A colloidal heterostructured quantum dot sensitized carbon nanotube–TiO2 hybrid photoanode for high efficiency hydrogen generation

Abstract

Solar-driven photoelectrochemical (PEC) hydrogen (H₂) generation is a promising approach to harvest solar energy for the production of a clean chemical fuel. However, the low photon-to-fuel conversion efficiency and long-term stability of PEC devices are major challenges to be addressed to enable large-scale commercialization. Here we report a simple, fast and cost-effective approach to fabricate high efficiency and stable PEC devices for H₂ generation, by fabricating a hybrid photoanode obtained by incorporating small amounts of multiwall carbon nanotubes (MWCNTs) into a TiO₂ mesoporous film and sensitizing with colloidal heterostructured CdSe/(CdSe_xS_1−x)₅/(CdS)₂ quantum dots (QDs). The latter were specially designed to accelerate the exciton separation through a band engineering approach. The PEC devices based on the TiO₂/QD–MWCNT (T/Q–M) hybrid photoanode with an optimized amount of MWCNTs (0.015 wt%) yield a saturated photocurrent density of 15.90 mA cm⁻² (at 1.0 V_RHE) under one sun illumination (AM 1.5G, 100 mW cm⁻²), which is 40% higher than that of the reference device based on TiO₂/QD (T/Q) photoanodes. This is attributed to a synergistic effect of the promising optoelectronic properties of the colloidal heterostructured QDs and improved electron transport (reduced charge transfer resistance) within the TiO₂–MWCNT hybrid anodes enabled by the directional path of MWCNTs for the photo-injected electrons towards FTO. Furthermore, the PEC device based on the T/Q–M hybrid photoanode is more stable (∼19% loss of its initial photocurrent density) when compared with the T/Q photoanode (∼35% loss) after two hours of continuous one sun illumination. Our results provide fundamental insights and a different approach to improve the efficiency and long-term stability of PEC devices and represent an essential step towards the commercialization of this emerging solar-to-fuel conversion technology.