Facet-Dependent Photoinduced Transformation of Cadmium Sulfide (CdS) Nanoparticles

Microbial-mediated transformation of anthropogenic Cd2+ controls its distribution, bioavailability, and potential risks. However, the processes readily form CdS nanoparticles (CdS-NPs), which exhibit dissolution behavior different from that of larger sized particles. Here, we investigated the effects of morphologies and facets of CdS-NPs on their photoinduced dissolution. Three CdS-NPs, CdS-sphere, CdS-rod, and CdS-sheet, and one nanosized biogenic CdS (Bio-CdS) were synthesized with different dominant facets of {101}, {100}, {001}, and {111} and thus distinct surface chemistry. As explored by HRTEM, EPR, and DFT calculations, photogenerated e(-)/h(+) pairs were more likely to generate on CdS-sheet surfaces due to higher surface energies and a narrower band gap, facilitating the formation of center dot OH and thereby faster dissolution (kobs = 6.126-6.261 x 10(-2) h(-1)). The wider band gaps of CdS-sphere and CdS-rod caused less formation of O-2(center dot-) and center dot OH, leading to slower oxidative dissolutions (kobs = 0.090-0.123 and 2.174-3.038 x 10(-2) h(-1), respectively). Given the similar surface energy as that of CdS-sheet, the dissolution rate of Bio-CdS was close to that of CdS-rod and CdS-sheet, which was 1.6-3.5 times faster than that of larger sized CdS, posing higher environmental risks than thought. Altogether, this work revealed the facet effects on the dissolution of CdS-NPs, manifesting a deeper understanding of metal sulfides' environmental behaviors.