Isotope effect in formaldehyde steam reforming on Pt/m-ZrO2: Insight into chemical promotion by alkalis

Michela Martinelli; Jonas Marcelle; Donald C. Cronauer; A. Jeremy Kropf; Gary Jacobs

doi:10.1016/j.catcom.2023.106668

Isotope effect in formaldehyde steam reforming on Pt/m-ZrO₂: Insight into chemical promotion by alkalis

Michela Martinelli
, Jonas Marcelle
, Donald C. Cronauer
, A. Jeremy Kropf
, Gary Jacobs

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

2 Scopus citations

Abstract

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO₂. In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO₂ and H₂. Alkali-doping of 2 wt% Pt/m-ZrO₂ increases catalyst basicity, which weakens the formate C–H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate ν(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H- to D-labeled formaldehyde in TP-reaction/MS.

Original language	English
Article number	106668
Journal	Catalysis Communications
Volume	178
DOIs	https://doi.org/10.1016/j.catcom.2023.106668
State	Published - May 2023

Bibliographical note

Publisher Copyright:
© 2023 The Authors

Funding

The work of Gary Jacobs and Jonas Marcelle was funded in part by a UTSA-SWRI Connect grant supported by The Office of the Vice President for Research, Economic Development, and Knowledge Enterprise at UTSA . Argonne's research was supported in part by the U.S. Department of Energy (DOE) , Office of Fossil Energy , National Energy Technology Laboratory (NETL) . The Advanced Photon Source was supported by the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences , under contract number DEAC02-06CH11357 . MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. CAER research was supported by the Commonwealth of Kentucky.

Funders	Funder number
Office of the Vice President for Research
UTSA-SWRI
U.S. Department of Energy
Office of Fossil Energy and Carbon Management
Office of Science Programs
DOE Basic Energy Sciences	DEAC02-06CH11357
National Energy Technology Laboratory

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Alkali
Formaldehyde steam reforming
Hydrogen production
Isotope effect
Platinum / zirconia
Sodium

ASJC Scopus subject areas

Catalysis
General Chemistry
Process Chemistry and Technology

Access to Document

10.1016/j.catcom.2023.106668

Cite this

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title = "Isotope effect in formaldehyde steam reforming on Pt/m-ZrO2: Insight into chemical promotion by alkalis",

abstract = "Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO2. In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO2 and H2. Alkali-doping of 2 wt\% Pt/m-ZrO2 increases catalyst basicity, which weakens the formate C{\textendash}H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate ν(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H- to D-labeled formaldehyde in TP-reaction/MS.",

keywords = "Alkali, Formaldehyde steam reforming, Hydrogen production, Isotope effect, Platinum / zirconia, Sodium",

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T2 - Insight into chemical promotion by alkalis

AU - Martinelli, Michela

AU - Marcelle, Jonas

AU - Cronauer, Donald C.

AU - Kropf, A. Jeremy

AU - Jacobs, Gary

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N2 - Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO2. In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO2 and H2. Alkali-doping of 2 wt% Pt/m-ZrO2 increases catalyst basicity, which weakens the formate C–H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate ν(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H- to D-labeled formaldehyde in TP-reaction/MS.

AB - Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO2. In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO2 and H2. Alkali-doping of 2 wt% Pt/m-ZrO2 increases catalyst basicity, which weakens the formate C–H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate ν(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H- to D-labeled formaldehyde in TP-reaction/MS.

KW - Alkali

KW - Formaldehyde steam reforming

KW - Hydrogen production

KW - Isotope effect

KW - Platinum / zirconia

KW - Sodium

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