The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions.
Bibliographical noteFunding Information:
A.W., K.T.B., and C.H.H. are supported by the Royal Society, the EPSRC (Grant EP/M009580/1) and the ERC (Grant 277757). D.O.S. and A.W. acknowledge membership of the Materials Design Network. A.M.G. acknowledges Diamond Light Source for the cosponsorship of a studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1). GAO is a Government of Canada Research Chair in Materials Chemistry and Nanochemistry. He deeply appreciates the strong and sustained support of his research from the Natural Sciences and Engineering Research Council of Canada. This work benefitted from access to the ARCHER, through the UK High Performance Computing Consortium, which is funded by EPSRC Grant EP/L000202, and access to XSEDE Grant Number AC-1053575.
All Science Journal Classification (ASJC) codes
- Chemical Engineering(all)
- Materials Chemistry