A First Principles View of Reactivity Trends in Heterogeneous Catalysis and Electrocatalysis

2013 Spring Symposium

Jef­frey Gree­ley
Depart­ment of Chem­i­cal Engi­neer­ing
Pur­due Uni­ver­si­ty
West Lafayette, IN 47907

Abstract — Het­ero­ge­neous catal­y­sis and elec­tro­catal­y­sis have, in recent years, con­tributed sig­nif­i­cant­ly to the devel­op­ment of renew­able and ener­gy-effi­cient tech­nolo­gies, rang­ing from the pro­duc­tion of biore­new­able fuels to the effi­cient gen­er­a­tion of elec­tric­i­ty in fuel cells. Com­pu­ta­tion­al tech­niques, based pri­mar­i­ly on Den­si­ty Func­tion­al The­o­ry (DFT) cal­cu­la­tions, have, at the same time, played an increas­ing­ly impor­tant role in sci­en­tif­ic and engi­neer­ing stud­ies of these cat­alyt­ic process­es. These tech­niques have per­mit­ted the elu­ci­da­tion of fun­da­men­tal cat­alyt­ic reac­tion mech­a­nisms and, in some cas­es, have con­tributed to the com­pu­ta­tion­al design of new cat­a­lysts.

In this talk, I will describe some recent devel­op­ments in the use of DFT-based analy­ses to describe trends in the sci­ence and engi­neer­ing of inter­fa­cial catal­y­sis. Draw­ing on exam­ples in both het­ero­ge­neous catal­y­sis and elec­tro­catal­y­sis, I will out­line some sim­ple strate­gies for com­pu­ta­tion­al analy­sis of com­plex cat­alyt­ic reac­tion net­works and will show how, by tak­ing advan­tage of fun­da­men­tal cor­re­la­tions between the ther­mo­dy­nam­ics and kinet­ics of the rel­e­vant react­ing species, it is often pos­si­ble to describe reac­tiv­i­ty trends in terms of sim­ple vol­cano plots. I will demon­strate the appli­ca­tion of these trends-based analy­ses to tra­di­tion­al con­cepts of cat­alyt­ic activ­i­ty and will fur­ther illus­trate how impor­tant ques­tions of cat­a­lyst selec­tiv­i­ty and elec­tro­chem­i­cal cor­ro­sion may fur­ther be addressed. Next, I will describe how it is now becom­ing pos­si­ble, using nov­el exten­sions of bond order con­ser­va­tion the­o­ries, to under­stand and describe trends in com­plex bio­cat­alyt­ic reac­tion net­works that have pre­vi­ous­ly been beyond the reach of elec­tron­ic struc­ture cal­cu­la­tions. I will close with a dis­cus­sion of a nov­el het­ero­ge­neous cat­alyt­ic and elec­tro­cat­alyt­ic mate­ri­als, includ­ing bifunc­tion­al mate­ri­als, to which these tech­niques may be applied in the future.

Jeffrey Greeley

Jef­frey Gree­ley

Biog­ra­phy — Dr. Jef­frey Gree­ley obtained his PhD from the Uni­ver­si­ty of Wis­con­sin-Madi­son in 2004. He then postdoc’d with Jens Nørskov at the Tech­ni­cal Uni­ver­si­ty of Den­mark and devel­oped meth­ods to rapid­ly screen tran­si­tion met­al alloys for promis­ing cat­alyt­ic prop­er­ties. From 2007 to 2013, he was a staff sci­en­tist at Argonne’s Cen­ter for Nanoscale Mate­ri­als where he devel­oped a research pro­gram in com­pu­ta­tion­al nanocatal­y­sis and elec­tro­chem­istry. In 2013, he joined the Depart­ment of Chem­i­cal Engi­neer­ing at Pur­due Uni­ver­si­ty as an asso­ciate pro­fes­sor.