Using Exciton/Trion Dynamics to Spatially Monitor the Catalytic Activities of MoS2 during the Hydrogen Evolution Reaction.

The adsorption and desorption of electrolyte ions strongly modulates the carrier density or carrier type on the surface of monolayer-MoS2 catalyst during the hydrogen evolution reaction (HER). The buildup of electrolyte ions onto the surface of monolayer MoS2 during the HER may also result in the formation of excitons and trions, similar to those observed in gate-controlled field-effect transistor devices. Using the distinct carrier relaxation dynamics of excitons and trions of monolayer MoS2 as sensitive descriptors, an in situ microcell-based scanning time-resolved liquid cell microscope is set up to simultaneously measure the bias-dependent exciton/trion dynamics and spatially map the catalytic activity of monolayer MoS2 during the HER. This operando probing technique used to monitor the interplay between exciton/trion dynamics and electrocatalytic activity for two-dimensional transition metal dichalcogenides provides an excellent platform to investigate the local carrier behaviors at the atomic layer/liquid electrolyte interfaces during electrocatalytic reaction.

Atomic-Layer Controlled Interfacial Band Engineering at Two-Dimensional Layered PtSe2/Si Heterojunctions for Efficient Photoelectrochemical Hydrogen Production.

Platinum diselenide (PtSe2) is a group-10 two-dimensional (2D) transition metal dichalcogenide that exhibits the most prominent atomic-layer-dependent electronic behavior of "semiconductor-to-semimetal" transition when going from monolayer to bulk form. This work demonstrates an efficient photoelectrochemical (PEC) conversion for direct solar-to-hydrogen (H2) production based on 2D layered PtSe2/Si heterojunction photocathodes. By systematically controlling the number of atomic layers of wafer-scale 2D PtSe2 films through chemical vapor deposition (CVD), the interfacial band alignments at the 2D layered PtSe2/Si heterojunctions can be appropriately engineered. The 2D PtSe2/p-Si heterojunction photocathode consisting of a PtSe2 thin film with a thickness of 2.2 nm (or 3 atomic layers) exhibits the optimized band alignment and delivers the best PEC performance for hydrogen production with a photocurrent density of -32.4 mA cm-2 at 0 V and an onset potential of 1 mA cm-2 at 0.29 V versus a reversible hydrogen electrode (RHE) after post-treatment. The wafer-scale atomic-layer controlled band engineering of 2D PtSe2 thin-film catalysts integrated with the Si light absorber provides an effective way in the renewable energy application for direct solar-to-hydrogen production.

Multilayer-graphene-stabilized lithium deposition for anode-Free lithium-metal batteries.

The will to circumvent capacity fading, Li dendrite formation, and low coulombic efficiency in anode-free Li-metal batteries (AFLMBs) requires a radical change in the science underpinning new materials discovery, battery design, and understanding electrode interfaces. Herein, a Cu current collector formed with ultrathin multilayer graphene grown via chemical vapor deposition (CVD) was used as an artificial layer to stabilize the electrode interface and sandwich-deposited Li with Cu. A multilayer graphene film's superior strength, chemical stability, and flexibility make it an excellent choice to modify a Cu electrode. Fabricating an anode bigger than the cathode improved the alignment of the electrodes during assembly, minimizing interfacial stress. Here, 19 mm electrodes when paired with a commercial LiFePO4 cathode (mass loading: ∼12 mg cm-2) delivered the first-cycle discharge capacities of 147 and 151 mA h g-1 for bare and multilayer-graphene-protected electrodes, respectively, which could alleviate the big hurdle (initial capacity loss) in anode-free batteries. After 100 round-trip cycles, bare Cu and multilayer-graphene-protected electrodes retained ∼46 and ∼61% of their initial capacities, respectively, in an ether-based electrolyte at the rate of 0.1 C.