One pot microwave synthesis of highly stable AuPd@Pd supported core-shell nanoparticles.

A series of 1 wt% supported Au, Pd and AuPd nanoalloy catalysts were prepared via microwave assisted reduction of PdCl2 and HAuCl4 in a facile, one pot process. The resulting materials showed excellent activity for the direct synthesis of hydrogen peroxide from hydrogen and oxygen, with a synergistic effect observed on the addition of Au into a Pd catalyst. Detailed electron microscopy showed that the bimetallic particles exhibited a core-shell morphology, with an Au core surrounded by an Au-Pd shell, with a size between 10-20 nm. The presence of Au in the shell was confirmed by EDX studies, with corroborating data from XPS measurements showing a significant contribution of both Au and Pd in the spectra, with the Au signal increasing as the total Au content of the catalyst increased. No PdO was observed, suggesting a complete reduction of the metal chloride nanoparticles. Unlike similar catalysts prepared by sol-immobilisation methodology, the core-shell structures showed excellent stability during the hydrogen peroxide synthesis reaction, and no catalyst deactivation was observed over 4 reuse cycles. This is the first time the preparation of stable core-shell particles have been reported using microwave assisted reduction. The observation that these particles are core-shell, without the need of a complicated synthesis or high thermal treatment and form in just 15 minutes presents an exciting opportunity for this experimental technique.

Ordered clustering of single atomic Te vacancies in atomically thin PtTe2 promotes hydrogen evolution catalysis.

Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However, preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure, adsorption energy, and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized, ordered Te-SAV clusters, which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result, the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced, which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction.

Platinum Nanoparticle Inclusion into a Carbonized Polymer of Intrinsic Microporosity: Electrochemical Characteristics of a Catalyst for Electroless Hydrogen Peroxide Production.

The one-step vacuum carbonization synthesis of a platinum nano-catalyst embedded in a microporous heterocarbon (Pt@cPIM) is demonstrated. A nitrogen-rich polymer of an intrinsic microporosity (PIM) precursor is impregnated with PtCl62- to give (after vacuum carbonization at 700 °C) a nitrogen-containing heterocarbon with embedded Pt nanoparticles of typically 1⁻4 nm diameter (with some particles up to 20 nm diameter). The Brunauer-Emmett-Teller (BET) surface area of this hybrid material is 518 m² g-1 (with a cumulative pore volume of 1.1 cm³ g-1) consistent with the surface area of the corresponding platinum-free heterocarbon. In electrochemical experiments, the heterocarbon-embedded nano-platinum is observed as reactive towards hydrogen oxidation, but essentially non-reactive towards bigger molecules during methanol oxidation or during oxygen reduction. Therefore, oxygen reduction under electrochemical conditions is suggested to occur mainly via a 2-electron pathway on the outer carbon shell to give H2O2. Kinetic selectivity is confirmed in exploratory catalysis experiments in the presence of H2 gas (which is oxidized on Pt) and O2 gas (which is reduced on the heterocarbon surface) to result in the direct formation of H2O2.