New Dion–Jacobson Phase Three-Layer Perovskite CsBa₂Ta₃O₁₀ and Its Conversion to Nitrided Ba₂Ta₃O₁₀ Nanosheets via a Nitridation–Protonation–Intercalation–Exfoliation Route for Water Splitting

Abstract

We report on the synthesis of new Dion−Jacobson phase threelayer perovskite CsBa 2 Ta 3 O 10 crystals by conventional solid-state reaction and fabrication of their nitrided Ba 2 Ta 3 O 10 nanosheets via a nitridation−protonation− intercalation−exfoliation route for visible-light-driven photocatalytic water splitting application. The two-dimensional crystal structure of CsBa 2 Ta 3 O 10 refined by the Rietveld refinement method belongs to the simple tetragonal system and consists of corner-shared distorted TaO 6 octahedra and Ba cations in cuboctahedral sites forming triple-layer perovskite slabs. The valence and conduction band edge potentials estimated by density functional theory with respect to vacuum scale and normal hydrogen electrode indicate that CsBa 2 Ta 3 O 10 is a UV-light-active semiconductor that can be used for photocatalytic water splitting and decomposition of organic pollutants. The projected electronic wave functions contour plot of CsBa 2 Ta 3 O 10 in the (1 0 0) plane exhibited two different Ta−O bonds. The nitridation at 800 °C for 5 h under NH 3 atmosphere was found to be suitable for retaining the phase-purity of nitrided CsBa 2 Ta 3 O 10 crystals. The fabricated nanosheets of nitrided Ba 2 Ta 3 O 10 with lateral sizes ranging from several hundred nanometers to a few micrometers and height of about 2.3 nm can be applied for visible-light-driven photocatalytic water splitting.

Two‐Dimensional Halide Perovskites in Solar Cells: 2D or not 2D?

“…However, unlike RP phases, DJ perovskites form slabs that stack exactly on top of each other (Scheme ). Hybrid 2D perovskites that adopted the DJ structure were crystallized and implemented in solar cells for the first time by Kanatzidis and co‐workers by using 3‐ or 4‐(ammoniomethyl)piperidinium and MA (Scheme ) …”

“…Akin to the RP perovskites, DJ perovskites are named because of their similarity with their inorganic counterparts and also share the general formula (A') 2 A nÀ1 M n X 3n + 1 .H owever, unlike RP phases,D Jp erovskites form slabs that stack exactly on top of each other (Scheme4). Hybrid 2D perovskites that adopted the DJ structure [29,30] were crystallized and implemented in solar cellsf or the first time by Kanatzidis and co-workers by using 3-or 4-(ammoniomethyl)piperidinium and MA (Scheme 3). [25] Another interesting subclass of DJ perovskites is the alternating cations in the interlayer space family (or ACI perovskites), whichi ss tabilized by alternating guanidinium( A ')a nd MA (A) cations, with the formula (A') 2 (A) n B n X 3n + 1 .T he combination of thesec ations results in ad ifferent stacking motifw ith higher crystal symmetry (Scheme4), and ab and-gap decrease relative to their RP counterparts.…”

Electronic, optical and photocatalytic properties of three-layer perovskite Dion–Jacobson phase CsBa2M3O10(M = Ta, Nb): a DFT study

“…Table 2 showed that the MO 6 octahedra in CBTO and CBNO is distorted from O h point group to centrosymmetric (D 4h ) and non-centrosymmetric (C 4v ) point groups, as shown in Figure 1b. In the MO 6 15 . In the MO 6 15 .…”

“…The stability of cubic structure depends on the relative ionic size, in which a slight buckling and distortion, such as tilting of BO 6 phase; where Aʹ is monovalent alkali metal ion, A is divalent alkaline earth metal ion, and B is tetravalent or pentavalent transition metal ion. Most perovskites have a cubic symmetry structure in which the B cation is in 6-fold coordination surrounded by an octahedron of anions and A cation is in 12-fold cuboctahedral coordination.…”

UVA- and visible-light-driven photocatalytic activity of three-layer perovskite Dion-Jacobson phase CsBa2M3O10 (M=Ta, Nb) and oxynitride crystals in the removal of caffeine from model wastewater

“…1a-g are well indexed as the orthorhombic CaTaO2N (PDF# 50-1174), cubic SrTaO2N (PDF# 40-0662), cubic BaTaO2N (PDF# 84-1748), monoclinic LaTaON2 (PDF# 53-0960), orthorhombic LaTiO2N (PDF# 48-1230), tetragonal CsBa2Nb3O10 (PDF# 70-7833) and CsBa2Ta3O10[46]. No indicative diffraction peaks assignable to impurity phases can be observed, implying that the flux method was favorable for the direct growth of phase-pure oxide and oxynitride crystals.…”