Efficient base-metal NiMn/TiO2 catalyst for CO2 methanation

Wilbert Vrijburg, E. Moioli, Wei Chen, Min Zhang, B.J.P. Terlingen, Bart Zijlstra, Ivo Filot, A. Züttel, Evgeny A. Pidko, Emiel Hensen (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Energy storage solutions are a vital component of the global transition toward renewable energy sources. The power-to-gas (PtG) concept, which stores surplus renewable energy in the form of methane, has therefore become increasingly relevant in recent years. At present, supported Ni nanoparticles are preferred as industrial catalysts for CO2 methanation due to their low cost and high methane selectivity. However, commercial Ni catalysts are not active enough in CO2 methanation to reach the high CO2 conversion (>99%) required by the specifications for injection in the natural gas grid. Herein we demonstrate the promise of promotion of Ni by Mn, another low-cost base metal, for obtaining very active CO2 methanation catalysts, with results comparable to more expensive precious metal-based catalysts. The origin of this improved performance is revealed by a combined approach of nanoscale characterization, mechanistic study, and density functional theory calculations. Nanoscale characterization with scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray absorption spectroscopy shows that NiMn catalysts consist of metallic Ni particles decorated by oxidic Mn2+ species. A mechanistic study combining IR spectroscopy of surface adsorbates, transient kinetic analysis with isotopically labeled CO2, density functional theory calculations, and microkinetics simulations ascertains that the MnO clusters enhance CO2 adsorption and facilitate CO2 activation. A macroscale perspective was achieved by simulating the Ni and NiMn catalytic activity in a Sabatier reactor, which revealed that NiMn catalysts have the potential to meet the demanding PtG catalyst performance requirements and can largely replace the need for expensive and scarce noble metal catalysts.

LanguageEnglish
Pages7823-7839
Number of pages17
JournalACS Catalysis
Volume9
DOIs
StatePublished - 17 Jul 2019

Fingerprint

Methanation
Carbon Monoxide
Metals
Catalysts
Methane
Precious metals
Density functional theory
Gases
X ray absorption spectroscopy
Catalyst selectivity
Adsorbates
Energy storage
Costs
Infrared spectroscopy
Catalyst activity
Natural gas
Chemical activation
Nanoparticles
Transmission electron microscopy
Specifications

Keywords

  • CO hydrogenation
  • manganese
  • mechanism
  • nickel
  • synergy

Cite this

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title = "Efficient base-metal NiMn/TiO2 catalyst for CO2 methanation",
abstract = "Energy storage solutions are a vital component of the global transition toward renewable energy sources. The power-to-gas (PtG) concept, which stores surplus renewable energy in the form of methane, has therefore become increasingly relevant in recent years. At present, supported Ni nanoparticles are preferred as industrial catalysts for CO2 methanation due to their low cost and high methane selectivity. However, commercial Ni catalysts are not active enough in CO2 methanation to reach the high CO2 conversion (>99{\%}) required by the specifications for injection in the natural gas grid. Herein we demonstrate the promise of promotion of Ni by Mn, another low-cost base metal, for obtaining very active CO2 methanation catalysts, with results comparable to more expensive precious metal-based catalysts. The origin of this improved performance is revealed by a combined approach of nanoscale characterization, mechanistic study, and density functional theory calculations. Nanoscale characterization with scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray absorption spectroscopy shows that NiMn catalysts consist of metallic Ni particles decorated by oxidic Mn2+ species. A mechanistic study combining IR spectroscopy of surface adsorbates, transient kinetic analysis with isotopically labeled CO2, density functional theory calculations, and microkinetics simulations ascertains that the MnO clusters enhance CO2 adsorption and facilitate CO2 activation. A macroscale perspective was achieved by simulating the Ni and NiMn catalytic activity in a Sabatier reactor, which revealed that NiMn catalysts have the potential to meet the demanding PtG catalyst performance requirements and can largely replace the need for expensive and scarce noble metal catalysts.",
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author = "Wilbert Vrijburg and E. Moioli and Wei Chen and Min Zhang and B.J.P. Terlingen and Bart Zijlstra and Ivo Filot and A. Z{\"u}ttel and Pidko, {Evgeny A.} and Emiel Hensen",
year = "2019",
month = "7",
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Efficient base-metal NiMn/TiO2 catalyst for CO2 methanation. / Vrijburg, Wilbert; Moioli, E.; Chen, Wei; Zhang, Min; Terlingen, B.J.P.; Zijlstra, Bart; Filot, Ivo; Züttel, A.; Pidko, Evgeny A.; Hensen, Emiel (Corresponding author).

In: ACS Catalysis, Vol. 9, 17.07.2019, p. 7823-7839.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - Efficient base-metal NiMn/TiO2 catalyst for CO2 methanation

AU - Vrijburg,Wilbert

AU - Moioli,E.

AU - Chen,Wei

AU - Zhang,Min

AU - Terlingen,B.J.P.

AU - Zijlstra,Bart

AU - Filot,Ivo

AU - Züttel,A.

AU - Pidko,Evgeny A.

AU - Hensen,Emiel

PY - 2019/7/17

Y1 - 2019/7/17

N2 - Energy storage solutions are a vital component of the global transition toward renewable energy sources. The power-to-gas (PtG) concept, which stores surplus renewable energy in the form of methane, has therefore become increasingly relevant in recent years. At present, supported Ni nanoparticles are preferred as industrial catalysts for CO2 methanation due to their low cost and high methane selectivity. However, commercial Ni catalysts are not active enough in CO2 methanation to reach the high CO2 conversion (>99%) required by the specifications for injection in the natural gas grid. Herein we demonstrate the promise of promotion of Ni by Mn, another low-cost base metal, for obtaining very active CO2 methanation catalysts, with results comparable to more expensive precious metal-based catalysts. The origin of this improved performance is revealed by a combined approach of nanoscale characterization, mechanistic study, and density functional theory calculations. Nanoscale characterization with scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray absorption spectroscopy shows that NiMn catalysts consist of metallic Ni particles decorated by oxidic Mn2+ species. A mechanistic study combining IR spectroscopy of surface adsorbates, transient kinetic analysis with isotopically labeled CO2, density functional theory calculations, and microkinetics simulations ascertains that the MnO clusters enhance CO2 adsorption and facilitate CO2 activation. A macroscale perspective was achieved by simulating the Ni and NiMn catalytic activity in a Sabatier reactor, which revealed that NiMn catalysts have the potential to meet the demanding PtG catalyst performance requirements and can largely replace the need for expensive and scarce noble metal catalysts.

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KW - CO hydrogenation

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KW - mechanism

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