Solid Catalysts Design: From Fundamental Knowledge To Catalytic Application

Meeting Program — April 2017

Professor Avelino Corma
Pro­fes­sor Aveli­no Cor­ma
Pro­fes­sor and founder of the Insti­tu­to de Tec­nología Quími­ca (UPV-CSIC)
Valen­cia, Spain

 

Abstract — The key point in catal­y­sis is to define and syn­the­size the spe­cif­ic active site that will min­i­mize the acti­va­tion ener­gy of the reac­tion, while form­ing selec­tive­ly the desired prod­uct.

In the case of homo­ge­neous catal­y­sis, high­ly selec­tive mol­e­c­u­lar cat­a­lysts can be designed and/or opti­mized from the fun­da­men­tal knowl­edge accu­mu­lat­ed on chem­i­cal reac­tiv­i­ty, and the pos­si­bil­i­ties offered by mol­e­c­u­lar mod­el­ling, in situ or operan­do spec­troscopy, kinet­ics and advanced cat­a­lyst syn­the­sis. Then, when the cat­alyt­i­cal­ly active cen­ters are defined, and their inter­ac­tion with reac­tants and prod­ucts can be ratio­nal­ized, it could, in prin­ci­ple, be pos­si­ble to pre­dict and pre­pare more active and selec­tive cat­a­lysts. In the case of sol­id cat­a­lysts it becomes more dif­fi­cult to define and specif­i­cal­ly build the active sites due to sur­face het­ero­geneities present in most of the solids. Indeed, one should con­sid­er that the pres­ence of non-con­trol­lable sur­face defects and the fact that sur­face recon­struc­tion may occur dur­ing the cat­alyt­ic reac­tion, makes the iden­ti­fi­ca­tion and syn­the­sis of the active sites in sol­id cat­a­lysts a big chal­lenge.

From the point of view of max­i­miz­ing active sites, and since catal­y­sis with solids is a sur­face phe­nom­e­non, high sur­face sol­id cat­a­lysts are most of the times pre­ferred. In this case it is not a sim­ple task to iden­ti­fy the assem­bly of atoms, and there­fore to estab­lish the enthalpy and entropy effects at the inter­face of the sol­id-gas or sol­id-liq­uid, that will be respon­si­ble for the cat­alyt­ic effect at the mol­e­c­u­lar lev­el. More­over, even when the above is achieved, to syn­the­size the solids with well defined, homo­ge­neous sin­gle or mul­ti­ple cat­alyt­i­cal­ly active sites it is a dif­fi­cult task. Notice that reac­tion selec­tiv­i­ty will depend on the capac­i­ty to pre­pare the sol­id avoid­ing the pres­ence of sites oth­er than the desired ones.

It was our objec­tive, since the first moment, to design and syn­the­size sol­id cat­a­lysts in where we could build with­in the struc­ture (almost like in a lego), on the bases of the knowl­edge devel­oped on reac­tion mech­a­nisms, adsorp­tion inter­ac­tions and mate­ri­als syn­the­sis pro­ce­dures, the poten­tial cat­alyt­ic active sites. We expect­ed that, if suc­cess­ful, this could be one way to achieve sol­id cat­a­lysts with well defined, uni­form sin­gle or mul­ti­ple active sites. It also appeared to us that work­ing in that way it should be pos­si­ble to build bridges between the homo­ge­neous and het­ero­ge­neous catal­y­sis. We are aware that in the case of the sol­id cat­a­lysts would not be pos­si­ble to achieve the fine tun­ing of elec­tron­ic, geo­met­ric and chi­ral effects obtained by means of the lig­ands and mol­e­c­u­lar struc­ture, with tran­si­tion met­al com­plex­es, and organ­ic mol­e­cules in homo­ge­neous catal­y­sis. Nev­er­the­less, we attempt­ed to use the sur­face topol­o­gy, tex­tur­al char­ac­ter­is­tics and chem­i­cal com­po­si­tion of the sol­id to mas­ter mol­e­c­u­lar dif­fu­sion and adsorp­tion of reac­tants, while select­ing one among the dif­fer­ent pos­si­ble tran­si­tion states.

