RESUMEN
Transition metal tungstates (TMTs) possess a wolframite-like lattice structure and preferably form via an electrostatic interaction between a divalent transition metal cation (MII) and an oxyanion of tungsten ([WO4]2-). A unit cell of a TMT is primarily composed of two repeating units, [MO6]oh and [WO6]oh, which are held together via several M-µ2-O-W bridging links. The bond character (ionic or covalent) of this bridging unit determines the stability of the lattice and influences the electronic structure of the bulk TMT materials. Recently, TMTs have been successfully employed as an electrode material for various applications, including electrochemical water splitting. Despite the wide electrocatalytic applications of TMTs, the study of the structure-activity correlation and electronic factors responsible for in situ structural evolution to electroactive species during electrochemical reactions is still in its infancy. Herein, a series of TMTs, MIIWVIO4 (M = Mn/Fe/Co/Ni), have been prepared and employed as electrocatalysts to study the oxygen evolution reaction (OER) under alkaline conditions and to scrutinize the role of transition metals in controlling the energetics of the formation of electroactive species. Since the [WO6]oh unit is common in the TMTs considered, the variation of the central atom of the corresponding [MO6]oh unit plays an intriguing role in controlling the electronic structure and stability of the lattice under anodic potential. Under the OER conditions, a potential-dependent structural transformation of MWO4 is noticed, where MnWO4 appears to be the most labile, whereas NiWO4 is stable up to a high anodic potential of â¼1.68 V (vs RHE). Potential-dependent hydrolytic [WO4]2- dissolution to form MOx active species, traced by in situ Raman and various spectro-/microscopic analyses, can directly be related to the electronic factors of the lattice, viz., crystal field splitting energy (CFSE) of MII in [MO6]oh, formation enthalpy (ΔHf), decomposition enthalpy (ΔHd), and Madelung factor associated with the MWO4 ionic lattice. Additionally, the magnitude of the Löwdin and Bader charges on M of the M-µ2-O-W bond is directly related to the degree of ionicity or covalency in the MWO4 lattice, which indirectly influences the electronic structure and activity. The experimental results substantiated by the computational study explain the electrochemical activity of the TMTs with the help of various structural and electronic factors and bonding interactions in the lattice, which has never been realized. Therefore, the study presented here can be taken as a general guideline to correlate the reactivity to the structure of the inorganic materials.
RESUMEN
Hybrid halide perovskites (HHPs), whose every branch generates intrusiveness, have been utilized in solar cells from a broader perspective. However, the inclusiveness of employing HHP as a photocatalyst is in its initial stage. This study mainly focuses on the unexpected utilization of, so far, undesirable material vacancy-ordered MA2SnBr6 quantum dots synthesized from MASnBr3 nanosheets. Here, the quantum confinement grounded a large blue shift in ultraviolet (UV) and photoluminescence (PL) spectra with a Stokes shift of 420 meV, where the band gap increase is observed as size decreases in MA2SnBr6. Remarkably, MA2SnBr6 exhibits air and moisture stability, better charge transfer, and high oxidation potential compared to MASnBr3. The first-principles-based atomistic computations reveal the strain relaxation in the Sn-Br framework that structurally stabilizes the MA2SnBr6 lattice. Furthermore, the direct band gap and strongly localized valence band edge give rise to a new potential photocatalyst MA2SnBr6 for efficient solar-driven C(sp3)âH activation of cyclohexane and toluene under ambient conditions.
RESUMEN
The critical photophysical properties of lead-free halide double perovskites (HDPs) must be substantially improved for various applications. In this regard, strain engineering is a powerful tool for enhancing optoelectronic performance with precise control. Here, we employ ab initio simulations to investigate the impact of mild compressive and tensile strains on the photophysics of Cs2AgB'X6 (B' = Sb, Bi; X = Cl, Br) perovskites. Depending on the pnictogen and halide atoms, the band gap and band edge positions of HDPs can be tuned to a significant extent by controlling the applied external strain. Cs2AgSbBr6 has the most substantial strain response under structural perturbations. The subtle electronic interactions among the participating orbitals and the band dispersion at the edge states are enhanced under compressive strain, reducing the carrier effective masses. The exciton binding energies for these Br-based HDPs are in the range 59-78 meV and weaken in the compressed lattices, suggesting improved free carrier generation. Overall, the study emphasizes the potential of lattice strain engineering to boost the photophysical properties of HDPs that can ultimately improve their optoelectronic performance.
