A DVD-MoS(2)/Ag(2)S/Ag Nanocomposite Thiol-Conjugated with Porphyrins for an Enhanced Light-Mediated Hydrogen Evolution Reaction

We have recently demonstrated in a previous work an appreciable photoelectrocatalytic (PEC) behavior towards hydrogen evolution reaction (HER) of a MoS(2)/Ag(2)S/Ag nanocomposite electrochemically deposited on a commercial writable Digital Versatile Disc (DVD), consisting therefore on an interesting strategy to convert a common waster product in an added-value material. Herein, we present the conjugation of this MoS(2)/Ag(2)S/Ag-DVD nanocomposite with thiol-terminated tetraphenylporphyrins, taking advantage of the grafting of thiol groups through covalent S-S bridges, for integrating the well-known porphyrins photoactivity into the nanocomposite. Moreover, we employ two thiol-terminated porphyrins with different hydrophilicity, demonstrating that they either suppress or improve the PEC-HER performance of the overall hybrid, as a function of the molecule polarity, sustaining the concept of a local proton relay. Actually, the active polar porphyrin—MoS(2)/Ag(2)S/Ag-DVD hybrid material presented, when illuminated, a better HER performance, compared to the pristine nanocomposite, since the porphyrin may inject photoelectrons in the conduction band of the semiconductors at the formed heterojunction, presenting also a stable operational behavior during overnight chopped light chronoamperometric measurement, thanks to the robust bond created.