Dihalogenation of alkenes to the high-added value vicinal dihalides is a prominent process in modern synthetic chemistry. However, their effective conversion still requires the use of expensive and hazardous agents, sacrificial half-reaction coupling or primary energy input. Here, we show a photocatalytically assisted shuttle (p-shuttle) strategy for redox-neutral and reversible vicinal dihalogenation using low-cost and stable 1,2-dihaloethane under visible light illumination. Energetic hot electrons from metal-halide perovskite QDs enable the challenging photocatalytic reactions. Ultrafast laser transient absorption spectroscopy have unveiled the energy matching of the hot electrons with the high reduction potential of 1,2-dihaloethane, via two consecutive photoexcitation process. Powered by the sustainable energy as the only energy input, our new catalytic system using metal-halide perovskite QDs for dibromination, dichlorination and even unexplored hetero-dihalogenation, shows good tolerance with a wide range of alkenes at room temperature. In contrast to homogeneous photocatalysts, chalcogenide QDs and other semiconductor catalysts, perovskite QDs deliver previously unattainable performance in photoredox shuttle vicinal dihalogenation with the turnover number over 120,000. This work provides new opportunities in visible-light-driven heterogeneous catalysis for unlocking novel chemical transformations.

Self-assembled InAs quantum dots (QDs) have been fabricated by depositing 1.6, 1.8, 2.0 and 2.5 monolayer (ML) InAs on surfaces of the undoped-n+ (UN+) type GaAs structure. Room temperature contactless electroreflectance (CER) was employed to study the built-in electric field and the surface Fermi level pinning of these QD-covered UN+ GaAs samples. The CER results show that 1.6 ML InAs QDs on GaAs do not modify the Fermi level, whereas for samples with more than 1.6 ML InAs coverage, the surface Fermi level is moved to the valence band maximum of GaAs by about 70 meV (which is independent of the InAs deposition thickness) compared to bare GaAs. It is concluded that the modification of InAs coverage on the Fermi level on the GaAs surface is due to the QDs, rather than to the wetting layer.