Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions
Abstract
The hydrogenation of CO2 into high energy density fuels such as methanol, where the required H2 is obtained from renewable sources, is of utmost importance for a sustainable society. In recent years, NiGa alloys have attracted attention as promising catalyst material systems for the hydrogenation of CO2 into methanol at ambient pressures. They thus represent an energy-saving alternative to the Cu-based catalysts employed in today's catalytic industry that require high pressures for the CO2 hydrogenation. However, the underlying reaction mechanisms for the NiGa system are still under debate. One of the challenges here is to unravel the evolution and coexistence of the different species in the heterogeneous NiGa catalyst system under activation and reaction conditions. To shed light on their evolution under activation in H2 and their catalytic roles under CO2 hydrogenation working conditions on well-defined Ni3Ga1 and Ni5Ga3 nanoparticle (NP) catalysts, we employed a multi-probe approach in this study. It included advanced machine learning-based analysis of operando X-ray absorption spectroscopy data combined with operando powder X-ray diffraction and near ambient pressure X-ray photoelectron spectroscopy measurements, as well as reactivity studies using bed-packed mass flow reactors. In addition, we employed atomic force microscopy and scanning transmission electron microscopy for structuralmore »
- Authors:
-
- Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
- Fritz Haber Institute of the Max Planck Society, Berlin (Germany); Ruhr Univ., Bochum (Germany)
- Ruhr Univ., Bochum (Germany); Univ. Politecnica de Catalunya (Spain)
- Ruhr Univ., Bochum (Germany)
- Ruhr Univ., Bochum (Germany); Max Planck Institute for Energy Conversion, Mülheim an der Ruhr (Germany)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); German Research Foundation (DFG); National Council on Science and Technology (CONACYT)
- OSTI Identifier:
- 1871829
- Report Number(s):
- BNL-223058-2022-JAAM
Journal ID: ISSN 0021-9517
- Grant/Contract Number:
- SC0012704; ERC-725915; EXC 2008-390540038; 708585
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 405; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; CO2 hydrogenation; Operando; Neural network; XAZ; XPS; XRD; Nanoparticles; Micelles; NiGa
Citation Formats
Hejral, Uta, Timoshenko, Janis, Kordus, David, Lopez Luna, Mauricio, Divins, Nuria J., Widrinna, Simon, Zegkinoglou, Ioannis, Pielsticker, Lukas, Mistry, Hemma, Boscoboinik, Jorge Anibal, Kuehl, Stefanie, and Roldan Cuenya, Beatriz. Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions. United States: N. p., 2021.
Web. doi:10.1016/j.jcat.2021.11.024.
Hejral, Uta, Timoshenko, Janis, Kordus, David, Lopez Luna, Mauricio, Divins, Nuria J., Widrinna, Simon, Zegkinoglou, Ioannis, Pielsticker, Lukas, Mistry, Hemma, Boscoboinik, Jorge Anibal, Kuehl, Stefanie, & Roldan Cuenya, Beatriz. Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions. United States. https://doi.org/10.1016/j.jcat.2021.11.024
Hejral, Uta, Timoshenko, Janis, Kordus, David, Lopez Luna, Mauricio, Divins, Nuria J., Widrinna, Simon, Zegkinoglou, Ioannis, Pielsticker, Lukas, Mistry, Hemma, Boscoboinik, Jorge Anibal, Kuehl, Stefanie, and Roldan Cuenya, Beatriz. Tue .
"Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions". United States. https://doi.org/10.1016/j.jcat.2021.11.024. https://www.osti.gov/servlets/purl/1871829.
@article{osti_1871829,
title = {Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions},
author = {Hejral, Uta and Timoshenko, Janis and Kordus, David and Lopez Luna, Mauricio and Divins, Nuria J. and Widrinna, Simon and Zegkinoglou, Ioannis and Pielsticker, Lukas and Mistry, Hemma and Boscoboinik, Jorge Anibal and Kuehl, Stefanie and Roldan Cuenya, Beatriz},
abstractNote = {The hydrogenation of CO2 into high energy density fuels such as methanol, where the required H2 is obtained from renewable sources, is of utmost importance for a sustainable society. In recent years, NiGa alloys have attracted attention as promising catalyst material systems for the hydrogenation of CO2 into methanol at ambient pressures. They thus represent an energy-saving alternative to the Cu-based catalysts employed in today's catalytic industry that require high pressures for the CO2 hydrogenation. However, the underlying reaction mechanisms for the NiGa system are still under debate. One of the challenges here is to unravel the evolution and coexistence of the different species in the heterogeneous NiGa catalyst system under activation and reaction conditions. To shed light on their evolution under activation in H2 and their catalytic roles under CO2 hydrogenation working conditions on well-defined Ni3Ga1 and Ni5Ga3 nanoparticle (NP) catalysts, we employed a multi-probe approach in this study. It included advanced machine learning-based analysis of operando X-ray absorption spectroscopy data combined with operando powder X-ray diffraction and near ambient pressure X-ray photoelectron spectroscopy measurements, as well as reactivity studies using bed-packed mass flow reactors. In addition, we employed atomic force microscopy and scanning transmission electron microscopy for structural characterization. Under H2 activation at 1 bar total pressure, we concluded the formation of metallic Ni, starting for Ni3Ga1 at 300 °C, and for Ni5Ga3 at 400 °C. At higher temperatures, the formation of NiGa alloys follows. The α'-Ni3Ga1 alloy phase is predominantly formed for the Ni3Ga1 NPs, while the coexistence of α'-Ni3Ga1, δ-Ni5Ga3 and Ga2O3 phases is observed for the Ni5Ga3 NPs after the H2 activation. The formation of the Ga2O3 phase also results in the presence of excess metallic Ni. Under CO2 hydrogenation reaction conditions, Ga partially oxidizes again to form a Ga2O3-rich particle shell for both NP compositions, yet, to a larger extent for the Ni3Ga1 NPs, which, in turn, feature a higher amount of excess Ni. We reveal that metallic Ni is responsible for the high selectivity of the Ni3Ga1 NPs towards the production of methane in our catalytic tests. In contrast, the Ni5Ga3 NPs display a strong selectivity toward methanol production (>92%), more than one order of magnitude higher than that for the Ni3Ga1 NPs, which we ascribe to the presence of the δ-Ni5Ga3 phase.},
doi = {10.1016/j.jcat.2021.11.024},
journal = {Journal of Catalysis},
number = ,
volume = 405,
place = {United States},
year = {Tue Nov 23 00:00:00 EST 2021},
month = {Tue Nov 23 00:00:00 EST 2021}
}
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