We will present what has been our evo­lu­tion on the design of three types of sol­id cat­a­lysts in where we fol­lowed the method­ol­o­gy describe above. They are:

  1. High sur­face area hybrid organ­ic-inor­gan­ic cat­a­lysts in where we attempt to reg­u­late the char­ac­ter­is­tics of the active sites and the geo­met­ri­cal flex­i­bil­i­ty to max­i­mize dis­per­sion forces.
  2. Ful­ly inor­gan­ic high­ly ther­mi­cal­ly sta­ble micro and meso­porous mate­ri­als with well defined sin­gle sites, while con­trol­ling mol­e­c­u­lar dif­fu­sion and adsorp­tion to achieve remark­able selec­tiv­i­ty effects.
  3. Gen­er­at­ing and sta­bi­liz­ing from sin­gle met­al atoms to clus­ters with a few atoms to nanopar­ti­cles, with reac­tiv­i­ties so high that remind those of enz­imes.

We will show that by fol­low­ing the method­ol­o­gy: “under­stand­ing for design­ing and syn­the­siz­ing”, we could also achieve what it is always a desir­able objec­tive in catal­y­sis: “Design­ing for indus­tri­al appli­ca­tion”.

Biog­ra­phy — Aveli­no Cor­ma, Pro­fes­sor and founder of the Insti­tu­to de Tec­nología Quími­ca (CSIC-UPV) in Valen­cia (Spain), he has been car­ry­ing out research in het­ero­ge­neous catal­y­sis in acad­e­mia and in col­lab­o­ra­tion with com­pa­nies for near­ly 35 years. He has worked on fun­da­men­tal aspects of acid-base and redox catal­y­sis with the aim of under­stand­ing the nature of the active sites, and reac­tion mech­a­nisms. With these bases has devel­oped cat­a­lysts that are being used com­mer­cial­ly in sev­er­al indus­tri­al process­es. He is an inter­na­tion­al­ly rec­og­nized expert in sol­id acid and bifunc­tion­al cat­a­lysts for oil refin­ing, petro­chem­istry and chem­i­cal process, espe­cial­ly in the syn­the­sis and appli­ca­tion of zeo­lite cat­a­lysts. He has pub­lished more than 900 research papers, and inven­tor on more than 130 patents. Cor­ma earned his BS in Chem­istry at Valen­cia Uni­ver­si­ty, PhD at Madrid under direc­tion of Prof. Anto­nio Cortes, and spent two years post­doc at Queen ́s Uni­ver­si­ty. He has received the Dupont Award on “Mate­ri­als Sci­ence”, Cia­pet­ta and Houdry Awards of the North Amer­i­can Catal­y­sis Soci­ety, the F. Gault Award of the Euro­pean Catal­y­sis Soci­ety, the M. Boudart Award on Catal­y­sis by the North Amer­i­can and Euro­pean Catal­y­sis Soci­eties, the G. J. Somor­jai ACS Award on Cre­ative Catal­y­sis, the Breck Award of the Inter­na­tion­al Zeo­lite Asso­ci­a­tion, the Nation­al Award of Sci­ence and tech­nol­o­gy of Spain, “Rey Jaume I” Prize for New Tech­nolo­gies (2000), the ENI
Award on Hydro­car­bon Chem­istry, the Roy­al Soci­ety of Chem­istry Cen­te­nary Prize, Solvay Pierre-Gilles de Gennes Prize for Sci­ence and Indus­try and Gold Medal for the Chem­istry Research Career 2001–2010 in Spain, La Grande Médaille de l’Académie des sci­ences de France 2011 and Hon­our Medal to the Inven­tion from the Fun­dación Gar­cía Cabreri­zo in Spain. Gold Medal Foro QUÍMICA y SOCIEDAD to all his research career, Gran Medaille of the Sci­ence French Acad­e­my, Edith Flani­gen Lec­ture­ship, East­man Lec­ture, Direc­tor ́s Dis­tin­guished Lec­ture Series Pacif­ic North­west Nation­al Lab­o­ra­to­ry ́s. Prince of Asturias Award for Sci­ence & Tech­nol­o­gy 2014, 48th W. N. Lacey Lec­ture­ship in Chem­i­cal Engi­neer­ing-Cal­tech (2015) and The Jacobus van ‘t Hoff Lec­ture 2015 at TU Delft Process Tech­nol­o­gy Insti­tute (2015), The Hoyt C. Hot­tel Lec­tur­er in Chem­i­cal Engi­neer­ing at MIT Chem­i­cal Engi­neer­ing Depart­ment (2015), J.T. Don­ald Lec­ture series 2015–2016 at McGill Uni­ver­si­ty, Spiers Memo­r­i­al Award RSC (2016), IZA Award of the Inter­na­tion­al Zeo­lite Asso­ci­a­tion (2016), George C.A. Schuit Award lec­ture at the Uni­ver­si­ty of Delaware (2016).

