Electrocatalysis of oxygen evolution of perovskite-type oxides.

Bibliographic Details
Main Author: Otagawa, Takaaki
Other Authors: Lunsford, Jack H. (degree committee member.), Rosynek, Michael P. (degree committee member.), White, Ralph E. (degree committee member.)
Format: Thesis Book
Language:English
Published: 1983.
Subjects:
Online Access:Link to ProQuest Copy
Link to OAKTrust copy

MARC

Tag First Indicator Second Indicator Subfields
LEADER 00000ctm a2200000Ia 4500
001 in00000513421
005 20220103135150.0
008 840725s1983 xx a bm 000 0 eng d
035 |9 ACG1453AM 
035 |a (OCoLC)10986161 
035 |a (OCoLC)ocm10986161 
040 |a TXA  |b eng  |c TXA  |d OCLCQ  |d OCLCF  |d OCLCQ  |d OCLCO  |d TXA 
049 |a TXAM 
050 4 |a QD572.O85  |b O72 
099 |a 1983  |a Dissertation  |a O87 
100 1 |a Otagawa, Takaaki 
245 1 0 |a Electrocatalysis of oxygen evolution of perovskite-type oxides. 
260 |c 1983. 
300 |a xxii, 334 leaves :  |b illustrations ;  |c 29 cm 
336 |a text  |b txt  |2 rdacontent 
337 |a unmediated  |b n  |2 rdamedia 
338 |a volume  |b nc  |2 rdacarrier 
500 |a "Major subject: Chemistry." 
500 |a Typescript (photocopy). 
500 |a Vita. 
502 |b Ph. D. in Philosophy  |c Texas A & M University  |d 1983 
504 |a Includes bibliographical references (leaves 313-333). 
520 3 |a A systematic investigation was made to correlate the electrocatalytic properties of perovskites, ABO(,3) (A is a lanthanide, B is a first row transition metal), for oxygen evolution with their electronic structures. The perovskites were prepared by high temperature solid state chemical reactions. Electrodes were made by pressing powders into pellets, followed by a sintering process. The surface areas of powders (by BET) and electrodes (by double layer changing curves) were (TURN) 15 m('2) g('-1) and 100-1000 in terms of roughness factor, respectively. The Hall effect and impedance measurements showed that the electrodes were all p-type semiconductors with carrier densities of 10('17)-10('18) cm('-3), mobilities of (TURN) 30 cm('2) V('-1) sec('-1) and flat-band potentials of 0.2-0.5 V (vs. NHE) in 1 M NaOH. A paramagnetism, a weak ferromagnetism and a strong ferromagnetism were observed on LaNiO(,3), La(,0.9)Sr(,0.1)CoO(,3), and LaMnO(,3), respectively. The acid/base titration experiments on powders showed a high coverage of OH('-) species with zpc of 7-9 (pH). The XPS analysis on the La(,0.9)Sr(,0.1)CoO(,3) electrode showed that the untreated surface consisted largely of Co('II) and Co('III); upon anodic polarization the surface became entirely Co('III). The Tafel slopes of oxygen evolution were 2RT/3F, RT/F. and 2RT/F for nickelates, cobaltates and ferrites or manganites, respectively. The reaction order with respect to OH('-) was close to unity. It was concluded, based on the kinetic parameters and an examination of various rate correlations, that a common mechanism for oxygen evolution occurs on perovskites, i.e., the electrochemical adsorption of OH('-), followed by the rate-determining electrochemical desorption of OH, forming H(,2)O(,2) as an intermediate.The electrocatalytic activity increases with the increase of number of d-electrons, which is associated with the decrease of the M('z)-OH bond strength. A qualitative MO model suggests that the occupancy of the antibonding orbitals maximizes the catalytic activity. Thus, LaNiO(,3) (d('7)) gives the fastest oxygen evolution rate. 
650 0 |a Catalysis. 
650 0 |a Electrochemistry. 
650 0 |a Electrodes, Oxide. 
650 0 |a Electrodes, Oxygen. 
650 0 |a Transition metal compounds. 
650 4 |a Chemistry 
655 7 |a Academic theses  |2 lcgft 
700 1 |a Bockris, John O'M,  |e degree supervisor. 
700 1 |a Lunsford, Jack H.,  |e degree committee member. 
700 1 |a Rosynek, Michael P.,  |e degree committee member. 
700 1 |a White, Ralph E.,  |e degree committee member. 
710 2 |a Texas A & M University,  |e degree granting institution. 
856 4 1 |u http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=753883131&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD  |z Link to ProQuest Copy  |t 0 
856 4 1 |u https://hdl.handle.net/1969.1/DISSERTATIONS-537929  |z Link to OAKTrust copy  |t 0 
994 |a C0  |b TXA 
999 f f |s e52d73a9-47a2-3e9a-9abb-ea7cdff37606  |i 947439d0-1b61-3345-a81d-baee50eb4633  |t 0 
952 f f |p noncirc  |a Texas A&M University  |b J.J. Pickle Campus  |c High Density Repository  |s HDR  |d Remote Storage  |t 0  |e 1983 Dissertation O87  |h Other scheme  |i unmediated -- volume  |m A14840932707 
952 f f |a Texas A&M University  |b College Station  |c Electronic Resources  |s www_evans  |d Available Online  |t 0  |e 1983 Dissertation O87  |h Other scheme 
998 f f |a 1983 Dissertation O87  |t 0  |l Remote Storage 
998 f f |a 1983 Dissertation O87  |t 0  |l Available Online