Silica-Supported PdGa Nanoparticles: Metal Synergy for Highly Active and Selective CO2-to-CH3OH Hydrogenation
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Date
2021-04-26
Publication Type
Journal Article, Journal Article
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yes
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Abstract
The direct conversion of CO2 to CH3OH represents an appealing strategy for the mitigation of anthropogenic CO2 emissions. Here, we report that small, narrowly distributed alloyed PdGa nanoparticles, prepared via surface organometallic chemistry from silica-supported GaIII isolated sites, selectively catalyze the hydrogenation of CO2 to CH3OH. At 230 °C and 25 bar, high activity (22.3 molMeOH molPd–1 h–1) and selectivity for CH3OH/DME (81%) are observed, while the corresponding silica-supported Pd nanoparticles show low activity and selectivity. X-ray absorption spectroscopy (XAS), IR, NMR, and scanning transmission electron microscopy–energy-dispersive X-ray provide evidence for alloying in the as-synthesized material. In situ XAS reveals that there is a dynamic dealloying/realloying process, through Ga redox, while operando diffuse reflectance infrared Fourier transform spectroscopy demonstrates that, while both methoxy and formate species are observed in reaction conditions, the relative concentrations are inversely proportional, as the chemical potential of the gas phase is modulated. High CH3OH selectivities, across a broad range of conversions, are observed, showing that CO formation is suppressed for this catalyst, in contrast to reported Pd catalysts.
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Publication status
published
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Book title
Journal / series
Volume
1 (4)
Pages / Article No.
450 - 458
Publisher
American Chemical Society
Event
Edition / version
Methods
Software
Geographic location
Date collected
Date created
Subject
CO2 hydrogenation; Heterogeneous catalysis; Alloys; Nanoparticles; Operando spectroscopy; Hydrogenation
Organisational unit
03872 - Copéret, Christophe / Copéret, Christophe
02513 - Laboratorium für Anorganische Chemie / Laboratory of Inorganic Chemistry
Notes
Funding
183495 - Tailored CO2 Hydrogenation Catalysts for Selective Methanol Synthesis via Structure-Activity Relationship across Time and Length Scale (SNF)
169134 - Molecular Approach to Heterogeneous Catalysis (SNF)
169134 - Molecular Approach to Heterogeneous Catalysis (SNF)
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