A More Realistic View of Gold Based Catalysts Using Aberration Corrected Analytical Electron Microscopy

2009 Spring Symposium

 
Dr Christo­pher J. Kiely
Cen­ter for Advanced Mate­ri­als and Nan­otech­nol­o­gy
Lehigh Uni­ver­si­ty
Beth­le­hem, PA


Abstract — Sup­port­ed gold clus­ters and gold-pal­la­di­um nanopar­ti­cles are intense­ly stud­ied mate­ri­als pri­mar­i­ly because of their excit­ing poten­tial appli­ca­tions in catal­y­sis. The recent avail­abil­i­ty of aber­ra­tion cor­rect­ed ana­lyt­i­cal elec­tron micro­scopes is rev­o­lu­tion­iz­ing our abil­i­ty to char­ac­ter­ize the mor­phol­o­gy, crys­tal­log­ra­phy and chem­i­cal com­po­si­tion of such nanoscop­ic vol­umes of mate­ri­als and for the first time are giv­ing us more real­is­tic views of these cat­a­lyst sys­tems. To illus­trate the supe­ri­or imag­ing per­for­mance of this new gen­er­a­tion of elec­tron micro­scopes, we will present a high angle annu­lar dark field (HAADF) imag­ing study of a sys­tem­at­ic set of gold on iron oxide CO oxi­da­tion cat­a­lysts, rang­ing from those with lit­tle or no activ­i­ty, to oth­ers with very high activ­i­ties. Using this approach, com­bined with XPS analy­sis, we will unam­bigu­ous­ly demon­strate that the high cat­alyt­ic activ­i­ty for CO oxi­da­tion derives from the pres­ence of bi-lay­er clus­ters which are ~0.5 nm in diam­e­ter. We will also demon­strate that core-shell struc­tures in sub-5nm Au+Pd, Pd@Au and Au@Pd bimetal­lic nanopar­ti­cles can be direct­ly visu­al­ized using the z-con­trast sen­si­tiv­i­ty of the HAADF imag­ing tech­nique. To illus­trate the chem­i­cal analy­sis capa­bil­i­ties of aber­ra­tion cor­rect­ed ana­lyt­i­cal micro­scopes, we will describe the poten­tial advan­tages of com­bin­ing X-ray Ener­gy Dis­per­sive Spec­troscopy (XEDS) spec­trum imag­ing with mul­ti­vari­ate sta­tis­ti­cal analy­sis (MSA) tech­niques. Through sev­er­al case stud­ies of the Au-Pd bimetal­lic cat­a­lyst sys­tems, we will demon­strate that STEM-XEDS can pro­vide invalu­able high spa­tial res­o­lu­tion com­po­si­tion­al infor­ma­tion on (i) alloy homo­gene­ity and phase seg­re­ga­tion effects with­in indi­vid­ual nanopar­ti­cles, (ii) par­ti­cle size — alloy com­po­si­tion cor­re­la­tions, and (iii) alloy com­po­si­tion changes that can occur as these cat­a­lysts are used.

Speaker’s Biog­ra­phy — Chris Kiely obtained his BSc in Chem­i­cal Physics (1983) and PhD in Microstruc­tur­al Physics (1986) from Bris­tol Uni­ver­si­ty. From 1986–89 he was a vis­it­ing post­doc­tor­al research asso­ciate in the Mate­ri­als Research Lab­o­ra­to­ry at the Uni­ver­si­ty of Illi­nois at Urbana-Cham­paign. He joined the Mate­ri­als Sci­ence and Engi­neer­ing Depart­ment at Liv­er­pool Uni­ver­si­ty as a Lec­tur­er in 1989, where he worked his way through the ranks until even­tu­al­ly being award­ed a Per­son­al Chair in Mate­ri­als Chem­istry in 1999. Kiely joined Lehigh Uni­ver­si­ty (Penn­syl­va­nia, USA) as Pro­fes­sor of Mate­ri­als Sci­ence and Engi­neer­ing in 2002. He is cur­rent­ly the Direc­tor of the Cen­ter of the Nanochar­ac­ter­i­za­tion Lab­o­ra­to­ry at Lehigh Uni­ver­si­ty, which hous­es an array of twelve elec­tron micro­scopes, includ­ing two aber­ra­tion cor­rect­ed instru­ments. He also serves as the Direc­tor of the Lehigh Microscopy Schools. His research exper­tise lies in the appli­ca­tion and devel­op­ment of trans­mis­sion elec­tron microscopy tech­niques for the study of nanoscale fea­tures in mate­ri­als. His areas of inter­est include cat­a­lyst mate­ri­als, nanopar­ti­cle self-assem­bly, car­bona­ceous mate­ri­als, and het­eroepi­tax­i­al inter­face struc­tures. He is also involved in microscopy tech­nique devel­op­ment, and his cur­rent inter­ests include X-Ray Ultra­mi­croscopy (XuM) and aber­ra­tion cor­rect­ed Ana­lyt­i­cal Elec­tron Microscopy (AEM).