Oxidation of Carbon Monoxide Over Ceria and Alumina Supported Palladium Catalysts

2018·15.4 MB·English

by  John Davis Gary

COLUMBUS STATE UNIVERSITY
OXIDATION OF CARBON MONOXIDE OVER CERIA AND
ALUMINA SUPPORTED PALLADIUM CATALYSTS
A THESIS SUBMITTED TO THE COLLEGE OF LETTERS AND
SCIENCES IN THE PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE
DEPARTMENT OF CHEMISTRY
BY
JOHN DAVIS GARY
COLUMBUS, GEORGIA
DECEMBER 2018
OXIDATION OF CARBON MONOXIDE OVER CERIA AND
ALUMINA SUPPORTED PALLADIUM CATALYSTS
BY
JOHN DAVIS GARY
Committee Chair:
Dr. Anil C. Banerjee

Committee Members:
Dr. Daniel Holley
Dr. Jonathan Meyers
Columbus State University
December 2018
©2018 by John Davis Gary
ABSTRACT
Palladium catalysts on both Al,O3 and CeO, supports were studied for efficacy in
low temperature carbon monoxide oxidation. Calcination temperatures were
varied between 500-900°C for alumina supported catalysts and shown to have no
significant difference in activity. X-Ray Photoelectron Spectroscopy studies
revealed structural changes associated with palladium states and reacted
catalysts and displayed a change from palladium oxide (PdO) to native palladium
oxide (PdOx) and elemental palladium (Pd). Activity studies were conducted on all
catalysts synthesized and indicated that Pd/Al,Os achieved 100% CO conversion at
150°C when calcined at 500°C and pretreated with reduction process. Pd/CeO;
showed higher activity and achieved 100% CO conversion at 80°C. Stochiometric
mixtures of CO and O; as well as excess oxygen resulted in higher conversion CO.
ACKNOWLEDGEMENTS
| would like to thank my mentor and trusted advisor, Dr. Anil Banerjee, Professor of Chemistry
at Columbus State University, for continual encouragement and much needed criticism. |
would also like to thank my thesis committee, Dr. Daniel Holley, and Dr. Jonathan Meyers,
Professors of Chemistry at Columbus State University. | couldn’t have asked for a greater set of
mentors and teachers.
| would like to thank Dr. Michael Bozack, Professor of Physics at Auburn University for
contributing analysis and interpretations in XPS characterizations.
Thanks to Dr. Mehmet Billor at the University of Auburn for your help in XRD analysis and
interpretations.

Thanks to Dr. Kristina Golub, Georgia Institute of Technology, for catalyst characterization by
adsorption techniques.
| also want to thank Jacqueline Michelle McGuire for your persistence and encouragement. You
made all this possible.
A special thanks for Dr. Floyd Jackson for always being there, ready to listen and offer advice.
You have been an inspiration for me and elevate what | think is possible to achieve.
Thanks to the Student Research and Creative Endeavors (SRACE) grant for providing research
funding.
TABLE OF CONTENTS
LISTE OF FABLES «.oocso ci ioitnihsconniiiustnsissssesanssbsissnssst sisss ibsiashsts obinna s sbrssusomnsressssia s viii
LISIEOE FIGLIRES ...i. rvivcnsinsesssisssiarsitatessnssstoim sbts ssssnsaitisnansas sorsnssansssssnasssisbuionsas iX
|. INTRODUCTION AND BACKGROUND INFORMATION......c.cccecerrurruenn. 1
BARIOBUCHIBI .oieuvssstinarrinisssinmsssisnssssssisbisambfoisssisartniiasrss usrivniisns 2
B: Coron MIONOXIBA .......c...icsirsisissennssnsssssmosisnosisenhsbssiinssnnssaiinsii 2
C. PANARIIIN cc. siieni cic vissidinsinsnissnnssesnaness sabnadsauastasesrstanasnsratins 4
Dh CORIIIIN., iicsioeisssssnsinssslisusiasmnns sisninsmssnaabenissonnmsti th assis bannhei shana msgs bons 5
E. Objectives for this StUdy.........ccconnee.. STShs SER e h ts 8
I METISODOLBDIBY. ......coisicisecisniisisininisnsosrsiossssmmmmstansrsssmsts usndusnsiaasunrsis 8
A. Catalyst PraDAPatiON .........onssnmmisiinmisstemmsomsnssarssassseiississssssenanssns 9
I. Palladium on AMINE OXIAR...............ommtsmecssinesassissssorsse 9
i. Palladium on Cerium OXITE.......corissimmmmssreiisssssssssserssinss 10

