Atomically Thick Oxide Overcoating Stimulates Low-Temperature Reactive Metal-Support Interactions for Enhanced Catalysis.

J Am Chem Soc

Department of Chemical Physics, Hefei National Research Center for Physical Sciences at the Microscale, iChem, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei 230026, Anhui, China.

Published: March 2023


Article Synopsis

  • Reactive metal-support interactions (RMSIs) help create bimetallic alloys that improve catalysis, but they usually require high temperatures over 500 °C, limiting the variety of alloys that can be produced.
  • Researchers discovered that a thin layer of GaO on palladium (Pd) nanoparticles allows RMSIs to occur at a significantly lower temperature of around 250 °C.
  • The resulting Ga-rich PdGa alloys formed at this lower temperature dramatically enhance methanol and dimethyl ether production in the CO hydrogenation reaction, boosting yields about five times compared to traditional catalysts.

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Article Abstract

Reactive metal-support interactions (RMSIs) induce the formation of bimetallic alloys and offer an effective way to tune the electronic and geometric properties of metal sites for advanced catalysis. However, RMSIs often require high-temperature reductions (>500 °C), which significantly limits the tuning of bimetallic compositional varieties. Here, we report that an atomically thick GaO coating of Pd nanoparticles enables the initiation of RMSIs at a much lower temperature of ∼250 °C. State-of-the-art microscopic and spectroscopic studies disclose that low-temperature RMSIs initiate the formation of rarely reported Ga-rich PdGa alloy phases, distinct from the PdGa phase formed in traditional Pd/GaO catalysts after high-temperature reduction. In the CO hydrogenation reaction, the Ga-rich alloy phases impressively boost the formation of methanol and dimethyl ether ∼5 times higher than that of Pd/GaO. infrared spectroscopy reveals that the Ga-rich phases greatly favor formate formation as well as its subsequent hydrogenation, thus leading to high productivity.

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http://dx.doi.org/10.1021/jacs.2c12046DOI Listing

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