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

Combined hybDFT and GW study reveals surface properties and optoelectronic behaviour of Y2Ti2O5S2 for green hydrogen production

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

[Image: see text] 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 La(5)Ti(2)AgS(5)O(7) and La(5)Ti(2)CuS(5)O(7)—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)S(6–x) and tetragonal MS(4) 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 La(5)Ti(2)AgS(5)O(7) have band edge positions suitable for hydrogen evolution; however, the small overpotentials on the largest facets likely decrease the photocatalytic activity. In La(5)Ti(2)CuS(5)O(7), 72% of the surface area can support oxygen evolution thermodynamically and kinetically. Based on their similar electronic structures, La(5)Ti(2)AgS(5)O(7) and La(5)Ti(2)CuS(5)O(7) could be effectively employed in Z-scheme photocatalytic water splitting

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

Mixed Anion Systems for Green Hydrogen Generation

Hydrogen is the key element behind the global food supply due to its role in nitrogen fixing for ammonia fertiliser production. Currently, over 96% of hydrogen used worldwide is produced in processes associated with substantial carbon footprints like steam methane reforming or coal gasification. In addition to hydrocarbons, another major source of hydrogen on Earth is water. Hydrogen can be sustainably produced using photocatalytic water splitting – a biomimicry of photosynthesis – where water is reduced over a photocatalyst using energy derived from light. This photocatalytic water splitting effect was first characterised on TiO2 in the 1970s and in the 50 years since, TiO2 and other d0 metal oxides have been extensively studied. However, their electronic band structure with band gaps in excess of 3 eV and low-lying oxygen-dominated valence band prevents efficient hydrogen evolution from water under visible light. Mixed anion compounds (ON, OX, OCh) opened a new paradigm in the search for better photocatalysts, as the second anion can be engineered to have a higher-lying p orbital to optimise the band edge positions for water redox. To this effect, in this thesis the optoelectronic and surface properties of three known oxysulphide photocatalysts Y2Ti2O5S2, La5Ti2CuS5O7 and La5Ti2AgS5O7 are investigated using first principles density functional theory (DFT) calculations. As photocatalysis is heavily dictated by surface phenomena, special attention is paid to the simulations of different surfaces by establishing a complete workflow for surface simulations in DFT. The last part of this thesis delves into computational prediction of new oxychalcogenide photocatalysts from the Ln2M2O5Ch2 family, assessing the materials stability and also suitability for applications beyond photocatalysis

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