Phase and sulfur vacancy engineering in cadmium sulfide for boosting hydrogen production from catalytic plastic waste photoconversion

TL;DR

This study develops a novel sulfur vacancy-rich, phase-engineered CdS photocatalyst that significantly enhances hydrogen production and plastic waste conversion efficiency, offering a promising approach for sustainable energy and waste management.

Contribution

It introduces a new phase and vacancy engineering strategy in CdS, achieving a 23-fold increase in catalytic performance without co-catalysts.

Findings

Sulfur vacancies act as active catalytic sites.

Hexagonal phase has a lower bandgap and narrows further with vacancies.

The new catalyst outperforms commercial CdS in hydrogen and plastic degradation.

Abstract

Cadmium sulfide (CdS) is a well-known low-bandgap photocatalyst, but its efficiency is often hindered by rapid photo-generated carrier recombination and a limited number of active catalytic sites. To overcome these challenges, this study introduces an efficient CdS photocatalyst through a novel strategy combining metastable-to-stable phase transformation and sulfur vacancy generation. This strategy integrates hydrothermal treatment and a high-pressure process to create sulfur vacancies, which serve as active catalytic sites, within a thermodynamically stable wurtzite (hexagonal) phase known for its superior photocatalytic properties. The resulting CdS photocatalyst demonstrates exceptional performance in photoreforming for hydrogen production and the conversion of polyethylene terephthalate (PET) plastic into valuable materials. Compared to commercial CdS catalysts, this new material shows a 23-fold increase in both hydrogen production and plastic degradation without the need for co-catalysts. Quenching experiments reveal that holes and hydroxyl radicals play crucial roles in the photoreforming process of this vacancy-rich CdS. First-principles calculations via density functional theory (DFT) indicate that the hexagonal phase possesses a lower bandgap and it exhibits further bandgap narrowing with the introduction of sulfur vacancies. These findings not only present an innovative approach to CdS processing but also highlight the critical role of sulfur vacancies as effective defects for the catalytic photoreforming of microplastics.