Laser-induced pinpoint hydrogen evolution from benzene and water using metal free single-walled carbon nanotubes with high quantum yields

Metal-free photocatalytic hydrogen evolution occurred efficiently in benzene containing single-walled carbon nanotubes under laser irradiation at 532 nm with an extremely high turnover number of 2000000 and a high quantum yield of 130%. The rate of hydrogen evolution increased with increasing laser intensity to exhibit a fourth power dependence, suggesting that hydrogen was evolved via four-photon processes in which the coupling of two radical anions derived from benzene is the rate-determining step and the benzene radical anion is produced by electron transfer from benzene to the doubly excited state of single-walled carbon nanotubes, which requires two photons. Polymerisation of benzene was induced by the photogenerated C₆H₆^-, accompanied by hydrogen evolution, resulting in a leverage effect to increase the quantum yield of hydrogen evolution to well over the 25% expected for the four-photon process. Laser-induced hydrogen evolution also occurred in water containing single-walled carbon nanotubes. In contrast to the case of benzene, water was not oxidized but hydrogen evolution from water was accompanied by the multi-oxidation of single-walled carbon nanotubes. The yield of hydrogen based on one mole of single-walled carbon nanotubes with 1.4 nm diameter and 1-5 mm length was determined to be 2700000%, when oxidations of single-walled carbon nanotubes occurred to produce the polyhydroxylated product.