Effect of sodium loading on Pt/ZrO2 during ethanol steam reforming

Martinelli, Michela; Castro, Jonathan D.; Alhraki, Nour; Matamoros, Maria E.; Kropf, A. Jeremy; Cronauer, Donald C.; Jacobs, Gary

doi:10.1016/j.apcata.2020.117947

Effect of sodium loading on Pt/ZrO₂ during ethanol steam reforming

Journal Article · Fri Dec 04 23:00:00 EST 2020 · Applied Catalysis. A, General

DOI:https://doi.org/10.1016/j.apcata.2020.117947· OSTI ID:1829997

Martinelli, Michela ^[1]; Castro, Jonathan D. ^[2]; ^[3]; ^[4]; ^[5]; Cronauer, Donald C. ^[5]; Jacobs, Gary ^[3]

Univ. of Kentucky, Lexington, KY (United States). Center for Applied Energy Research
Univ. of Texas at San Antonio, TX (United States); John Jay Science and Engineering Academy, San Antonio, TX (United States)
Univ. of Texas at San Antonio, TX (United States)
Univ. of Texas at San Antonio, TX (United States); Samuel V. Champion High School, Boerne, TX (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Ethanol steam reforming (ESR) was investigated on unpromoted and several sodium promoted Pt/ZrO₂ catalysts. From DRIFTS experiments, the following steps during ESR were inferred: dissociation of ethanol to produce ethoxy species; oxidative dehydrogenation of ethoxy species to acetate; and acetate decomposition. Acetate decomposition depends on the catalyst formulation. Decarboxylation is the most favored route at high sodium loading (2.5 and 5 wt.%); acetate decomposes in the forward direction to CH₄ and a carbonate, which further decomposes to CO₂. In contrast, decarbonylation is prevalent for the unpromoted catalyst or catalysts having low sodium loading. Furthermore, acetate likely decomposes to CH₃OH and CO. Adsorbed methanol may undergo further steam reforming by oxidative dehydrogenation to formate species, which decarbonylates via reverse decomposition to CO and H₂O. Temperature programmed desorption/reaction and activity data confirmed that alkali promotion, especially at 1.8 %Na and higher loading, facilitates the forward acetate decomposition step, favoring decarboxylation over decarbonylation.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1829997

