There is a diverse family of palladium selenide compounds,
including
semiconducting orthorhombic PdSe2 (O-PdSe2)
and monoclinic PdSe2 (M-PdSe2), which are unusual
among transition-metal dichalcogenides as they are composed of diselenide
dianions Se2
2–. Thus far, the solution
syntheses of materials with Se–Se bonds typically require the
in situ reduction of Se precursors. Here, we explore the use of electrochemically
precise reactions between Na2Se2 and a Pd2+ source, Na2PdCl4, as a solution-phase
route to selectively form different PdSe2 polymorphs in
the absence of surfactants. By altering the reactant molar ratios
and time, we map out a synthetic phase space diagram that shows how
to create a wide variety of palladium selenide phases. With increasing
Se2
2–/Pd2+ molar ratios, regions
are identified where Pd17Se15, M-PdSe2, and O-PdSe2 exist as the dominant or exclusive thermodynamic
product. Additionally, we discover Pd3Se10,
a superatomic crystal composed of Pd6Se20 cube-shaped
clusters held together by van der Waals forces, which forms as a kinetic
product under short reaction times. In total, the use of the diselenide
dianion precursor allows for the selective solution-phase synthesis
of M-PdSe2 or O-PdSe2, as well as the discovery
of a previously unreported palladium selenide phase.