Unique Optoelectronic Structure and Photoreduction Properties of Sulfur-Doped Lead Chromates Explaining Their Instability in Paintings.

Chrome yellow refers to a group of synthetic inorganic pigments that became popular as an artist's material from the second quarter of the 19th century. The color of the pigment, in which the chromate ion acts as a chromophore, is related to its chemical composition (PbCr1-xSxO4, with 0 ≤ x ≤ 0.8) and crystalline structure (monoclinic/orthorhombic). Their shades range from the yellow-orange to the paler yellow tones with increasing sulfate amount. These pigments show remarkable signs of degradation after limited time periods. Pure PbCrO4 (crocoite in its natural form) has a deep yellow color and is relatively stable, while the coprecipitate with lead sulfate (PbCr1-xSxO4) has a paler shade and seems to degrade faster. This degradation is assumed to be related to the reduction of Cr(VI) to Cr(III). We show that, when the the sulfur(S)-content in chrome yellow increases, the band gap increases. Typically, when increasing the band gap, one might assume that a decrease in photoactivity is the result. However, the photoactivity relative to the Cr content and, thus, Cr reduction of sulfur-rich PbCr1-xSxO4 is found to be much higher compared to the sulfur-poor or nondoped lead chromates. This discrepancy can be explained by the evolution of the crystal and electronic structure as a function of the sulfur content: first-principles density functional theory calculations show that both the absorption coefficient and reflection coefficients of the lead chromates change as a result of the sulfate doping in such a way that the generation of electron-hole pairs under illumination relative to the total Cr content increases. These changes in the material properties explain why paler shade yellow colors of this pigment are more prone to discoloration. The electronic structure calculations also demonstrate that lead chromate and its coprecipitates are p-type semiconductors, which explains the observed reduction reaction. Because understanding this phenomenon is valuable in the field of cultural heritage, this study is the first joint action of photoelectrochemical measurements and first-principles calculations to approve the higher tendency of sulfur-rich lead chromates to darken.