Molybdenum Disulfide Nanosheets Decorated with Platinum Nanoparticle as a High Active Electrocatalyst in Hydrogen Evolution Reaction

Electrochemical hydrogen evolution reaction (HER) refers to the process of generating hydrogen by splitting water molecules with applied external voltage on the active catalysts. HER reaction in the acidic medium can be studied by different mechanisms such as Volmer reaction (adsorption), Heyrovsky reaction (electrochemical desorption) or Tafel reaction (recombination). In this paper, facile hydrothermal methods are utilized to synthesis a high-performance metal-inorganic composite electrocatalyst, consisting of platinum nanoparticles (Pt) and molybdenum disulfide nanosheets (MoS2) with different platinum loading. The as-synthesized composite is further used as an electrocatalyst for HER. The as-synthesized Pt/Mo-90-modified glassy carbon electrode shows the best electrocatalytic performance than pure MoS2 nanosheets. It exhibits Pt-like performance with the lowest Tafel slope of 41 mV dec−1 and superior electrocatalytic stability in an acidic medium. According to this, the HER mechanism is related to the Volmer-Heyrovsky mechanism, where hydrogen adsorption and desorption occur in the two-step process. According to electrochemical impedance spectroscopy analysis, the presence of Pt nanoparticles enhanced the HER performance of the MoS2 nanosheets because of the increased number of charge carriers transport.

Grain-boundary-rich Pt nanoparticle assembly for catalytic hydrogen sensing at room temperature

We report a facile method of synthesizing grain-boundary(GB)-rich platinum nanoparticle assembly. GBs are formed between platinum nanoparticles during their random collision and attachment in solution driven by water electrolysis. The GB-rich nanoparticle assembly exhibits ~400-fold higher catalytic hydrogen oxidation rate than platinum nanoparticles before assembly, enabling catalytic hydrogen sensing at room temperature without external heating. Our sensor also demonstrates fast response/recovery (~7 s at >1% H2), nearly no signal variation during a 280-hour-long stability test, and high selectivity toward hydrogen over 36 interference gases. Furthermore, this sensor can be easily fabricated from commercial thermometers at a low cost (< $5 per unit). Theoretical calculation results reveal that the high performance of GB-rich platinum nanoparticle assembly arises from tensile strain at the GBs.

Examining Thermal Management Strategies for a Microcombustion Power Device

Microcombustion attracts interest with its promise of energy dense power generation for electronics. Yet, challenges remain to develop this technology further. Thermal management of heat losses is a known hurdle. Simultaneously, non-uniformities in heat release within the reaction regions also affect the device performance. Therefore a combination of thermal management strategies are necessary for further performance enhancements. Here, a bench top platinum nanoparticle based microcombustion reactor, coupled with thermoelectric generators is used. Methanol-air mixtures achieve room temperature ignition within a catalytic cartridge. In the current study, the reactor design is modified to incorporate two traditional thermal management strategies. By limiting enthalpic losses through the exhaust and reactor sides, using multi-pass preheating channels and heat recirculation, expected improvements are achieved. The combined strategies doubled the power output to 1.01 W when compared to the previous design. Furthermore, a preliminary study of catalyst distribution is presented to mitigate non-uniform catalytic activity within the substrate. To do this, tailored distribution of catalyst particles was investigated. This investigation shows a proof-of-concept to achieve localized control, thus management, over heat generation within substrates. By optimizing heat generation, a highly refined combustion-based portable power devices can be envisioned.

Twin boundary migration in an individual platinum nanocrystal during catalytic CO oxidation

At the nanoscale, elastic strain and crystal defects largely influence the properties and functionalities of materials. The ability to predict the structural evolution of catalytic nanocrystals during the reaction is of primary importance for catalyst design. However, to date, imaging and characterising the structure of defects inside a nanocrystal in three-dimensions and in situ during reaction has remained a challenge. We report here an unusual twin boundary migration process in a single platinum nanoparticle during CO oxidation using Bragg coherent diffraction imaging as the characterisation tool. Density functional theory calculations show that twin migration can be correlated with the relative change in the interfacial energies of the free surfaces exposed to CO. The x-ray technique also reveals particle reshaping during the reaction. In situ and non-invasive structural characterisation of defects during reaction opens new avenues for understanding defect behaviour in confined crystals and paves the way for strain and defect engineering.