Doc­tor Hon­oris Causa” by Utrecht Uni­ver­si­ty (2006), UNED (2008), München Tech­no­log­i­cal Uni­ver­si­ty (2008), Uni­ver­si­dad Jaime I de Castel­lón (2008), Uni­ver­si­dad de Valen­cia (2009), Bochüm Uni­ver­si­ty (2010), Uni­ver­si­dad de Ali­cante (2010), Ottawa Uni­ver­si­ty (2012) Delft Tech­no­log­i­cal Uni­ver­si­ty (2013) Jilin Uni­ver­si­ty (Chi­na) (2013), Uni­ver­si­ty of Bucarest (2014), Jaen (2016), Cantabria (2016).

Parallel between UOP’s Reforming and Dehydrogenation Technologies and Catalysts

Meeting Program — March 2017

Manuela Serban
Manuela Ser­ban
Prin­ci­pal Research Sci­en­tist,
Hon­ey­well UOP

 

Abstract — With sig­nif­i­cant expe­ri­ence in Con­tin­u­ous Cat­a­lyst Regen­er­a­tion (CCR) reform­ing tech­nol­o­gy, i.e., Plat­form­ing™ process, Honeywell’s UOP was unique­ly posi­tioned to invent, devel­op and com­mer­cial­ize 25 years ago, a CCR-type light paraf­fins dehy­dro­gena­tion tech­nol­o­gy, i.e., Ole­flex™ process, lever­ag­ing on the Plat­form­ing tech­nol­o­gy. These two tech­nolo­gies rep­re­sent two of UOP’s core tech­nolo­gies and togeth­er with their cat­a­lysts, are being con­tin­u­ous­ly improved and opti­mized to max­i­mize end-user prof­itabil­i­ty. Cur­rent­ly there are 300+ CCR Plat­form­ing units and 25+ Ole­flex units oper­at­ing world­wide, with more in con­struc­tion or in com­mis­sion. This pre­sen­ta­tion will high­light sim­i­lar­i­ties and dif­fer­ences between the Plat­form­ing and Ole­flex tech­nolo­gies and cat­a­lysts. We will dis­cuss the chem­i­cal and phys­i­cal require­ments and prop­er­ties for the two types of cat­a­lysts, the main cat­a­lysts deac­ti­va­tion routes, and high­light some of UOP’s char­ac­ter­i­za­tion tools and exper­tise used to devel­op new reform­ing and dehy­dro­gena­tion cat­a­lysts and diag­nose dif­fer­ent symp­toms relat­ed to aged com­mer­cial cat­a­lysts.

Biog­ra­phy — Manuela Ser­ban is a Prin­ci­pal Research Sci­en­tist in the Olefins and Deter­gents Devel­op­ment Group lead­ing teams respon­si­ble for the devel­op­ment of new Ole­flex cat­a­lyst gen­er­a­tions. Manuela has over 12 years of expe­ri­ence with UOP, includ­ing reform­ing tech­nol­o­gy and cat­a­lysts, cat­alyt­ic hydrodesul­fu­r­iza­tion, flue gas desul­fu­r­iza­tion for coal gasi­fi­ca­tion plants, break­through liq­uid fuels decon­t­a­m­i­na­tion tech­niques. She is the author of sev­er­al arti­cles in peer reviewed Chem­i­cal Engi­neer­ing jour­nals and has 38 US patents. She has a PhD in Chem­i­cal Engi­neer­ing from Worces­ter Poly­tech­nic Insti­tute and post-doc­tor­al expe­ri­ence at Argonne Nation­al Lab­o­ra­to­ry.

Biomass and Natural Gas Valorization by Zeolite Catalysis

Meeting Program — February 2017

Raul Lobo
Raul Lobo
Claire D. LeClaire pro­fes­sor of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing,
Uni­ver­si­ty of Delaware

 

Abstract — Prof. Lobo’s research group is inter­est­ed in devel­op­ing and under­stand­ing catal­y­sis sys­tems to enable the trans­for­ma­tion abun­dant, inex­pen­sive and—when possible—renewable car­bon sources into feed­stocks for the chem­i­cal indus­try. We com­bine exper­tise in mate­ri­als syn­the­sis, catal­y­sis and kinet­ics, and reac­tion engi­neer­ing to devel­op nov­el cat­a­lysts and cat­alyt­ic process­es that pro­duce valu­able prod­ucts.

