Exploring PtSO₄ and PdSO₄ phases: an evolutionary algorithm based investigation

Metal sulfate formation is one of the major challenges to the emissions aftertreatment catalysts. Unlike the incredibly sulfation prone nature of Pd to form PdSO$_4$, no experimental evidence exits for the PtSO$_4$ formation. Given the mystery of nonexistence of the PtSO$_4$, we explore the PtSO$_4$ using a combined approach of evolutionary algorithm based search technique and quantum mechanical computations. Experimentally known PdSO$_4$ is considered for the comparison and validation of our results. We predict many possible low-energy phases of the PtSO$_4$ and PdSO$_4$ at 0K, which are further investigated under wide range of temperature-pressure conditions. An entirely new low-energy (tetragonal $P4_2/m$) structure of the PtSO$_4$ and PdSO$_4$ is predicted, which appears to be the most stable phase of the PtSO$_4$ and a competing phase of the experimentally known monoclinic $C_2/c$ phase of PdSO$_4$. Phase stability at finite temperature is further examined and verified by free energy calculations of sulfates towards their possible decomposition products. Finally, temperature-pressure phase diagrams are computationally established for both PtSO$_4$ and PdSO$_4$.