Journal Information:: Applied Catalysis. A, General, Journal Name: Applied Catalysis. A, General Vol. 610; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Glycerol Reforming for Hydrogen Production: A Review Vaidya, P. D.; Rodrigues, A. E. Chemical Engineering & Technology, Vol. 32, Issue 10 https://doi.org/10.1002/ceat.200900120	journal	October 2009
Design of Nanocatalysts for Green Hydrogen Production from Bioethanol Bion, Nicolas; Duprez, Daniel; Epron, Florence ChemSusChem, Vol. 5, Issue 1 https://doi.org/10.1002/cssc.201100400	journal	December 2011
Reactant-Promoted Reaction Mechanism for Water-Gas Shift Reaction on Rh-Doped CeO2 Shido, T.; Iwasawa, Y. Journal of Catalysis, Vol. 141, Issue 1 https://doi.org/10.1006/jcat.1993.1119	journal	May 1993
Electronic effects and effects of particle morphology in n-hexane conversion over zeolite-supported platinum catalysts Menacherry, P.; Haller, G. Journal of Catalysis, Vol. 177, Issue 2 https://doi.org/10.1006/jcat.1998.2048	journal	July 1998
Structure and Surface and Catalytic Properties of Mg-Al Basic Oxides Di Cosimo, J. I.; Dı́ez, V. K.; Xu, M. Journal of Catalysis, Vol. 178, Issue 2 https://doi.org/10.1006/jcat.1998.2161	journal	September 1998
A Study of the Reactions of Ethanol on CeO2 and Pd/CeO2 by Steady State Reactions, Temperature Programmed Desorption, and In Situ FT-IR Yee, A.; Morrison, S. J.; Idriss, H. Journal of Catalysis, Vol. 186, Issue 2 https://doi.org/10.1006/jcat.1999.2563	journal	September 1999
A Study of Ethanol Reactions over Pt/CeO2 by Temperature-Programmed Desorption and in Situ FT-IR Spectroscopy: Evidence of Benzene Formation Yee, Anna; Morrison, Scott J.; Idriss, Hicham Journal of Catalysis, Vol. 191, Issue 1 https://doi.org/10.1006/jcat.1999.2765	journal	April 2000
Promoting Mechanism of Potassium in the Reforming of Ethanol on Pt/Al2O3 Catalyst Dömök, M.; Baán, K.; Kecskés, T. Catalysis Letters, Vol. 126, Issue 1-2 https://doi.org/10.1007/s10562-008-9616-0	journal	September 2008
Synthesis, characterization and catalytic application of Ni catalysts supported on alumina–zirconia mixed oxides Ángel-Soto, J.; Martínez-Rosales, M.; Ángel-Soto, P. Bulletin of Materials Science, Vol. 40, Issue 7 https://doi.org/10.1007/s12034-017-1493-y	journal	November 2017
Analysis of multiple-scattering XAFS data using theoretical standards Newville, M.; Ravel, B.; Haskel, D. Physica B: Condensed Matter, Vol. 208-209 https://doi.org/10.1016/0921-4526(94)00655-F	journal	March 1995
Oxidative reforming of biomass derived ethanol for hydrogen production in fuel cell applications Fierro, V.; Klouz, V.; Akdim, O. Catalysis Today, Vol. 75, Issue 1-4 https://doi.org/10.1016/S0920-5861(02)00056-1	journal	July 2002
Production of hydrogen for fuel cells by reformation of biomass-derived ethanol Fatsikostas, Athanasios N.; Kondarides, Dimitris. I.; Verykios, Xenophon E. Catalysis Today, Vol. 75, Issue 1-4 https://doi.org/10.1016/S0920-5861(02)00057-3	journal	July 2002
Production of hydrogen for fuel cells by steam reforming of ethanol over supported noble metal catalysts Liguras, Dimitris K.; Kondarides, Dimitris I.; Verykios, Xenophon E. Applied Catalysis B: Environmental, Vol. 43, Issue 4 https://doi.org/10.1016/S0926-3373(02)00327-2	journal	July 2003
On the role of additives to platinum catalysts for reforming reactions Fukunaga, T.; Ponec, V. Applied Catalysis A: General, Vol. 154, Issue 1-2 https://doi.org/10.1016/S0926-860X(96)00374-2	journal	June 1997