In the first part I will focus on C-C bond form­ing reac­tions that are help­ful in the trans­for­ma­tion of furans (pro­duced from glu­cose or xylose by dehy­dra­tion) into valu­able com­mod­i­ty chem­i­cals. To this end we have devel­oped and opti­mized zeo­lite cat­a­lyst com­po­si­tions to form aro­mat­ic species out of the furans via Diels-Alder reac­tions and Friedel-Craft acy­la­tion reac­tions. We will describe efforts to pro­duc­ing ben­zoic acid and α-methyl­styrene from furans in high selec­tiv­i­ty and high yield, along with the elu­ci­da­tion of the reac­tion mech­a­nisms of these reac­tions.

In the sec­ond part I will dis­cuss on-going research direct­ed towards the devel­op­ment of cat­a­lysts for the selec­tive oxi­da­tion of methane into methanol. We will show that zeo­lites can serve as hosts of tran­si­tion met­als oxide clus­ters (cop­per or iron) that are anal­o­gous to met­al oxide clus­ters observed in a num­ber of impor­tant enzymes such as par­tic­u­late methane monooxy­ge­nase (pMMO). These clus­ters are capa­ble of oxi­diz­ing methane to methanol, car­bon monox­ide and CO2. By selec­tive­ly choos­ing mate­ri­als that com­part­men­tal­ize Cu-O clus­ters, we have iden­ti­fied zeo­lite struc­tures that are able to selec­tive­ly oxi­dize methane to methanol with very high selec­tiv­i­ty in a three-step cyclic process. We will describe the poten­tial and the draw­backs of trans­form­ing such cyclic process into a cat­alyt­ic process for methanol pro­duc­tion.

Despite the matu­ri­ty of the field of catal­y­sis this talk will show that tan­ta­liz­ing new oppor­tu­ni­ties emerge from the dis­cov­ery of new cat­a­lyst struc­tures and com­po­si­tions, and from improve­ments in our con­trol of the com­po­si­tion of met­al clus­ters in nanoscop­ic envi­ron­ments.

Biog­ra­phy — Raul F. Lobo is the Claire D. LeClaire pro­fes­sor of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing at the Uni­ver­si­ty of Delaware and Direc­tor of the Cen­ter for Cat­alyt­ic Sci­ence and Tech­nol­o­gy. His research inter­ests span the devel­op­ment of nov­el porous mate­ri­als for catal­y­sis and sep­a­ra­tions, the chem­istry of zeo­lites, catal­y­sis for ener­gy and the envi­ron­ment, and the sci­en­tif­ic aspects of cat­a­lyst syn­the­sis. He has pub­lished over one hun­dred fifty ref­er­eed reports and he is co-inven­tor in three US patents. He obtained his under­grad­u­ate degree in Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Cos­ta Rica in 1989 and lat­er moved to Cal­i­for­nia to pur­sue grad­u­ate stud­ies in Chem­i­cal Engi­neer­ing at Cal­tech. He worked for one year at Los Alam­os Nation­al Lab­o­ra­to­ry, New Mex­i­co as a post­doc­tor­al fel­low and he start­ed his aca­d­e­m­ic career at the Uni­ver­si­ty of Delaware in 1995.

Prof. Lobo has con­duct­ed research in the use of zeo­lites for nitrogen/oxygen sep­a­ra­tions, and car­bon diox­ide sep­a­ra­tions from flue gas­es. He has con­tributed to the fun­da­men­tals of zeo­lite nucle­ation and crys­tal growth and to the appli­ca­tion of zeo­lites for a num­ber of cat­alyt­ic appli­ca­tions. In par­tic­u­lar his group research helped under­stand the mech­a­nisms of reac­tion and sta­bil­i­ty of zeo­lite cat­a­lysts used for the removal of NOx gas­es from com­bus­tion exhaust, devel­oped cat­alyt­ic mate­ri­als for the trans­for­ma­tion of bio­mass-derived furans into com­mod­i­ty aro­mat­ic mol­e­cules such as xylenes and ben­zoic acid and dis­cov­ered mate­ri­als for the selec­tive acti­va­tion of methane using cop­per oxide clus­ters.

