Nanoparticles, thin films and temperature-dependent oxidation characteristics of metallic bismuth synthesized via solventless pyrolysis of bismuth(III) dithiolates: Polymorphism and photocatalytic dye degradation of bismuth sesquioxide
Xianglong Liu, Tingting Wang, Longhua Li, Junli Wang
Inorganic Chemistry Communications·2026
In this study, we report the preparation of Bi nanoparticles (NPs) and thin films via the solventless pyrolysis of bismuth(III) dithiolates (Bi2(S2CnH2n)3, n = 3, 4) at 160–220 °C, whose thermolysis features the absence of the precursor melting and finishes before the product (Bi metal) melting, and then we demonstrate their oxidation conversion to Bi2O3 NPs and thin films at different temperatures. The polymorphs and phase transitions of so-formed Bi2O3 are highly dependent on the oxidation temperature. Pure-phase β-Bi2O3 (tetragonal), formed by thermally oxidizing Bi NPs at 400 °C, will transform to α-Bi2O3 (monoclinic) by the traditionally known phase transition or β’-Bi2O3 by the c-oriented lattice thermal expansion as the oxidation temperature increases to 500 and 600 °C, which normally leads to an incomplete β → α transition and a mixed product of β’(β)/α phases. Compared to the β phase, the lattice-expanded variant β’-Bi2O3 is found to be stable at both high temperature (500–600 °C) and room temperature (RT) and to display a wide bandgap (∼3.0 eV), a narrow visible-light absorption range and thus relatively poor activity in RhB photodegradation. Moreover, Bi NPs are also found to be oxidized to bismuth oxycarbonate (Bi2O2CO3) at RT in the presence of H2O and CO2. This work opens a novel avenue to synthesize Bi and Bi2O3 NPs and thin films and presents new findings and insights regarding the phase regulation, polymorphism and photocatalytic performance of Bi2O3.