English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Plus monthly

Global: Zendy Tools annual

Global: Zendy Tools monthly

Global: Zendy Free Plan

Preparation of solid solutions represents an effective means to improve thephotocatalytic properties of semiconductor-based materials. Nevertheless, theeffects of site-occupancy disorder on the mixing stability and electronicproperties of the resulting compounds are difficult to predict and consequentlymany experimental trials may be required before achieving enhancedphotocatalytic activity. Here, we employ first-principles methods based ondensity functional theory to estimate the mixing free energy and the structuraland electronic properties of (GaP)$_{x}$(ZnS)$_{1-x}$ solid solutions, arepresentative semiconductor-based optoelectronic material. Our method relieson a multi-configurational supercell approach that takes into account theconfigurational and vibrational contributions to the free energy. Phasecompetition among the zinc-blende and wurtzite polymorphs is also considered.We demonstrate overall excellent agreement with the available experimentaldata: (1)~zinc-blende emerges as the energetically most favorable phase,(2)~the solid solution energy band gap lies within the $2$--$3$~eV range forall compositions, and (3)~the energy band gap of the solid solution is directfor compositions $x \le 75$\%. We find that at ambient conditions most(GaP)$_{x}$(ZnS)$_{1-x}$ solid solutions are slightly unstable againstdecomposition into GaP- and ZnS-rich regions. Nevertheless, compositions $x\approx 25$, 50, and 75\% render robust metastable states that owing to theirfavorable energy band gaps and band levels relative to vacuum are promisinghydrogen evolution photocatalysts for water splitting under visible light. Theemployed theoretical approach provides valuable insights into thephysicochemical properties of potential solid-solution photocatalysts andoffers useful guides for their experimental realization.

Mixing thermodynamics and photocatalytic properties of GaP-ZnS solid solutions