Ciapetta Award Lecture: Novel Zeolite Catalysts for Diesel Emission Applications

Meeting Program — January 2017

Ahmad Moini
Ahmad Moi­ni
BASF Cor­po­ra­tion

 

Abstract — Auto­mo­tive exhaust con­di­tions present unique chal­lenges for the design of effec­tive cat­a­lysts. In addi­tion to the need for cat­alyt­ic activ­i­ty over a wide tem­per­a­ture range, the cat­a­lyst must show dura­bil­i­ty towards extreme hydrother­mal aging con­di­tions. The use of zeolitic mate­ri­als under such con­di­tions is espe­cial­ly chal­leng­ing due to the vul­ner­a­bil­i­ty of zeo­lites to steam aging. The BASF dis­cov­ery of the Cu-CHA cat­a­lyst for selec­tive cat­alyt­ic reduc­tion (SCR) of NOx demon­strat­ed an effec­tive bal­ance between favor­able active sites and zeo­lite frame­work dura­bil­i­ty. It also paved the way for the imple­men­ta­tion of urea SCR as the key approach for NOx reduc­tion in diesel vehi­cles. This pre­sen­ta­tion will high­light the devel­op­ment of Cu-CHA as the lead­ing tech­nol­o­gy for diesel emis­sion appli­ca­tions. Spe­cif­ic focus will be placed on the syn­the­sis and struc­tur­al fea­tures of the zeo­lite. In addi­tion, there will be a dis­cus­sion of spe­cif­ic char­ac­ter­i­za­tion and mod­el­ing approach­es focus­ing on the unique attrib­ut­es of the met­al active sites and the inter­ac­tion of these met­al species with the zeo­lite frame­work.

Biog­ra­phy — Dr. Ahmad Moi­ni is a Research Fel­low at BASF Cor­po­ra­tion in Iselin, NJ. He obtained his Ph.D. in Chem­istry from Texas A&M Uni­ver­si­ty, and held a post­doc­tor­al appoint­ment at Michi­gan State Uni­ver­si­ty. Dr. Moi­ni start­ed his career at Mobil Research & Devel­op­ment Cor­po­ra­tion (now Exxon­Mo­bil), where he con­duct­ed research on micro­p­orous mate­ri­als. With a focus on explorato­ry zeo­lite syn­the­sis, he stud­ied the mech­a­nism of zeo­lite crys­tal­liza­tion and the role of spe­cif­ic class­es of organ­ic direct­ing agents in the for­ma­tion of var­i­ous zeo­lite frame­works. He joined Engel­hard Cor­po­ra­tion (now BASF) in 1996. Since then, his pri­ma­ry research inter­ests have been in the area of mate­ri­als syn­the­sis, direct­ed at a range of cat­alyt­ic and func­tion­al appli­ca­tions. He applied high through­put meth­ods for the syn­the­sis and eval­u­a­tion of cat­alyt­ic mate­ri­als, and used these tools for the devel­op­ment of new prod­ucts. A sig­nif­i­cant part of his work has been direct­ed towards cat­a­lysts for envi­ron­men­tal appli­ca­tions. These efforts, in col­lab­o­ra­tion with the extend­ed BASF team, led to the dis­cov­ery and devel­op­ment of Cu-CHA cat­a­lyst for selec­tive cat­alyt­ic reduc­tion (SCR) of NOx from diesel vehi­cles. He holds 48 US patents relat­ing to var­i­ous aspects of mate­ri­als and cat­a­lyst devel­op­ment.

Unraveling Catalytic Mechanisms and Kinetics: Lessons from Electrical Networks

Meeting Program — November 2016

Ravindra Datta
Pro­fes­sor Ravin­dra Dat­ta
Pro­fes­sor in the Depart­ment of Chem­i­cal Engi­neer­ing,
Fuel Cell Cen­ter,
Worch­ester Poly­tech­nic Insti­tute

 

Abstract — Cat­alyt­ic reac­tion net­works, in gen­er­al, com­prise of mul­ti­ple steps and path­ways. While one can now read­i­ly pre­dict kinet­ics of these mol­e­c­u­lar steps from first prin­ci­ples, there is not yet avail­able a com­pre­hen­sive frame­work for: 1) visu­al­iz­ing and ana­lyz­ing these reac­tion net­works in their full com­plex­i­ty; and 2) unequiv­o­cal­ly iden­ti­fy­ing the ger­mane steps and path­ways.

