Facile and General Method to Synthesize Pt-Based High-Entropy-Alloy Nanoparticles

Pt-based high-entropy-alloy nanoparticles (HEA-NPs) have excellent physical and chemical properties due to the diversity of composition, complexity of surface structure, high mixing entropy, and properties of nanoscale, and they are used in a wide range of catalytic applications such as catalytic ammoxidation, the electrolysis of water to produce hydrogen, CO₂/CO reduction, and ethanol/methanol oxidation reaction. However, offering a facile, low-cost, and large-scale method for preparing Pt-based HEA-NPs still faces great challenges. In this study, we employed a spray drying technique combined with thermal decomposition reduction (SD-TDR) method to synthesize a single-phase solid solution from binary nanoparticles to denary Pt-based HEA-NPs containing 10 dissimilar elements loaded on carbon supports in an H₂ atmosphere with a moderate heating rate (3 °C/min), thermal decomposition temperature (300-850 °C), duration time (30 min), and low cooling rate (5-10 °C/min). The Pt autocatalytic behavior was found and investigated, confirming that Pt element could decrease the reduction temperature of other metals via autocatalytic behavior. Therefore, using the feature of Pt autocatalytic behavior, we have achieved Pt-based HEA-NPs at a minimum temperature of 300 °C. We not only prepared a series of Pt-based HEA-NPs with targetable ingredient, size, and phase using the SD-TDR method but also proved the expandability of the SD-TDR technique by synthesizing Pt-based HEA-NPs loaded on different supports. Moreover, we investigated methanol oxidation reaction (MOR) on as-synthesized senary PtCoCuRuFeNi HEA-NPs, which presented superior electrocatalytic performance over commercial Pt/C catalyst.