Understanding the electronic structure of Y2Ti2O5S2 for green hydrogen production: a hybrid-DFT and GW study.

Utilising photocatalytic water splitting to produce green hydrogen is the key to reducing the carbon footprint of this crucial chemical feedstock. In this study, density functional theory (DFT) is employed to gain insights into the photocatalytic performance of an up-and-coming photocatalyst Y2Ti2O5S2 from first principles. Eleven non-polar clean surfaces are evaluated at the generalised gradient approximation level to obtain a plate-like Wulff shape that agrees well with the experimental data. The (001), (101) and (211) surfaces are considered further at hybrid-DFT level to determine their band alignments with respect to vacuum. The large band offset between the basal (001) and side (101) and (211) surfaces confirms experimentally observed spatial separation of hydrogen and oxygen evolution facets. Furthermore, relevant optoelectronic bulk properties were established using a combination of hybrid-DFT and many-body perturbation theory. The optical absorption of Y2Ti2O5S2 weakly onsets due to dipole-forbidden transitions, and hybrid Wannier-Mott/Frenkel excitonic behaviour is predicted to occur due to the two-dimensional electronic structure, with an exciton binding energy of 0.4 eV.

Y2Ti2O5S2 - a promising n-type oxysulphide for thermoelectric applications.

Thermoelectric materials offer an unambiguous solution to the ever-increasing global demand for energy by harnessing the Seebeck effect to convert waste heat to electrical energy. Mixed-anion materials are ideal candidate thermoelectric materials due to their thermal stability and potential for "phonon-glass, electron-crystal" behaviour. In this study, we use density-functional theory (DFT) calculations to investigate Y2Ti2O5S2, a cation-deficient Ruddlesden-Popper system, as a potential thermoelectric. We use hybrid DFT to calculate the electronic structure and band alignment, which indicate a preference for n-type doping with highly anisotropic in-plane and the out-of-plane charge-carrier mobilities as a result of the anisotropy in the crystal structure. We compute phonon spectra and calculate the lattice thermal conductivity within the single-mode relaxation-time approximation using lifetimes obtained by considering three-phonon interactions. We also calculate the transport properties using the momentum relaxation-time approximation to solve the electronic Boltzmann transport equations. The predicted transport properties and lattice thermal conductivity suggest a maximum in-plane ZT of 1.18 at 1000 K with a carrier concentration of 2.37 × 1020 cm-3. Finally, we discuss further the origins of the low lattice thermal conductivity, in particular exploring the possibility of nanostructuring to lower the phonon mean free path, reduce the thermal conductivity, and further enhance the ZT. Given the experimentally-evidenced high thermal stability and the favourable band alignment found in this work, Y2Ti2O5S2 has the potential to be a promising high-temperature n-type thermoelectric.

Understanding the Photocatalytic Activity of La5Ti2AgS5O7 and La5Ti2CuS5O7 for Green Hydrogen Production: Computational Insights.

Green production of hydrogen is possible with photocatalytic water splitting, where hydrogen is produced while water is reduced by using energy derived from light. In this study, density functional theory (DFT) is employed to gain insights into the photocatalytic performance of La5Ti2AgS5O7 and La5Ti2CuS5O7-two emerging candidate materials for water splitting. The electronic structure of both bulk materials was calculated by using hybrid DFT, which indicated the band gaps and charge carrier effective masses are suitable for photocatalytic water splitting. Notably, the unique one-dimensional octahedral TiO x S6-x and tetragonal MS4 channels formed provide a structural separation for photoexcited charge carriers which should inhibit charge recombination. Band alignments of surfaces that appear on the Wulff constructions of 12 nonpolar symmetric surface slabs were calculated by using hybrid DFT for each of the materials. All surfaces of La5Ti2AgS5O7 have band edge positions suitable for hydrogen evolution; however, the small overpotentials on the largest facets likely decrease the photocatalytic activity. In La5Ti2CuS5O7, 72% of the surface area can support oxygen evolution thermodynamically and kinetically. Based on their similar electronic structures, La5Ti2AgS5O7 and La5Ti2CuS5O7 could be effectively employed in Z-scheme photocatalytic water splitting.