Spectroscopic and electrochemical examination of the dark and photo-catalysed redox reactions that occur at the interface between solidα-[Hex_4N]_4(S_2Mo_(18)O_(62)]，solid triphenylphosphine and water

摘要

Solid α-[Hex_4N]_4(S_2Mo_(18)O_(62)] was found to be reduced by solid triphenylphosphine when the two species were ground together as powders and left for periods of several days in the presence of atmospheric water vapour. Electrospray mass spectrometry confirmed that the final product formed by oxidation of the phosphine was PPh_3O, while experiments in the presence of H_2~(17)O demonstrated that the oxygen source was atmospheric water vapour rather than [S_2Mo_(18)O_(62)]~(4-). Voltammetry and UV/visible spectroscopy of samples of reacted solids dissolved in MeCN imply that the two-electron, two-proton reduced species [Hex_4N]_4[H_2S_2Mo_(18)O_(62)] was the major product formed upon reaction of an equimolar solid mixture of PPh_3 and [Hex_4N]_4[S_2Mo_(18)O_(62)]. The rate of this process is accelerated by irradiation with 300-400 nm light, corresponding to the eaelength of an aborption band of [S_2Mo_(18)O_(62)]~(4-). When PPh_3 was in excess, three-electron and four-electron reduced forms of [S_2Mo_(18)O_(62)]~(4-) were detected by EPR spectroscopy and voltammetry, respectively. Direct evidence for the photooxidation of PPh_3 was obtained through solid-state photovoltammetric experiments in which a phototransient response for the oxidation of reduced forms of [S_2Mo_(18)O_(62)]~(4-) was recorded for solid state mixtures which were mechanically attached to a pyrolytic graphite electrode surface in contact with an aqueous medium.