Modulation of photocatalytic properties through counter-ion substitution: tuning the bandgaps of aromatic sulfonium octamolybdates for efficient photo-degradation of rhodamine B.

Modulating the photocatalytic properties of polyoxometalate-organic hybrids through counterion substitution is a less explored concept. In this study, a new series of aromatic sulfonium counterions (ASCs) having the general formula X-C 6 H 4 -S(Me 2 ) + , where X represents different functional substituents such as -H, -Cl, -Me, and -CHO at the para -position of the sulfonium moiety on a benzene ring, have been used for fine-tuning the optical bandgaps and adsorption properties of octamolybdate [Mo 8 O 26 ] 4- hybrids for photocatalytic dye degradation applications. The photodegradation of rhodamine B (RhB) is used as a model reaction, which follows pseudo-first-order kinetics exhibiting counterion-dependent degradation rate constants. The hybrid catalyst bearing a -CHO substituent on the ASC showed the lowest bandgap (2.91 eV) and the highest degradation rate constant (0.0141 min -1 ) of the series. A possible mechanism of photocatalytic dye degradation by hybrids involving the generation of reactive oxygen species (ROS) has been proposed, supported by radical scavenging studies. The intermediates formed during the photodegradation of RhB were analyzed and identified using electrospray ionization mass spectrometry (ESI-MS). The present study reveals a new strategy for tuning the photocatalytic properties of hybrids using differently functionalized ASCs and opens up new avenues for novel POM-hybrids as potential photocatalysts for environmental remediation applications.