Review of fuel processing catalysts for hydrogen production in PEM fuel cell systems Faur Ghenciu, Anca Current Opinion in Solid State and Materials Science, Vol. 6, Issue 5, p. 389-399 https://doi.org/10.1016/S1359-0286(02)00108-0	journal	October 2002
In situ DRIFTS investigation of the steam reforming of methanol over Pt/ceria Jacobs, Gary; Davis, Burtron H. Applied Catalysis A: General, Vol. 285, Issue 1-2 https://doi.org/10.1016/j.apcata.2005.02.006	journal	May 2005
Low temperature water-gas shift: Characterization of Pt-based ZrO2 catalyst promoted with Na discovered by combinatorial methods Pigos, John M.; Brooks, Christopher J.; Jacobs, Gary Applied Catalysis A: General, Vol. 319 https://doi.org/10.1016/j.apcata.2006.11.014	journal	March 2007
Low temperature water–gas shift: The effect of alkali doping on the CH bond of formate over Pt/ZrO2 catalysts Pigos, John M.; Brooks, Christopher J.; Jacobs, Gary Applied Catalysis A: General, Vol. 328, Issue 1 https://doi.org/10.1016/j.apcata.2007.04.001	journal	August 2007
Ethanol decomposition and steam reforming of ethanol over CeZrO2 and Pt/CeZrO2 catalyst: Reaction mechanism and deactivation de Lima, Sania M.; Silva, Adriana M.; Graham, Uschi M. Applied Catalysis A: General, Vol. 352, Issue 1-2 https://doi.org/10.1016/j.apcata.2008.09.040	journal	January 2009
Fluorine-modified Mg–Al mixed oxides: A solid base with variable basic sites and tunable basicity Wu, Gongde; Wang, Xiaoli; Wei, Wei Applied Catalysis A: General, Vol. 377, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.01.023	journal	April 2010
Water-gas shift: Characterization and testing of nanoscale YSZ supported Pt catalysts Martinelli, Michela; Jacobs, Gary; Graham, Uschi M. Applied Catalysis A: General, Vol. 497 https://doi.org/10.1016/j.apcata.2014.12.055	journal	May 2015
YSZ monoliths promoted with Co as catalysts for the production of H 2 by steam reforming of ethanol Gaudillere, Cyril; González, Juan Jose; Chica, Antonio Applied Catalysis A: General, Vol. 538 https://doi.org/10.1016/j.apcata.2017.03.008	journal	May 2017
Low temperature water-gas shift: Optimization of K loading on Pt/m-ZrO2 for enhancing CO conversion Watson, Caleb D.; Martinelli, Michela; Cronauer, Donald C. Applied Catalysis A: General, Vol. 598 https://doi.org/10.1016/j.apcata.2020.117572	journal	May 2020
Water-gas shift: an examination of Pt promoted MgO and tetragonal and monoclinic ZrO2 by in situ drifts Chenu, Emilie; Jacobs, Gary; Crawford, Adam C. Applied Catalysis B: Environmental, Vol. 59, Issue 1-2 https://doi.org/10.1016/j.apcatb.2004.12.013	journal	July 2005
MnO_x–CeO₂ mixed oxide catalysts for complete oxidation of formaldehyde: Effect of preparation method and calcination temperature Tang, Xingfu; Li, Yonggang; Huang, Xiumin Applied Catalysis B: Environmental, Vol. 62, Issue 3-4, p. 265-273 https://doi.org/10.1016/j.apcatb.2005.08.004	journal	February 2006
Rh(1%)@CexZr1−xO2–Al2O3 nanocomposites: Active and stable catalysts for ethanol steam reforming Montini, T.; Derogatis, L.; Gombac, V. Applied Catalysis B: Environmental, Vol. 71, Issue 3-4 https://doi.org/10.1016/j.apcatb.2006.09.003	journal	February 2007
Low temperature catalytic steam reforming of ethanol. 1. The effect of the support on the activity and stability of Pt catalysts Ciambelli, P.; Palma, V.; Ruggiero, A. Applied Catalysis B: Environmental, Vol. 96, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.01.029	journal	April 2010
