First Observation of an Inverse Ruddlesden‐Popper Series: (A_3n+1ON_n−1)Bi_n+1 with A = Sr, Ba and n = 1, 3

Abstract

Single crystals ((Ba0.78(1)Sr0.22)4O)Bi2 and ((Ba0.62(1)Sr0.38)10N2O)Bi4 were successfully prepared from melt beads of Ba, Sr, and Bi in nitrogen atmosphere with oxygen impurities. The phases can be prepared in single phase from the appropriate mixtures of alkaline‐earth metal, bismuth, and bismuth oxide upon heating in pure nitrogen atmosphere. ((Ba0.78(1)Sr0.22)4O)Bi2 crystallizes in the K2NiF4 structure type (space group I4/mmm, No. 139, a = 522.34(5) pm, c = 1844.0(2) pm, Z = 2, Rgt(F) = 0.039) with layers of vertex‐sharing octahedra ((Ba,Sr)4/2Ba2O). ((Ba0.62(1)Sr0.38)10N2O)Bi4 crystallizes as an isotype of Sr4Ti3O10 (space group I4/mmm, No. 139, a = 531.3(1) pm, c = 3983.2(4) pm, Z = 2, Rgt(F) = 0.050) containing slabs of three layers of vertex‐sharing octahedra further connected via corners. These compounds are interpreted in terms of members of an inverse Ruddlesden‐Popper series with the general formula n (A3ONn−1)Bi · ABi or (A3n+1ONn−1)Bin+1, respectively, with n = 1, 3. Partial order of the alkaline‐earth metal ions is analyzed.

Na2Fe2OS2, a new earth abundant oxysulphide cathode material for Na-ion batteries

“…A few n ¼ 1 compounds have been reported in the anti-RP series, 14,44 but the only higher n member reported is the n ¼ 3 ((Ba,Sr) 3n+1 ON nÀ1 )Bi n+1 anti-RP compound. 54 The theoretical capacity is expected to decrease with increasing values of n (191 mA h g À1 for n ¼ 2, 178 mA h g À1 for n ¼ 3 and converging to 150 mA h g À1 for n ¼ N, corresponding to the anti-perovskite NaFe 2 OS) but these values remain attractive and higher order structures could present improved structural stability with cycling or other more valuable features compared to Na 2 Fe 2 OS 2 . It is interesting to note that the previously reported antiperovskite Li 2 FeOS, which has a much higher theoretical capacity (455 mA h g À1 ), is the end member of another anti-RP series [FeS][Li 2 FeOS] n , and shows more promise to increase the capacity.…”

“…This has been observed previously in compounds with similar structures and was attributed to the preferred ve-fold coordination of O over the six-fold coordination. 54 Sulphur atoms are slightly off plane with the sodium atoms of the same layer (z(Na)-z(S) ¼ 0.052(5)), such that S is displaced towards the closest Fe 2 O layer (Fig. 2f).…”

Metal‐Rich Ternary Perovskite Nitrides

“…Furthermore, an inverse Ruddlesden–Popper series of the general composition ( A 3 n +1 Z n )Bi n +1 with Z = N, O and n = 1, 3 was observed . Crystal structure arrangements are depicted in Figure .…”

Festkörperchemie 2007

“…• Die Synthese der beiden Verbindungen ((Ba0,78Sr0,224O)Bi2 und ((Ba0,62Sr0,3810N2O)Bi4 zeigt, dass sich unter geeigneten Bedingungen auch inverse Strukturen der Ruddlesden‐Popper‐Serien bilden (Abbildung 8, S. 262) 17. Das eigentliche Ziel der Arbeit war die Synthese eines reinen Nitrids; dabei schlich sich, wie so oft, Sauerstoff als Unreinheit im Stickstoffgas ein.…”