In Situ Spectroscopic Studies of Metal Oxide Electrodes During Water Oxidation

Meeting Program — April 2013

John Kitchin
Depart­ment of Chem­i­cal Engi­neer­ing,
Carnegie Mel­lon Uni­ver­si­ty

Abstract — Elec­tro­chem­i­cal water split­ting may be in inte­gral part of future ener­gy stor­age strate­gies by enabling ener­gy stor­age in chem­i­cal bonds. One of the pri­ma­ry sources of inef­fi­cien­cy in the water split­ting reac­tion is the oxy­gen evo­lu­tion reac­tion, which has high reac­tion bar­ri­ers that require addi­tion­al applied elec­tric poten­tial to dri­ve the reac­tions at prac­ti­cal rates. The most active elec­trode mate­ri­als in acid elec­trolytes include ruthe­ni­um and irid­i­um oxides, which are expen­sive but nec­es­sary for sta­bil­i­ty. In alka­line envi­ron­ments, many base met­al oxides become sta­ble, although they are still less active than Ru and Ir oxides. It has been known that small amounts of Fe can pro­mote the elec­tro­chem­i­cal activ­i­ty of nick­el oxides, mak­ing it almost as active as cobalt oxide. We have inves­ti­gat­ed the mech­a­nisms behind the pro­mo­tion using in situ Raman and syn­chro­tron spec­tro­scopies as well as ex situ char­ac­ter­i­za­tion tech­niques. Inter­est­ing­ly, we found the elec­trode changes under oxy­gen evo­lu­tion con­di­tions, turn­ing from an oxide to an oxy­hy­drox­ide phase. Fur­ther­more, the com­po­si­tion of the elec­trolyte has a sig­nif­i­cant effect on the oxy­gen evo­lu­tion activ­i­ty. We will dis­cuss these results and their impli­ca­tions in find­ing bet­ter oxy­gen evo­lu­tion elec­tro­cat­a­lysts.

John Kitchin

John Kitchin

Biog­ra­phy — John Kitchin com­plet­ed his B.S. in Chem­istry at North Car­oli­na State Uni­ver­si­ty. He com­plet­ed a M.S. in Mate­ri­als Sci­ence and a PhD in Chem­i­cal Engi­neer­ing at the Uni­ver­si­ty of Delaware in 2004 under the advise­ment of Dr. Jing­guang Chen and Dr. Mark Barteau. He received an Alexan­der von Hum­boldt post­doc­tor­al fel­low­ship and lived in Berlin, Ger­many for 1 ½ years study­ing alloy seg­re­ga­tion with Karsten Reuter and Matthias Schef­fler in the The­o­ry Depart­ment at the Fritz Haber Insti­tut. Pro­fes­sor Kitchin began a tenure-track fac­ul­ty posi­tion in the Chem­i­cal Engi­neer­ing Depart­ment at Carnegie Mel­lon Uni­ver­si­ty in Jan­u­ary of 2006. He is cur­rent­ly an Asso­ciate Pro­fes­sor. At CMU, Pro­fes­sor Kitchin is active in a major research effort with­in the Nation­al Ener­gy Tech­nol­o­gy Lab­o­ra­to­ry Region­al Uni­ver­si­ty Alliance in CO2 cap­ture, chem­i­cal loop­ing and super­al­loy oxi­da­tion. Pro­fes­sor Kitchin also uses com­pu­ta­tion­al meth­ods to study adsor­bate-adsor­bate inter­ac­tions on tran­si­tion met­al sur­faces for appli­ca­tions in catal­y­sis. He was award­ed a DOE Ear­ly Career award in 2010 to inves­ti­gate mul­ti­func­tion­al oxide elec­tro­cat­a­lysts for the oxy­gen evo­lu­tion reac­tion in water split­ting using exper­i­men­tal and com­pu­ta­tion­al meth­ods. He received a Pres­i­den­tial Ear­ly Career Award for Sci­en­tists and Engi­neers in 2011.
Recent Pub­li­ca­tions
  1. Sne­ha A. Akhade and John R. Kitchin*, “Effects of strain, d-band fill­ing and oxi­da­tion state on the sur­face elec­tron­ic struc­ture and reac­tiv­i­ty of 3d per­ovskite sur­face”, J. Chem. Phys. 137, 084703 (2012).
  2. James Lan­don, Ethan Deme­ter, Nilay İnoğlu, Chris Ketu­rakis, Israel E. Wachs, Rel­ja Vasić, Ana­toly I. Frenkel, John R. Kitchin, “Spec­tro­scop­ic char­ac­ter­i­za­tion of mixed Fe-Ni oxide elec­tro­cat­a­lysts for the oxy­gen evo­lu­tion reac­tion in alka­line elec­trolytes”, ACS Catal­y­sis, 2, 1793–1801 (2012).
  3. Sne­ha A. Akhade and John R. Kitchin*, Effects of strain, d-band fill­ing and oxi­da­tion state on the bulk elec­tron­ic struc­ture of cubic 3d per­ovskites, J. Chem. Phys. 135, 104702 (2011).
  4. N. Inoglu, and J.R. Kitchin, Iden­ti­fi­ca­tion of sul­fur tol­er­ant bimetal­lic sur­faces using DFT para­me­ter­ized mod­els and atom­istic ther­mo­dy­nam­ics, ACS Catal­y­sis, 1, 399–407 (2011).
  5. Isabela C. Man, Hai-Yan Su, Fed­eri­co Calle-Valle­jo, Heine A. Hansen, José I. Martínez, Nilay G. Inoglu, John Kitchin, Thomas F. Jaramil­lo, Jens K. Nørskov, Jan Ross­meisl, Uni­ver­sal­i­ty in Oxy­gen Evo­lu­tion Elec­tro-Catal­y­sis on Oxide Sur­faces, Chem­CatChem, 3, (2011).
  6. Spencer D. Miller, Nilay İnoğlu, and John R. Kitchin, Con­fig­u­ra­tional cor­re­la­tions in the cov­er­age depen­dent adsorp­tion ener­gies of oxy­gen atoms on late tran­si­tion met­al fcc (111) sur­faces, J. Chem­i­cal Physics, 134, 104709 (2011).
  7. R. Chao, J. R. Kitchin, K. Gerdes, E. M. Sabol­sky, and P. A. Sal­vador, Prepa­ra­tion of Meso­porous La0.8Sr0.2MnO3 Infil­trat­ed Coat­ings in Porous SOFC Cath­odes Using Evap­o­ra­tion-Induced Self-Assem­bly Meth­ods, ECS Trans­ac­tions, 35 (1) 2387–2399 (2011).
  8. W. Richard Ale­si Jr., McMa­han Gray, John R. Kitchin, CO2 Adsorp­tion on Sup­port­ed Mol­e­c­u­lar Ami­dine Sys­tems on Acti­vat­ed Car­bon, Chem­SusChem, 3(8), 948–956 (2010) Spe­cial issue on CO2 cap­ture and Seques­tra­tion.
  9. Nilay Inoglu, John R. Kitchin, Sim­ple mod­el explain­ing and pre­dict­ing cov­er­age-depen­dent atom­ic adsorp­tion ener­gies on tran­si­tion met­al sur­faces, Phys­i­cal Review B, 82, 045414 (2010).