Behavior of steam reforming reaction for bio-ethanol over Pt/ZrO2 catalysts Yamazaki, Tatsuya; Kikuchi, Naoko; Katoh, Masahiro Applied Catalysis B: Environmental, Vol. 99, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.06.003	journal	August 2010
Utilization of greenhouse gases through carbon dioxide reforming of methane over Ni–Co/MgO–ZrO2: Preparation, characterization and activity studies Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash Applied Catalysis B: Environmental, Vol. 100, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.08.013	journal	October 2010
Transesterification of dimethyl carbonate with tetrahydrofurfuryl alcohol on the K2CO3/ZrO2 catalyst—Function of the surface carboxylate species Zhang, Bin; Ding, Guoqiang; Zheng, Hongyan Applied Catalysis B: Environmental, Vol. 152-153 https://doi.org/10.1016/j.apcatb.2014.01.027	journal	June 2014
High efficiency of Pt2+- CeO2 novel thin film catalyst as anode for proton exchange membrane fuel cells Fiala, Roman; Figueroba, Alberto; Bruix, Albert Applied Catalysis B: Environmental, Vol. 197 https://doi.org/10.1016/j.apcatb.2016.02.036	journal	November 2016
Highly active Pt/Na TiO2 catalyst for low temperature formaldehyde decomposition Wang, Lei; Yue, Haiqin; Hua, Zelin Applied Catalysis B: Environmental, Vol. 219 https://doi.org/10.1016/j.apcatb.2017.07.073	journal	December 2017
Evolution of the structure of unpromoted and potassium-promoted ceria-supported nickel catalysts in the steam reforming of ethanol Słowik, Grzegorz; Greluk, Magdalena; Rotko, Marek Applied Catalysis B: Environmental, Vol. 221 https://doi.org/10.1016/j.apcatb.2017.09.052	journal	February 2018
H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts Frusteri, F.; Freni, S.; Spadaro, L. Catalysis Communications, Vol. 5, Issue 10 https://doi.org/10.1016/j.catcom.2004.07.015	journal	October 2004
Cr, Zr-incorporated hydrotalcites and their application in the synthesis of isophorone Liu, Yanxia; Sun, Kunpeng; Ma, Haowen Catalysis Communications, Vol. 11, Issue 10 https://doi.org/10.1016/j.catcom.2010.03.014	journal	May 2010
H2 production through steam reforming of ethanol over Pt/ZrO2, Pt/CeO2 and Pt/CeZrO2 catalysts de Lima, Sania M.; Silva, Adriana M.; da Cruz, Ivna O. Catalysis Today, Vol. 138, Issue 3-4 https://doi.org/10.1016/j.cattod.2008.06.014	journal	November 2008
An overview of hydrogen production technologies Holladay, J. D.; Hu, J.; King, D. L. Catalysis Today, Vol. 139, Issue 4 https://doi.org/10.1016/j.cattod.2008.08.039	journal	January 2009
Effect of the transition metal oxide supports on hydrogen production from bio-ethanol reforming He, Zhong; Yang, Min; Wang, Xianqin Catalysis Today, Vol. 194, Issue 1 https://doi.org/10.1016/j.cattod.2012.05.004	journal	October 2012
Effect of alkali on C H bond scission over Pt/YSZ catalyst during water-gas-shift, steam-assisted formic acid decomposition and methanol steam reforming Martinelli, Michela; Jacobs, Gary; Shafer, Wilson D. Catalysis Today, Vol. 291 https://doi.org/10.1016/j.cattod.2016.12.003	journal	August 2017
Surface chemistry of electrodeposited Cu2O films studied by XPS Zhu, Changqiong; Osherov, Anna; Panzer, Matthew J. Electrochimica Acta, Vol. 111 https://doi.org/10.1016/j.electacta.2013.08.038	journal	November 2013
Recent progress in ethanol steam reforming using non-noble transition metal catalysts: A review Ogo, Shuhei; Sekine, Yasushi Fuel Processing Technology, Vol. 199 https://doi.org/10.1016/j.fuproc.2019.106238	journal	March 2020