Thus, we have devel­oped an approach called the “Reac­tion Route (RR) Graph” approach, which allows: 1) direct enu­mer­a­tion of all the path­ways as walks on the RR Graph; 2) ther­mo­dy­nam­ic con­sis­tence of step kinet­ics; 3) elu­ci­da­tion of dom­i­nant path­ways that con­tribute mate­ri­al­ly to the over­all flux; 4) iden­ti­fi­ca­tion of bot­tle­neck steps in each of these path­ways; and 5) devel­op­ment of explic­it rate laws based on the elec­tri­cal anal­o­gy.

The elec­tri­cal net­work anal­o­gy is based on two aspects of RR Graphs, name­ly: 1) qua­si-steady state (QSS) mass bal­ance of inter­me­di­ate species, the equiv­a­lent of the Kirchhoff’s Cur­rent Law (KCL) of elec­tri­cal cir­cuits; and 2) Hess’s law, or ther­mo­dy­nam­ic con­sis­tence, the equiv­a­lent of the Kirchhoff’s Poten­tial Law (KPL), which makes RR Graphs pre­cise­ly equiv­a­lent to elec­tri­cal net­works. Fur­ther, we define the step resis­tance in terms of step kinet­ics to make the anal­o­gy com­plete. The approach is described with the help of the water-gas shift exam­ple.

Biog­ra­phy — Ravi Dat­ta is Pro­fes­sor of Chem­i­cal Engi­neer­ing and Direc­tor of WPI Fuel Cell Cen­ter. He obtained his Ph.D. degree from the Uni­ver­si­ty of Cal­i­for­nia, San­ta Bar­bara, in 1981. From then until 1998, he was a Pro­fes­sor of Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Iowa, when he moved to WPI, and served as Chem­i­cal Engi­neer­ing Depart­ment Head until 2005. Ravi’s research is focused on cat­alyt­ic and elec­tro­cat­alyt­ic reac­tion engi­neer­ing of Clean Ener­gy, includ­ing, fuel cells, hydro­gen, renew­able fuels, nov­el cat­a­lysts, and cat­alyt­ic reac­tion net­works. He is a coau­thor of 150 papers and 8 patents, and has been a men­tor to 25 doc­tor­al stu­dents.

Development of heterogeneous catalysts for the production of biomass-derived chemicals by selective C-O hydrogenolysis and deoxydehydration

Meeting Program — October 2016

Keiichi Tomishige
Kei­ichi Tomishige
Pro­fes­sor in the School of Engi­neer­ing,
Tohoku Uni­ver­si­ty

 

Keiichi Tomishige

Abstract — Chem­i­cal com­po­si­tion of the feed­stock from bio­mass and bio­mass-based build­ing blocks has much high­er oxy­gen con­tents than that from crude oil. It has been known that the tar­get prod­ucts such as monomers for the poly­mer syn­the­sis have com­par­a­tive­ly low­er oxy­gen con­tent, and the method­ol­o­gy for the decrease of the oxy­gen con­tent is more and more impor­tant. One of effec­tive meth­ods is the uti­liza­tion of the hydrogenol­y­sis of C-O bonds in the sub­strates. For exam­ple, C3-C6 sug­ar alco­hols (glyc­erol, ery­thri­tol, xyl­i­tol, and sor­bitol) are also regard­ed as promis­ing build­ing blocks in the bio­mass refin­ery. If the selec­tive hydrogenol­y­sis of the tar­get C-O bond among var­i­ous kinds of the C-O bonds is pos­si­ble, valu­able chem­i­cals such as diols, mono-ols, alka­nes can be pro­duced from bio­mass in high yield. ReOx-mod­i­fied Ir met­al cat­a­lyst (Ir-ReOx) is report­ed to be effec­tive to the selec­tive hydrogenol­y­sis of poly­ols and cyclic ethers in water sol­vent. Ir-ReOx/SiO2 cat­alyzes the hydrogenol­y­sis of glyc­erol to 1,3-propanediol. The hydrogenol­y­sis of ery­thri­tol over the cat­a­lyst pro­duces 1,4- and 1,3-butanediols. The selec­tive hydrogenol­y­sis of tetrahy­dro­fur­furyl alco­hol to 1,5-pentanediol also pro­ceeds using Ir-ReOx/SiO2. In addi­tion, the com­bi­na­tion of Ir-ReOx/SiO2 with H-ZSM-5 gives n-alka­nes and hexa­nols from cel­lu­lose, sug­ars, and sug­ar alco­hols in high yield with the total C-O hydrogenol­y­sis and with­out C-C bond dis­so­ci­a­tion and skele­tal iso­mer­iza­tion. Anoth­er inter­est­ing cat­a­lyst is ReOx-Pd/CeO2. The cat­a­lyst showed excel­lent per­for­mance for simul­ta­ne­ous hydrodeoxy­gena­tion of vic­i­nal OH groups in var­i­ous sub­strates. High yield (>99%), turnover fre­quen­cy, and turnover num­ber were obtained in the reac­tion of 1,4-anhydroerythritol to tetrahy­dro­fu­ran. This cat­a­lyst is also applic­a­ble to the con­ver­sion of sug­ar alco­hols mono-alco­hols and diols are obtained in high yields from sub­strates with even and odd num­bers of OH groups, respec­tive­ly. In addi­tion, ReOx-Au/CeO2 cat­alyzed the con­ver­sion of glyc­erol and ery­thri­tol to allyl alco­hol and 1,3-butadiene in high yield (91% and 81%), respec­tive­ly.