Hi: SEARAUS ov. oo roovisnmersinssbosdiiaa shseistinsamnei sassuss sninss svnsnssdos al
IV. Catalyst REIGEBNCE.......co.coivmmionissmsssmisssiossinsastisansondsbossnse 11
B. Catalytic ACKHIVIEY SUG ........ccoonesisssonscinssosimons ssoissanansssossnsnsasnviosasss 12
J, Reaction PYOCRALILE .....cociinsiserisiomivmmsmnmancrsnsessitisssnsnbossinss 12
i. ANSIVZING GAS (MHIXIUEES. cosine csesnicssnirnasisntessotsnnrssssnssp ossssos 14
CC. CharaciBRIZAtION ...........coicvnscinsniincsiritanss sshetis iinsdee eairdei tnannnninss 15
LoS crs io this viiaissomssiosuisbns iin niin sissies nanan dass Sts bens is ove 15
We MRD oi ciiioisssuimninsoiinsesi sinnstsnnoiosn ssasms asonninsrsiinsnasnsibanisuosstuiunisne s 16
Ji CNOIISOTDRION ro. sons sistas srsommesansmnisssnsssmsomaniinssinnsssssnsovinsss 18
iH. RESULTS AND DISCUSSION .....occovviornsnsnsssvmoinions isssssssissossssntsssssssss sannitas 19
BEACH... i. chvuisssinmmrieiiatsitanmsiivnssnmisnsss sissbensonsianistonmissssshinsassibosiaessin 20
Vi
i. Pd/AI203 a ens rete serena seas ib aS hh nao tia se 20
lie PAICBOD. ........conritisiatoismssstonmiins invsssmsonisnsonsinionsss sstatinsnostrashons 22
B. ChaC aarIZtatiO N. ....ccvioiiissumsississsesmsisnsmmisseriisnosssirsssiinsnnipssshonsanssa 26
J XRD AY IIYSIS ive vanioricritiorensiinislismsmninsibssessansessniosssuasassnsnsssnsss 27
I, XPS INVAIYSES... cai eorusistliatostiesnirsoititnamsssinsiin sesmonmisnnibssatssdinsisssasns 29
IH. ChCMISORPIION i. cees0iesesiun cinusssssumsessonsisanssssmmsiissnssmsssnmrassnansss 38
NV. CONCLUSIONS AND EUTURE WORK .........cooc00ur cisnmmionissinssissimnssyones 39
Be COCIUSIBNIS ci suintvrnisnissnnsiiinivursupsstossr ossaaioilisniseas sssesn isn aesesaonsssibsaianve 40
Be FURUEE WOH. ..oreissis sisiisvsntamntss snsodsistisnamisaishansmnabs atosrishssntrisassnhn se 42
NM. BIBLIOGRAPHY. .......covivnisieisnesnsimmsissnssoisibnusitss isnoosmssromirsstoisssstrsisssnmnumssns 45
ADBCITIN IRs... svi viinrsisthsetinmmsinuitaitspris oiisvsninsvmmsmssssitisnsisniunsasetossinasidsts sss stains 48
Appendix B
Vii
LIST OF TABLES
Table 2.1 Catalyst Index 8110 REIGIENCE. .....ccoviconiusissessissiinssisssssnsssanssanprsnens 12
Table 3.1 ACLIVILY FOF POZA 08. Jie. iocsisscinsaingrossrsiomiogthosisiinssisivsiosstorssnsiinssnssasmmss 21
Table 3.2 List of All Reactions Studied and Corresponding CO Conversion......23
Table 3.3 Reaction .over Pd/CeOs fOr SO MIMULES ........cccrermmssnsvsss sessasssasssssesss 24
Table 3.4 Chemisorplion ResUIS FOr PU/C, ........ccuccsmirmmimininscsmssnsissssasssansins 38
viii
LIST OF FIGURES
Figure 2.1 CO concentration vs. PeakSimple integration area.......cccecueeeeveerennnne. 15
Figure 3.1 Various Gas MIXEUres in CO OXIOATION:....cc.mveserisnnsns sisesenaiossnsssssissanses 23
Figure 3.2 CO Conversion vs Temperature over Cerlac.cm ....... d
Figure 3.3 XRD Analysis OF SPECIMBI TSLI-B...........cccvnicinsnsmssmmerssssanisssrsrissisossasnsaivs 26
Figure 3.4 XRD. ANALYSIS OF SPECIMEIT CSU-0.........ccinvmmsmsssissmmseissiosimhmmsdisssiniassssssrassss 27
Figure 3.5 XRD Analysis of Specimen CSU-10.............ivesssisinsssisinstrsssrssnsssosssnsssessrsssons 28
Figure 3.6 XRD Analysic OF SPECIMEBNICSU-T......coocceiss sslrnisiaimidanssasssisinsits ssoebossissos s 28
Eira 3.7 XPS SPCR OF CSU-1...00.... coi cod a hit tastes sian rive ness anisms nas sans sin snisans 29
Figure 3.8 XPS spectra of CSU-1 after SPULLEIING...ci....s0iim simeetimmsmmserassrssersansrenes 30
Figure 3.9 High Resolution Spectra over PA3d on CSU=1.............vicsmsenmssminssssssnnomes Sl
Figure 3.10 High Resolution Spectra over Pd3d of CSU-1 after Sputtering.............. 31
Fisure:3.1) XPS SPCR BRCSU=7........ coi coiirinisiiamiisisbatanssnenissisnssisnsasbsaissnsansanientsssh 32
Eistre 3.4.2 XPS SPactia OF ESU-8.......cc.ciiccnsinsiimssinssassniss sstni isannsas iiheat aissv ases sriassasvnss s 33

Figure 3.13 High Resolution Spectra over Ce3d, Sample CSU-8.........ccccerervernurnnen. 33
Figure 3.14 High Resolution Spectra of CSU-8 OVer (1S........cccceumerissssersssrinssssmssessass 34
Figure 3.15 High Resolution Spectra of CSU-8 over Pd3d.........ccoovrmvnrvnncennvcnnnenvennns 35
Figure 3.16 XPS High Resolution Spectra of CSU-9 over O1S..........c.vevnncsnsvnssesnssnsss3s9s
Figure 3.17 XPS High Resolution Spectra of CSU-9 over Pd3d.........cccoeevriveiniennunnncnns 36
Piura 3.18 XPS SPEctia OF COI-10.......c.cciicciiviivinissmisisinsirssnsssinisirssiavssnsntonssdsisaosnns 37
Il. INTRODUCTION