the atom­ic pre­ci­sion has been used to elu­ci­date reac­tion mech­a­nisms and cat­a­lyst struc­ture-prop­er­ty rela­tion­ships by cre­at­ing mate­ri­als with a con­trolled dis­tri­b­u­tion of size, com­po­si­tion, and active site. We high­light ways ALD has been uti­lized to design cat­a­lysts with improved activ­i­ty, selec­tiv­i­ty, and sta­bil­i­ty under a vari­ety of con­di­tions (e.g., high tem­per­a­ture, gas- and liq­uid-phase, and cor­ro­sive envi­ron­ments). In addi­tion, due to the flex­i­bil­i­ty and con­trol of struc­ture and com­po­si­tion, ALD can cre­ate myr­i­ad cat­alyt­ic struc­tures (e.g., high sur­face area oxides, met­al nanopar­ti­cles, bimetal­lic nanopar­ti­cles, bifunc­tion­al cat­a­lysts, con­trolled micro-envi­ron­ments, etc.) that con­se­quent­ly pos­sess applic­a­bil­i­ty for a wide-rang­ing num­ber of chem­i­cal reac­tions (e.g., CO2 con­ver­sion, elec­tro­catal­y­sis, pho­to­cat­alyt­ic and ther­mal water split­ting, methane con­ver­sion, ethane and propane dehy­dro­gena­tion, and bio­mass con­ver­sion). Final­ly, the out­look for ALD-derived cat­alyt­ic mate­ri­als is dis­cussed with empha­sis on the pend­ing chal­lenges as well as areas of sig­nif­i­cant poten­tial for build­ing sci­en­tif­ic insight and achiev­ing prac­ti­cal impacts.

George Huber
George W. Huber is a Pro­fes­sor of Chem­i­cal Engi­neer­ing at Uni­ver­si­ty of Wis­con­sin-Madi­son. His research focus is on devel­op­ing new cat­alyt­ic process­es for the pro­duc­tion of renew­able liq­uid fuels and chem­i­cals.

George is one of the most high­ly cit­ed young schol­ars in the chem­i­cal sci­ences being cit­ed over 3,200 times in 2014 and over 14,000 times in his career. He has authored over 100 peer-reviewed pub­li­ca­tions includ­ing three pub­li­ca­tions in Sci­ence. Patents and tech­nolo­gies he has helped devel­op have been licensed by three dif­fer­ent com­pa­nies. He has received sev­er­al awards includ­ing the NSF CAREER award, the Drey­fus Teacher-Schol­ar award, fel­low of the Roy­al Soci­ety of Chem­istry, and the out­stand­ing young fac­ul­ty award (2010) by the col­lege of engi­neer­ing at UMass-Amherst. He has been named one of the top 100 peo­ple in bioen­er­gy by Bio­fu­els Digest for the past 3 years. He is co-founder of Anel­lotech a bio­chem­i­cal com­pa­ny focused on com­mer­cial­iz­ing, cat­alyt­ic fast pyrol­y­sis, a tech­nol­o­gy to pro­duce renew­able aro­mat­ics from bio­mass. George serves on the edi­to­r­i­al board of Ener­gy and Envi­ron­men­tal Sci­ence, Chem­CatChem, and The Cat­a­lyst Review. In June 2007, he chaired a NSF and DOE fund­ed work­shop enti­tled: Break­ing the Chem­i­cal and Engi­neer­ing Bar­ri­ers to Lig­no­cel­lu­losic Bio­fu­els (www​.ecs​.umass​.edu/​b​i​o​f​u​els).

George did a post-doc­tor­al stay with Aveli­no Cor­ma at the Tech­ni­cal Chem­i­cal Insti­tute at the Poly­tech­ni­cal Uni­ver­si­ty of Valen­cia, Spain (UPV-CSIC) where he stud­ied bio-fuels pro­duc­tion using petro­le­um refin­ing tech­nolo­gies. He obtained his Ph.D. in Chem­i­cal Engi­neer­ing from Uni­ver­si­ty of Wis­con­sin-Madi­son (2005). He obtained his B.S. (1999) and M.S.(2000) degrees in Chem­i­cal Engi­neer­ing from Brigham Young Uni­ver­si­ty.