Computer modeling of nanostructured photocatalyst for efficient hydrogen production from water

Project acronym

PI: Yuri Zhukovskii

Duration: 2016-2018


Solar energy has the capacity to fulfill global human energy demands in an environmentally and socially responsible manner, provided efficient, low-cost systems can be developed for its capture, conversion, and storage. Toward these ends, hydrogen fuel production with semiconductor photocatalysts is one very promising route for harvesting solar energy. Conventional photocatalyst electrodes such as titanium dioxide that use sunlight to split water and produce hydrogen can operate with high efficiency under ultraviolet irradiation, but it remains a challenge of primary importance to drive them with visible light. Engineering the electronic energy band structure of nanostructured semiconductor photoelectrodes through judicious control of their atomic composition is a promising route to increase visible light photo response. In this respect, before time-consuming and expensive experimental synthesis of nanophotocatalyst combined with spectroscopy and electrochemical measurements, thorough theoretical modeling of the mid-gap states and band edge positions of promising nanostructured photoelectrodes is unavoidable.

The main goal of our project is to elaborate a reliable approach for the prediction of the band structure of doped nanostructured photocatalysts through large-scale quantum chemical calculations based on density functional theory (DFT). Our approach will take advantage of fast prediction for defect-induced mid-gap energy levels by means of hybrid DFT, while time-dependent DFT allows the investigation of photoexcited electron transfer processes at the water/photocatalyst interface. The applicability of the proposed approach will not be limited to the rational design of photoelectrodes for redox reactions in water splitting, but also aids the molecular-level understanding of various aspects of interfacial charge transfer in molecular electronics, photovoltaics, electrolysis, catalysis, photochemistry, and photosynthesis.