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Modulation of the superficial electronic structure via metal-support interaction for H₂ evolution over Pd catalysts.

ABSTRACT: Electronic interactions can radically enhance the performance of supported metal catalysts and are critical for fundamentally understanding the nature of catalysts. However, at the microscopic level, the details of such interactions tuning the electronic properties of the sites on the metal particle's surface and metal-support interface remain obscure. Herein, we found polarized electronic metal-support interaction (pEMSI) in oxide-supported Pd nanoparticles (NPs) describing the enhanced accumulation of electrons at the surface of NPs (superficial Pd ^δ-) with positive Pd atoms distributed on the interface (interfacial Pd ^δ+). More superficial Pd ^δ- species mean stronger pEMSI resulting from the synergistic effect of moderate Pd-oxide interaction, high structural fluxionality and electron transport activity of Pd NPs. The surface Pd ^δ- species are responsible for improved catalytic performance for H₂ evolution from metal hydrides and formates. These extensive insights into the nature of supported-metal NPs may open new avenues for regulating a metal particle's electronic structure precisely and exploiting high-performance catalysts.

SUBMITTER: Wang J

PROVIDER: S-EPMC8179383 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Biodiesel is of high interest due to increased demand for energy with the concern regarding more sustainable production processes. However, an inevitable by-product is glycerol. Hence, the conversion of this by-product to higher-value chemicals, especially 1,3-propanediol (1,3-PDO) via glycerol hydrogenolysis reaction, is one of the most effective pathways towards a profitable process. In general, this process is catalyzed by a highly active Pt-based catalyst supported on γ-Al2O3. However, its low 1,3-PDO selectivity and stability due to surface deactivation of such catalysts remained. This led to the surface modification by WOx to improve both the selectivity by means of the increased Brønsted acidity and the stability in terms of Pt leaching-resistance. Hence, we applied experimental and density functional theory (DFT)-based techniques to study the fundamentals of how WOx modified the catalytic performance in the Pt/γ-Al2O3 catalyst and provided design guidelines. The effects of WOx promoter on improved activity were due to the shifting of the total density of states towards the antibonding region evident by the total density of states (TDOS) profile. On the improved 1,3-PDO selectivity, the main reason was the increasing number of Brønsted acid sites due to the added WOx promoter. Interestingly, the stability improvement was due to the strong metal-support interaction (SMSI) that occurred in the catalyst, like typical high leaching-resistant catalysts. Also, the observed strong metal-support-promoter interaction (SMSPI) is an additional effect preventing leaching. The SMSPI stemmed from additional bonding between the WOx species and the Pt active site, which significantly strengthened Pt adsorption to support and a high electron transfer from both Pt and Al2O3 to WOx promoter. This suggested that the promising promoter for our reaction performed in the liquid phase would improve the stability if SMSI occurred, where the special case of the WOx promoter would even highly improve the stability through SMSPI. Nevertheless, various promoters that can promote SMSPI need investigations.

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Modulation of the superficial electronic structure via metal-support interaction for H₂ evolution over Pd catalysts.

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Modulation of the superficial electronic structure via metal-support interaction for H₂ evolution over Pd catalysts.