01617nas a2200265 4500008004100000022001400041245010300055210006900158260000800227300001400235490000600249520073700255653001800992653002001010653001501030653000901045653003001054653000901084100002301093700002101116700002201137700003601159700002501195856013101220 2020 eng d a2574-096200aTweaking palladium electronic structure to attain oxygen reduction activity superior to platinum/C0 aTweaking palladium electronic structure to attain oxygen reducti cJUL a6127-61320 v33 a

Enhancing oxygen reduction (ORR) activity through alloying is crucial to improve the performance of a fuel-cell catalysts. In this work, we have studied the alloying effects of 4f rare-earth (RE) metals with palladium. The modified catalyst exhibits better activity (E-onset = 1 V and E-1/2 = 0.88 V) and higher selectivity toward H2O (similar to 97%) compared to the state-of-the-art catalysts due to complete dissociation of O-2. Hirshfeld charge analysis and 2D-electron localization function reveal improved adsorbate-adsorbent interaction on the catalyst surface. This work paves a strategy to design highly selective non-Pt-based catalysts for the ORR by controlling electronic structures and surface oxide formation.

10ad-band center10aDFT calculation10adurability10aEuPd10aoxygen reduction reaction10aYbPd1 aSarma, Saurav, Ch.1 aKaja, Sai, Manoj1 aMishra, Vidyanshu1 aVinod, Chathakudath, Prabhakara1 aPeter, Sebastian, C. uhttps://library.ncl.res.in/content/tweaking-palladium-electronic-structure-attain-oxygen-reduction-activity-superior-platinumc01804nas a2200205 4500008004100000022001400041245009700055210006900152260000800221300001400229490000700243520108500250100002701335700002501362700002201387700002101409700001801430700002501448856012501473 2023 eng d a0897-475600aMetal deficiency tailored by the 18-electron rule stabilizes metal-based inorganic compounds0 aMetal deficiency tailored by the 18electron rule stabilizes meta cJUL a6050-60580 v353 a

The 18-electron (18-e(-)) rule is typicallyrestrictedto predicting the stability of transition-metal-based complexes. Herein,we report the use of the 18-e(-) to predict the stabilityin a family of intermetallics MNiSn (M = V, Cr, Fe, and Co) crystallizingin the Co1.75Ge structure type. Site deficiencies at theM site obtained from single-crystal X-ray diffraction are understoodas attaining a stable noble gas electronic configuration. The densityfunctional theory -based structure calculation confirms that the deficientstructure is more stable than the ideal occupation available at thecrystal lattice. MnNiSn, which crystallizes in the half-Heusler crystalstructure, depicts the role of covalent radii of the constituent elementsin determining the crystal structure. Using X-ray absorption spectroscopyand X-ray photoelectron spectroscopy, the local structure of the above-mentionedcompounds was also elucidated, supporting the role of deficiency tunedvalence fluctuation to attain a 18-e(-) configurationthat eventually leads to the formation of stable compounds.

1 aSingh, Ashutosh, Kumar1 aMumbaraddi, Dundappa1 aMishra, Vidyanshu1 aRoy, Soumyabrata1 aVinod, C., P.1 aPeter, Sebastian, C. uhttps://library.ncl.res.in/content/metal-deficiency-tailored-18-electron-rule-stabilizes-metal-based-inorganic-compounds