Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal “onsite electrostatic polarization” mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.

Monolayer transition metal dichalcogenides (TMDs) possess large second-order nonlinear responses due to the broken inversion symmetry, which can extend their intriguing applications in nonlinear nanophotonics and optoelectronics. However, the atomic thickness of monolayer TMDs severely decreases the interaction length with free light with respect to bulk materials, leading to rather low second-harmonic generation (SHG) conversion efficiency. Here, we demonstrate a hybrid structure consisting of a monolayer MoS2 on a suspended perforated silver film, on which the SHG signal emitted from the monolayer MoS2 is enhanced by more than three orders of magnitude at room temperature. The pronounced SHG enhancement is attributed to the distinct electric field amplification nearby the nanoholes, which is induced by the symmetric surface plasmon polaritons (SPPs) existing in the ultrathin suspended silver grating. Our results reported here may establish the substrate-free engineering of nonlinear optical effects via plasmonic nanostructures on demand.

Plasmonic nanostructures have garnered tremendous interest in enhanced light–matter interaction because of their unique capability of extreme field confinement in nanoscale, especially beneficial for boosting the photoluminescence (PL) signals of weak light–matter interaction materials such as transition metal dichalcogenides atomic crystals. Here we report the surface plasmon polariton (SPP)-assisted PL enhancement of MoS2 monolayer via a suspended periodic metallic (SPM) structure. Without involving metallic nanoparticle–based plasmonic geometries, the SPM structure can enable more than two orders of magnitude PL enhancement. Systematic analysis unravels the underlying physics of the pronounced enhancement to two primary plasmonic effects: concentrated local field of SPP enabled excitation rate increment (45.2) as well as the quantum yield amplification (5.4 times) by the SPM nanostructure, overwhelming most of the nanoparticle-based geometries reported thus far. Our results provide a powerful way to boost two-dimensional exciton emission by plasmonic effects which may shed light on the on-chip photonic integration of 2D materials.