Biog­ra­phy — Kei­ichi Tomishige received his B.S., M.S. and Ph.D. from Grad­u­ate School of Sci­ence, Depart­ment of Chem­istry, The Uni­ver­si­ty of Tokyo with Prof. Y. Iwa­sawa. Dur­ing his Ph.D. course in 1994, he moved to Grad­u­ate School of Engi­neer­ing, The Uni­ver­si­ty of Tokyo as a research asso­ciate and worked with Prof. K. Fuji­mo­to. In 1998, he became a lec­tur­er, and then he moved to Insti­tute of Mate­ri­als Sci­ence, Uni­ver­si­ty of Tsuku­ba as a lec­tur­er in 2001. Since 2004 he has been an asso­ciate pro­fes­sor, Grad­u­ate School of Pure and Applied Sci­ences, Uni­ver­si­ty of Tsuku­ba. Since 2010, he is a pro­fes­sor, School of Engi­neer­ing, Tohoku Uni­ver­si­ty.
His research inter­ests are the devel­op­ment of het­ero­ge­neous cat­a­lysts for

  1. pro­duc­tion of bio­mass-derived chem­i­cals
  2. direct syn­the­sis of organ­ic car­bon­ates from CO2 and alco­hols
  3. steam reform­ing of bio­mass tar
  4. syn­gas pro­duc­tion by nat­ur­al gas reform­ing

He is Asso­ciate Edi­tor of Fuel Pro­cess­ing Tech­nol­o­gy (2014/2-), Edi­to­r­i­al board of Applied Catal­y­sis A:General (2009/4-), Edi­to­r­i­al advi­so­ry board of ACS Catal­y­sis (2013/11-), Inter­na­tion­al Advi­so­ry Board of Chem­SusChem (2015/1-) and Advi­so­ry Board of Green Chemistry(2016/8-).

In Silico Prediction of Materials for Energy Applications

Meeting Program — September 2016

 
Dion Vlachos
Dion Vla­chos
Eliz­a­beth Inez Kel­ley Pro­fes­sor of Chem­i­cal
& Bio­mol­e­c­u­lar Engi­neer­ing and Pro­fes­sor of Physics,
Uni­ver­si­ty of Delaware

 
 
 
 
 
Abstract — In this talk, the need for new mate­ri­als in var­i­ous ener­gy domains will be dis­cussed. Mul­ti­scale sim­u­la­tion will then briefly be intro­duced as an enabling tech­nol­o­gy to address diverse engi­neer­ing top­ics. A spe­cif­ic appli­ca­tion of mul­ti­scale sim­u­la­tion is the pre­dic­tion of macro­scop­ic behav­ior from first prin­ci­ples. A more impact­ful avenue of research is how one could use mul­ti­scale mod­el­ing in reverse engi­neer­ing for pre­dict­ing new mate­ri­als for pro­duc­tion of ener­gy and chem­i­cals and ener­gy stor­age. We will demon­strate how descrip­tor-based mod­el­ing can enable such a search of nov­el mate­ri­als with emer­gent behav­ior and assess this frame­work with exper­i­ments. An out­stand­ing ques­tion is how reli­able and robust are mod­el pre­dic­tions in com­par­ing to data and our quest for search­ing new mate­ri­als. We will demon­strate this method­ol­o­gy for the spe­cif­ic exam­ple of ammo­nia decom­po­si­tion for hydro­gen pro­duc­tion for fuel cells and briefly touch upon renew­able chem­i­cals and fuels from lig­no­cel­lu­losic bio­mass.
 
