Construction of novel photocatalysts for efficient hydrogen evolution: The key role of natural halloysite nanotubes

Abstract

Hydrogen (H2) evolution by photocatalytic water splitting is a potential strategy to solve worldwide energy shortage. Sulfide nanocatalysts showed great potential for H2 evolution, but suffered from low charge separation efficiency and easy agglomeration. In this work, ZnIn2S4 (ZIS) nanoflowers were anchored onto the surface of halloysite nanotubes (HNTs) modified by ethylenediaminetetraacetic acid (EDTA). Photocatalyst 3ZnIn2S4-HNTs/EDTA3 (3ZIS-HNTs/E3) displayed the optimum H2 evolution rate of 10.4 mmol·g−1·h−1, being 3.4 times as that of the original ZIS. Moreover, 3ZIS-HNTs/E3 presented satisfied property in the photocatalytic hydrogenation reaction of 4-nitrophenol to produce 4-aminophenol. HNTs as substrates not only hindered the growth and agglomeration of ZIS, but also induced more S vacancies in ZIS. The production of Schottky junctions between ZIS and Pt, the high utilization of light energy in tubular HNTs, and the trapping effect of EDTA for photogenerated h+ were all favorable for enhancing the catalytic property. The density functional theory (DFT) calculations showed that 3ZIS-HNTs/E3 with more S vacancies had the lowest adsorption energy and the most appropriate ΔGH* for H* to enhance the H2 evolution efficiency, which was consistent with the experimental catalytic results. This study contributes a novel thought for synthesizing composites on the basis of natural minerals for taking part in and enhancing the catalytic performance.