A review on reforming bio-ethanol for hydrogen production Ni, Meng; Leung, Dennis Y. C.; Leung, Michael K. H. International Journal of Hydrogen Energy, Vol. 32, Issue 15 https://doi.org/10.1016/j.ijhydene.2007.04.038	journal	October 2007
Catalysts for H 2 production using the ethanol steam reforming (a review) Contreras, J. L.; Salmones, J.; Colín-Luna, J. A. International Journal of Hydrogen Energy, Vol. 39, Issue 33 https://doi.org/10.1016/j.ijhydene.2014.08.072	journal	November 2014
Hydrogen: Trends, production and characterization of the main process worldwide da Silva Veras, Tatiane; Mozer, Thiago Simonato; da Costa Rubim Messeder dos Santos, Danielle International Journal of Hydrogen Energy, Vol. 42, Issue 4 https://doi.org/10.1016/j.ijhydene.2016.08.219	journal	January 2017
Sodium doping of Pt/m-ZrO2 promotes C–C scission and decarboxylation during ethanol steam reforming Martinelli, Michela; Watson, Caleb D.; Jacobs, Gary International Journal of Hydrogen Energy, Vol. 45, Issue 36 https://doi.org/10.1016/j.ijhydene.2019.08.111	journal	July 2020
Low-temperature water?gas shift: impact of Pt promoter loading on the partial reduction of ceria and consequences for catalyst design Jacobs, G.; Graham, U.; Chenu, E. Journal of Catalysis, Vol. 229, Issue 2 https://doi.org/10.1016/j.jcat.2004.11.031	journal	January 2005
Hydrogen production for fuel cell applications by ethanol partial oxidation on Pt/CeO2 catalysts: the effect of the reaction conditions and reaction mechanism Mattos, L.; Noronha, F. Journal of Catalysis, Vol. 233, Issue 2 https://doi.org/10.1016/j.jcat.2005.04.022	journal	July 2005
Steam reforming of ethanol over Pt/ceria with co-fed hydrogen Jacobs, G.; Keogh, R.; Davis, B. Journal of Catalysis, Vol. 245, Issue 2 https://doi.org/10.1016/j.jcat.2006.10.018	journal	January 2007
Steam reforming, partial oxidation, and oxidative steam reforming of ethanol over Pt/CeZrO2 catalyst de Lima, Sania M.; da Cruz, Ivna O.; Jacobs, Gary Journal of Catalysis, Vol. 257, Issue 2 https://doi.org/10.1016/j.jcat.2008.05.017	journal	July 2008
Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility Song, H.; Ozkan, U. Journal of Catalysis, Vol. 261, Issue 1 https://doi.org/10.1016/j.jcat.2008.11.006	journal	January 2009
Vapour-phase C–C coupling reactions of biomass-derived oxygenates over Pd/CeZrOx catalysts Kunkes, Edward L.; Gürbüz, Elif I.; Dumesic, James A. Journal of Catalysis, Vol. 266, Issue 2 https://doi.org/10.1016/j.jcat.2009.06.014	journal	September 2009
Structural effects of Na promotion for high water gas shift activity on Pt–Na/TiO2 Zhu, Xinli; Shen, Min; Lobban, Lance L. Journal of Catalysis, Vol. 278, Issue 1 https://doi.org/10.1016/j.jcat.2010.11.023	journal	February 2011
Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol Gao, Peng; Li, Feng; Zhan, Haijuan Journal of Catalysis, Vol. 298 https://doi.org/10.1016/j.jcat.2012.10.030	journal	February 2013
Reforming of ethanol on Co/Al2O3 catalysts reduced at different temperatures Ferencz, Zs.; Varga, E.; Puskás, R. Journal of Catalysis, Vol. 358 https://doi.org/10.1016/j.jcat.2017.12.003	journal	February 2018
Enhanced bimetallic Rh-Ni supported catalysts on alumina doped with mixed lanthanum-cerium oxides for ethanol steam reforming Campos, Cristian H.; Pecchi, Gina; Fierro, José Luis G. Molecular Catalysis, Vol. 469 https://doi.org/10.1016/j.mcat.2019.03.007	journal	May 2019
Catalytic Reforming of Oxygenates: State of the Art and Future Prospects Li, Di; Li, Xinyu; Gong, Jinlong Chemical Reviews, Vol. 116, Issue 19 https://doi.org/10.1021/acs.chemrev.6b00099	journal	August 2016
