Hollow-shell hybrids with regulatable microelectronic structures for boosting photocatalytic H2 evolution via water splitting and isopropanol oxidation under visible light

Abstract

Herein, a series of heteroatoms doped-NMIL(Ti)/Cd0.5Zn0.5S are synthesized, where the Cd0.5Zn0.5S (CZS) uniformly grows in situ on the surface of NMIL(Ti) encapsulating ultra-trace Cu/Fe/Co atoms to form the mesoporous hollow-shell structures. The microelectronic structures of photocatalysts can be modulated via regulatable band potential of Cu/Fe/Co-doped NMIL(Ti) due to the intense interaction between heteroatoms and −NH2 groups. Moreover, the Ti3+-oxygen vacancy pairs as the photogenerated electron library and the heterojunction effectively facilitate the special separation and migration of carriers. The optimal hybrid (Cu1%-NMIL(Ti)/CZS) has a photocatalytic hydrogen evolution rate of 251.2 μmol g−1 (12,560.12 μmol g−1 h−1) in 0.35 M Na2S/0.25 M Na2SO3 under visible light, which is 4.34 and 1.74 times higher than that of CZS and NMIL(Ti)/CZS, respectively. Moreover, the H2 yield reaches 29,860 μmol g−1 h−1 in 0.35 M Na2S/0.25 M Na2SO3/2 M isopropanol system, which is 2.38 times than before, displaying that isopropanol oxidation not only consumes photo-holes to inhibit carries recombination, but also provides H+ to participate in H2 production. This work provides a new insight for developing a high-efficiency photocatalytic H2 evolution system.