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Title: Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity

Abstract

A δ-Ni5Ga3/SiO2 catalyst, which is highly active and stable for thermal CO2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD (X-ray Diffraction), TEM (Transmission Electron Microscopy), H2-TPR (Temperature Programmed Reduction), CO chemisorption, along with in-situ ETEM (Environmental Transmission Electron Microscopy), APXPS (Ambient Pressure X-ray Photoelectron Spectroscopy) and HERFD-XAS (High Energy Resolution Fluorescence Detected X-Ray Absorption Spectroscopy). Upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely only at high temperatures (above 600 °C); the temperature of the reducing activation treatment plays a crucial role on the catalytic activity. HERFD-XAS and APXPS measurements show that an amorphous Ga2O3 shell persists during catalysis after low temperature reductions, promoting methanol synthesis.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [4]; ORCiD logo [5];  [1]
  1. Stanford Univ., CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. Stanford Univ., CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  5. Stanford Univ., CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Univ. of Surrey, Guildford (United Kingdom)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1608259
Grant/Contract Number:  
AC02-76SF00515; DGE-114747
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 267; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ni-Ga; Intermetallic; Methanol synthesis; In-Situ characterization; Ga2O3; CO2; utilization

Citation Formats

Gallo, Alessandro, Snider, Jonathan L., Sokaras, Dimosthenis, Nordlund, Dennis, Kroll, Thomas, Ogasawara, Hirohito, Kovarik, Libor, Duyar, Melis S., and Jaramillo, Thomas F.. Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity. United States: N. p., 2019. Web. https://doi.org/10.1016/j.apcatb.2019.118369.
Gallo, Alessandro, Snider, Jonathan L., Sokaras, Dimosthenis, Nordlund, Dennis, Kroll, Thomas, Ogasawara, Hirohito, Kovarik, Libor, Duyar, Melis S., & Jaramillo, Thomas F.. Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity. United States. https://doi.org/10.1016/j.apcatb.2019.118369
Gallo, Alessandro, Snider, Jonathan L., Sokaras, Dimosthenis, Nordlund, Dennis, Kroll, Thomas, Ogasawara, Hirohito, Kovarik, Libor, Duyar, Melis S., and Jaramillo, Thomas F.. Mon . "Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity". United States. https://doi.org/10.1016/j.apcatb.2019.118369. https://www.osti.gov/servlets/purl/1608259.
@article{osti_1608259,
title = {Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity},
author = {Gallo, Alessandro and Snider, Jonathan L. and Sokaras, Dimosthenis and Nordlund, Dennis and Kroll, Thomas and Ogasawara, Hirohito and Kovarik, Libor and Duyar, Melis S. and Jaramillo, Thomas F.},
abstractNote = {A δ-Ni5Ga3/SiO2 catalyst, which is highly active and stable for thermal CO2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD (X-ray Diffraction), TEM (Transmission Electron Microscopy), H2-TPR (Temperature Programmed Reduction), CO chemisorption, along with in-situ ETEM (Environmental Transmission Electron Microscopy), APXPS (Ambient Pressure X-ray Photoelectron Spectroscopy) and HERFD-XAS (High Energy Resolution Fluorescence Detected X-Ray Absorption Spectroscopy). Upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely only at high temperatures (above 600 °C); the temperature of the reducing activation treatment plays a crucial role on the catalytic activity. HERFD-XAS and APXPS measurements show that an amorphous Ga2O3 shell persists during catalysis after low temperature reductions, promoting methanol synthesis.},
doi = {10.1016/j.apcatb.2019.118369},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 267,
place = {United States},
year = {2019},
month = {11}
}

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