Hydrogen Production Reactions from Carbon Feedstocks: Fossil Fuels and Biomass Navarro, R. M.; Peña, M. A.; Fierro, J. L. G. Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr0501994	journal	October 2007
Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation Mattos, Lisiane V.; Jacobs, Gary; Davis, Burtron H. Chemical Reviews, Vol. 112, Issue 7 https://doi.org/10.1021/cr2000114	journal	April 2012
A Common Single-Site Pt(II)–O(OH) _x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction Yang, Ming; Liu, Jilei; Lee, Sungsik Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja513292k	journal	March 2015
Ethanol steam reforming over Rh and Pt catalysts: effect of temperature and catalyst deactivation Bilal, Muhammad; Jackson, S. David Catal. Sci. Technol., Vol. 3, Issue 3 https://doi.org/10.1039/C2CY20703F	journal	January 2013
Reduction of CeO ₂ by hydrogen. Magnetic susceptibility and Fourier-transform infrared, ultraviolet and X-ray photoelectron spectroscopy measurements Laachir, Ahmidou; Perrichon, Vincent; Badri, Ahmed J. Chem. Soc., Faraday Trans., Vol. 87, Issue 10 https://doi.org/10.1039/FT9918701601	journal	January 1991
Contribution of shape resonance and Pt–H EXAFS in the Pt L2,3 X-ray absorption edges of supported Pt particles: Application and consequences for catalyst characterization Ramaker, Dave E.; Mojet, Barbara L.; Garriga Oostenbrink, Marc T. Physical Chemistry Chemical Physics, Vol. 1, Issue 9 https://doi.org/10.1039/a900716d	journal	January 1999
Estimation of mean size and shape of small metal particles by EXAFS Jentys, Andreas Physical Chemistry Chemical Physics, Vol. 1, Issue 17 https://doi.org/10.1039/a904654b	journal	January 1999
Conversion of glycerol to hydrogen rich gas Tran, Nguyen H.; Kannangara, G. S. Kamali Chemical Society Reviews, Vol. 42, Issue 24 https://doi.org/10.1039/c3cs60227c	journal	January 2013
WinXAS a Program for X-ray Absorption Spectroscopy Data Analysis under MS-Windows Ressler, T. Journal of Synchrotron Radiation, Vol. 5, Issue 2, p. 118-122 https://doi.org/10.1107/S0909049597019298	journal	March 1998
Methanol Steam Reforming: Na Doping of Pt/YSZ Provides Fine Tuning of Selectivity Martinelli, Michela; Jacobs, Gary; Graham, Uschi Catalysts, Vol. 7, Issue 5 https://doi.org/10.3390/catal7050148	journal	May 2017
Nanoparticle size evaluation of catalysts by EXAFS: Advantages and limitations Marinkovic, Nebojsa; Sasaki, Kotaro; Adzic, Radoslav Zastita materijala, Vol. 57, Issue 1 https://doi.org/10.5937/ZasMat1601101M	journal	January 2016

Similar Records

Promoting the Selectivity of Pt/m-ZrO₂ Ethanol Steam Reforming Catalysts with K and Rb Dopants

Journal Article · Sun Aug 29 00:00:00 EDT 2021 · Nanomaterials · OSTI ID:1818067

Influence of Cs Promoter on Ethanol Steam-Reforming Selectivity of Pt/m-ZrO₂ Catalysts at Low Temperature

Journal Article · Tue Sep 14 00:00:00 EDT 2021 · Catalysts · OSTI ID:1840021

Low temperature ethanol steam reforming: Selectivity control with lithium doping of Pt/m-ZrO₂

Journal Article · Fri Jun 17 00:00:00 EDT 2022 · Catalysis Today · OSTI ID:1909636

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DRIFTS
Electronic effect
Ethanol steam reforming
Sodium loading
Zirconia

Effect of sodium loading on Pt/ZrO2 during ethanol steam reforming

Citation Formats

References (67)

Similar Records

Related Subjects

Effect of sodium loading on Pt/ZrO₂ during ethanol steam reforming