Phosphorus-Doped Single-Crystalline Quaternary Sulfide Nanobelts Enable Efficient Visible-Light Photocatalytic Hydrogen Evolution

Facilitating charge separation and transport of semiconductors is pivotal to improving their solar-to-hydrogen conversion efficiency. To this end, manipulating the charge dynamics via element doping has attracted much attentions. Here, we doped phosphorus (P) into two-dimensional (2D) single-crystalline quaternary sulfide (SCQS) nanobelts, enabling significantly enhanced photocatalytic H₂ production. By carefully studying the carrier dynamics after P doping, we found that the introduction of P leads to a narrowed band gap, inhibits the recombination of photogenerated carriers, and increases the electric conductivity, all of which contributed to their improved catalytic performance. Meanwhile, the inherited single-crystalline structure and exposed (0001) facet favors carrier transport and photocatalytic hydrogen production. It has been found that the P-doped Cu-Zn-In-S (CZIS) nanobelts exhibit a visible-light photocatalytic hydrogen production rate of 12.2 mmol h^-1 g^-1 without cocatalysts, which is 3.5-fold higher than that of pristine CZIS nanobelts. Moreover, the P doping strategy is proven to be common to other semiconductors, such as single-crystalline Cu-Zn-Ga-S (CZGS) nanobelts. Our work provides an efficient way to manipulate charge carriers and will help develop high-efficiency photocatalysts.