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).