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

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

doi:10.1016/j.apcata.2020.117947

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

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

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

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. 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.

Original language	English
Article number	117947
Journal	Applied Catalysis A: General
Volume	610
DOIs	https://doi.org/10.1016/j.apcata.2020.117947
State	Published - Jan 25 2021

Bibliographical note

Publisher Copyright:
© 2020 Elsevier B.V.

Funding

Research carried out at UTSA was supported by UTSA, the State of Texas, and the STARs program . Studies conducted at the CAER were supported in part by funding provided by the Commonwealth of Kentucky . Jonathan D. Castro would like to thank ACS Project SEED and the UTSA College of Engineering (COE) for financial support, and Nour Alhraki would like to thank the UTSA COE for support. Argonne’s research was supported in part by the U.S. Department of Energy (DOE), Office of Fossil Energy, National Energy Technology Laboratory (NETL) . Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions . Research carried out at UTSA was supported by UTSA, the State of Texas, and the STARs program. Studies conducted at the CAER were supported in part by funding provided by the Commonwealth of Kentucky. Jonathan D. Castro would like to thank ACS Project SEED and the UTSA College of Engineering (COE) for financial support, and Nour Alhraki would like to thank the UTSA COE for support. Argonne's research was supported in part by the U.S. Department of Energy (DOE), Office of Fossil Energy, National Energy Technology Laboratory (NETL). Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions.

Funders	Funder number
Office of Basic Energy Sciences
Southwest Texas State University
U.S. Department of Energy EPSCoR
American Cancer Society-Michigan Cancer Research Fund
American Chemical Society
Office of Fossil Energy and Carbon Management
Office of Science Programs
DOE Basic Energy Sciences	DE-AC02-06CH11357
The University of Texas Health Science Center at San Antonio
National Energy Technology Laboratory

Keywords

DRIFTS
Electronic effect
Ethanol steam reforming
Sodium loading
Zirconia

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology

Access to Document

10.1016/j.apcata.2020.117947

Cite this

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title = "Effect of sodium loading on Pt/ZrO2 during ethanol steam reforming",

abstract = "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. 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.",

keywords = "DRIFTS, Electronic effect, Ethanol steam reforming, Sodium loading, Zirconia",

author = "Michela Martinelli and Castro, \{Jonathan D.\} and Nour Alhraki and Matamoros, \{Maria E.\} and Kropf, \{A. Jeremy\} and Cronauer, \{Donald C.\} and Gary Jacobs",

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doi = "10.1016/j.apcata.2020.117947",

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AU - Martinelli, Michela

AU - Castro, Jonathan D.

AU - Alhraki, Nour

AU - Matamoros, Maria E.

AU - Kropf, A. Jeremy

AU - Cronauer, Donald C.

AU - Jacobs, Gary

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Y1 - 2021/1/25

N2 - 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. 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.

AB - 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. 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.

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KW - Sodium loading

KW - Zirconia

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