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“Breaking structure sensitivity in CO2 hydrogenation by tuning metal–oxide interfaces in supported cobalt nanoparticles”. Parastaev A, Muravev V, Osta EH, Kimpel TF, Simons JFM, van Hoof AJF, Uslamin E, Zhang L, Struijs JJC, Burueva DB, Pokochueva EV, Kovtunov KV, Koptyug IV, Villar-Garcia IJ, Escudero C, Altantzis T, Liu P, Béché, A, Bals S, Kosinov N, Hensen EJM, Nature Catalysis 5, 1051 (2022). http://doi.org/10.1038/s41929-022-00874-4
Abstract: A high dispersion of the active metal phase of transition metals on oxide supports is important when designing efficient heterogeneous catalysts. Besides nanoparticles, clusters and even single metal atoms can be attractive for a wide range of reactions. However, many industrially relevant catalytic transformations suffer from structure sensitivity, where reducing the size of the metal particles below a certain size substantially lowers catalytic performance. A case in point is the low activity of small cobalt nanoparticles in the hydrogenation of CO and CO2. Here we show how engineering of catalytic sites at the metal–oxide interface in cerium oxide–zirconium dioxide (ceria–zirconia)-supported cobalt can overcome this structure sensitivity. Few-atom cobalt clusters dispersed on 3 nm cobalt(II)-oxide particles stabilized by ceria–zirconia yielded a highly active CO2 methanation catalyst with a specific activity higher than that of larger particles under the same conditions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Applied Electrochemistry & Catalysis (ELCAT)
Impact Factor: 37.8
Times cited: 32
DOI: 10.1038/s41929-022-00874-4
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“Halide-guided active site exposure in bismuth electrocatalysts for selective CO₂, conversion into formic acid”. Yang S, An H, Arnouts S, Wang H, Yu X, de Ruiter J, Bals S, Altantzis T, Weckhuysen BM, van der Stam W, Nature Catalysis 6, 796 (2023). http://doi.org/10.1038/S41929-023-01008-0
Abstract: It remains a challenge to identify the active sites of bismuth catalysts in the electrochemical CO2 reduction reaction. Here we show through in situ characterization that the activation of bismuth oxyhalide electrocatalysts to metallic bismuth is guided by the halides. In situ X-ray diffraction results show that bromide promotes the selective exposure of planar bismuth surfaces, whereas chloride and iodide result in more disordered active sites. Furthermore, we find that bromide-activated bismuth catalysts outperform the chloride and iodide counterparts, achieving high current density (>100 mA cm(-2)) and formic acid selectivity (>90%), suggesting that planar bismuth surfaces are more active for the electrochemical CO2 reduction reaction. In addition, in situ X-ray absorption spectroscopy measurements reveal that the reconstruction proceeds rapidly in chloride-activated bismuth and gradually when bromide is present, facilitating the formation of ordered planar surfaces. These findings show the pivotal role of halogens on selective facet exposure in activated bismuth-based electrocatalysts during the electrochemical CO2 reduction reaction.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Applied Electrochemistry & Catalysis (ELCAT)
Impact Factor: 37.8
Times cited: 13
DOI: 10.1038/S41929-023-01008-0
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“Atomically dispersed ruthenium hydride on beta zeolite as catalysts for the isomerization of muconates”. Khalil I, Rigamonti MG, Janssens K, Bugaev A, Arenas Esteban D, Robijns S, Donckels T, Beydokhti MT, Bals S, De Vos D, Dusselier M, Nature Catalysis 7, 921 (2024). http://doi.org/10.1038/S41929-024-01205-5
Abstract: Searching for sustainable polymers requires access to biomass-based monomers. In that sense, glucose-derived cis,cis-muconic acid stands as a high-potential intermediate. However, to unlock its potential, an isomerization to the value-added trans,trans-isomer, trans,trans-muconic acid, is required. Here we develop atomically dispersed low-loaded Ru on beta zeolite catalysts that produce trans,trans-muconate in ethanol with total conversion (to equilibrium) and a selectivity of >95%. We reach very high turnovers per Ru and productivity rates of 427 mM h(-1) (similar to 85 g l(-1) h(-1)), surpassing the bio-based cis,cis-muconic acid production rates by an order of magnitude. By coupling isomerization to Diels-Alder cycloaddition, terephthalate intermediates are produced in around 90% yields, circumventing the isomer equilibrium. Isomerization is promoted by Ru hydride species where the hydrides are generated from the alcohol solvent, as evidenced by Fourier transform infrared spectroscopy. Beyond isomerization, the Ru-zeolite and its hydride-forming capacity could be of use as a heterogeneous catalyst for other hydride chemistries, demonstrated by a successful hydride transfer hydrogenation.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 37.8
DOI: 10.1038/S41929-024-01205-5
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