New polymorph {\gamma}-CuWO4 inspired by {\gamma}-CuMoO4: experimental identification and theoretical verification

TL;DR

This paper reports the experimental discovery and theoretical validation of a new metastable polymorph of CuWO4, inspired by γ-CuMoO4, with potential implications for hydrogen gas sensor development.

Contribution

It introduces a novel metastable γ-CuWO4 phase, experimentally identified and theoretically confirmed as a local energy minimum, differing structurally from known stable phases.

Findings

The γ-CuWO4 phase is similar to γ-CuMoO4 in structure.

The phase is metastable and can be converted to stable form by annealing.

The formation is facilitated by kinetic factors and Cu-rich composition.

Abstract

In the context of our efforts to develop hydrogen gas sensors, two samples of ternary CuWO4 with the same crystalline structure have been prepared by two different non-equilibrium techniques. We show that the materials' structure is significantly different from the known stable one, and we identify that it is very similar to that of previously reported {\gamma}-CuMoO4. We use ab initio calculations to confirm that the newly identified phase, {\gamma}-CuWO4, represents a local energy minimum. We present very similar calculated and measured lattice constants and X-ray diffractograms. We make a case that the low-temperature formation of the metastable {\gamma}-CuWO4 phase is facilitated by easier kinetics and/or by Cu-rich composition of our samples, and we show that it converts to the stable phase after annealing to 600 {\deg}C.