Biog­ra­phy — Dion­i­sios (Dion) G. Vla­chos is the Eliz­a­beth Inez Kel­ley Pro­fes­sor of Chem­i­cal & Bio­mol­e­c­u­lar Engi­neer­ing and Pro­fes­sor of Physics at the Uni­ver­si­ty of Delaware and the Direc­tor of the Catal­y­sis Cen­ter for Ener­gy Inno­va­tion (CCEI), an Ener­gy Fron­tier Research Cen­ter (EFRC) fund­ed by the Depart­ment of Ener­gy (DOE). He obtained a five-year diplo­ma in Chem­i­cal Engi­neer­ing from the Nation­al Tech­ni­cal Uni­ver­si­ty of Athens, Greece in 1987, his M.S. and Ph.D. from the Uni­ver­si­ty of Min­neso­ta in 1990 and 1992 respec­tive­ly, and spent a post­doc­tor­al year at the Army High Per­for­mance Com­put­ing Research Cen­ter in Min­neso­ta. After that, Dr. Vla­chos joined the Uni­ver­si­ty of Mass­a­chu­setts as an assis­tant pro­fes­sor, was pro­mot­ed to an asso­ciate pro­fes­sor in 1998 and joined the Uni­ver­si­ty of Delaware in 2000. He was a vis­it­ing fel­low at Prince­ton Uni­ver­si­ty in the spring of 2000, a vis­it­ing fac­ul­ty mem­ber at Thomas Jef­fer­son Uni­ver­si­ty and Hos­pi­tal in the spring of 2007 and the George Pierce Dis­tin­guished Pro­fes­sor of Chem­i­cal Engi­neer­ing and Mate­ri­als Sci­ence at the Uni­ver­si­ty of Min­neso­ta in the fall of 2007.

Pro­fes­sor Vla­chos is the recip­i­ent of the R. H. Wil­helm Award in Chem­i­cal Reac­tion Engi­neer­ing from AIChE and is an AAAS Fel­low. He also received a NSF Career Award and an Office of Naval Research Young Inves­ti­ga­tor Award. He is a mem­ber of AIChE, ACS, the Com­bus­tion Insti­tute, MRS, the North Amer­i­can Catal­y­sis Soci­ety (NACS) and the Soci­ety for Indus­tri­al and Applied Math­e­mat­ics (SIAM).

Dr. Vla­chos’ main research thrust is mul­ti­scale mod­el­ing and sim­u­la­tion along with their appli­ca­tion to catal­y­sis, crys­tal growth, portable micro­chem­i­cal devices for pow­er gen­er­a­tion, pro­duc­tion of renew­able fuels and chem­i­cals, cat­a­lyst infor­mat­ics, detailed and reduced kinet­ic mod­el devel­op­ment and process inten­si­fi­ca­tion. He is the cor­re­spond­ing author of more than 340 ref­er­eed pub­li­ca­tions with near­ly 10,000 cita­tions and has giv­en over 200 ple­nary lec­tures, keynote lec­tures and oth­er invit­ed talks. Pro­fes­sor Vla­chos has served as an exec­u­tive edi­tor of the Chem­i­cal Engi­neer­ing Sci­ence jour­nal and also served or cur­rent­ly serves on the edi­to­r­i­al advi­so­ry board of ACS Catal­y­sis, Reac­tion Chem­istry & Engi­neer­ing, Indus­tri­al and Engi­neer­ing Chem­istry Research, Applied Catal­y­sis A: Gen­er­al, Pro­ceed­ings of the Com­bus­tion Insti­tute, the Open Ener­gy and Fuels Jour­nal, the Jour­nal of Nano Ener­gy and Pow­er Research and the Jour­nal of Chem­i­cal Engi­neer­ing & Process Tech­nol­o­gy.