Harmonious Heterointerfaces Formed on 2D-Pt Nanodendrites by Facet-Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction.

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D-Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer (e-Pd or e-Ni) was exclusively formed on the flat {110} surface of 2D-Pt, while a non-epitaxial Pd or Ni layer (n-Pd or n-Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D-2D interfaced e-Pd deposition and faster water dissociation on the edge-located n-Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n-Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

Crystal Facet-Manipulated 2D Pt Nanodendrites to Achieve an Intimate Heterointerface for Hydrogen Evolution Reactions.

Despite the Pt-catalyzed alkaline hydrogen evolution reaction (HER) progressing via oxophilic metal-hydroxide surface hybridization, maximizing Pt reactivity alongside operational stability is still unsatisfactory due to the lack of well-designed and optimized interface structures. Producing atomically flat two-dimensional Pt nanodendrites (2D-PtNDs) through our 2D nanospace-confined synthesis strategy, this study tackles the insufficient interfacial contact effect during HER catalysis by realizing an area-maximized and firmly bound lateral heterointerface with NiFe-layered double hydroxide (LDH). The well-oriented {110} crystal surface exposure of Pt promotes electronic interplay that bestows strong LDH binding. The charge-relocated interfacial bond in 2D-PtND/LDH accelerates the hydrogen generation steps and achieves nearly the highest reported Pt mass activity enhancement (∼11.2 times greater than 20 wt % Pt/C) and significantly improved long-term operational stability. This work uncovers the importance of the shape and facet of Pt to create heterointerfaces that provide catalytic synergy for efficient hydrogen production.

Visualization of Transition Metal Decoration on h-BN Surface.

Functional h-BN (hexagonal boron nitride) has been prepared via the incorporation of transition metal (TM) impurities like nanoparticles and single atoms. Herein, scanning transmission electron microscopy (STEM) combined with density functional theory (DFT) was employed to study Ta-, Co-, Ni-, and Ir-decorated h-BN monolayers to provide an overview of their preferential site occupancies and morphological evolutions on h-BN. Ta, Ni, Ir, and Co single atoms are all positioned on the nitrogen of h-BN; however DFT predicts the occupancy site can vary with their spin state. In terms of microstructural evolution, Co, Ni, and Ir atoms form 3D nanoclusters while Ta atoms are well dispersed and thus the single Ta atom can be decorated on h-BN. This study highlights on TM/h-BN interaction dynamics and presents an avenue for designing nanostructures for electrocatalytic application.

Resistive Switching in Few-Layer Hexagonal Boron Nitride Mediated by Defects and Interfacial Charge Transfer.

We present resistive switching (RS) behavior of few-layer hexagonal boron nitride (h-BN) mediated by defects and interfacial charge transfer. Few-layer h-BN is grown by metal-organic chemical vapor deposition and used as active RS medium in Ti/h-BN/Au structure, exhibiting clear bipolar RS behavior and fast switching characteristics about ∼25 ns without an initial electroforming process. Systematic investigation on microstructural and chemical characteristics of the h-BN reveals that there are structural defects such as homoelemental B-B bonds at grain boundaries and nitrogen vacancies, which can provide preferential pathways for the penetration of Tix+ ions through the h-BN film. In addition, the interfacial charge transfer from Ti to the h-BN is observed by in situ X-ray photoelectron spectroscopy. We suggest that the attractive Coulomb interaction between positively charged Tix+ ions and the negatively charged h-BN surface as a result of the interfacial charge transfer facilitates the migration of Tix+ ions at the Ti/h-BN interface, leading to the facile formation of conductive filaments. We believe that these findings can improve our understanding of the fundamental mechanisms involved in RS behavior of h-BN and contribute a significant step for the future development of h-BN-based nonvolatile memory applications.

Epitaxial van der Waals Contacts between Transition-Metal Dichalcogenide Monolayer Polymorphs.

We have achieved heteroepitaxial stacking of a van der Waals ( vdW) monolayer metal, 1T'-WTe2, and a semiconductor, 2H-WSe2, in which a distinctively low contact barrier was established across a clean epitaxial vdW gap. Our epitaxial 1T'-WTe2 films were identified as a semimetal by low temperature transport and showed the robust breakdown current density of 5.0 × 107 A/cm2. In comparison with a series of planar metal contacts, our epitaxial vdW contact was identified to possess intrinsic Schottky barrier heights below 100 meV for both electron and hole injections, contributing to superior ambipolar field-effect transistor (FET) characteristics, i.e., higher FET mobilities and higher on-off current ratios at smaller threshold gate voltages. We discuss our observations around the critical roles of the epitaxial vdW heterointerfaces, such as incommensurate stacking sequences and absence of extrinsic interfacial defects that are inaccessible by other contact methods.