Composition optimized trimetallic PtNiRu dendritic nanostructures as I versatile and active electrocatalysts for alcohol oxidation

Platinum-based nano crystals are the most effective electrocatalysts for accelerati ng the chemical tran sformatio ns on the anode in direct alcohol fuel cells. To facilitate practical applications and overcome the drawbacks of diverse alcohols, it is significant to develop electrocatalysts with high activities and a wide fuel flexibility. Here, we demonstrate a practicable solution method for fabricating composition tun able trimetallic PtNiRu den dritic nano structures (DNSs) which can serve as versatile and active catalysts for electrooxidatio n of a variety of liquid alcohols. A series of trimetallic DNSs with tun able Pt/Ni/Ru atomic ratios were successfully syn thesized by simply adjusti ng the feeding of precursors. Detailed electrochemical test indicates that, among other compositions, the Pt66Ni27Ru7 DNSs present much superior electroactivity in catalyzing electrooxidation of liquid alcohols in acidic mediums. Specifically, the mass activity and specific activity on the Pt66Ni27Ru7 DNSs, for electrooxidation of methanol, ethanol, and ethylene glycol, are 4.57 and 4.34 times, 3.55 and 3.42 times, and 2.37 and 2.28 times that of the commercial Pt black, respectively. X-ray photoelectron spectroscopy and CO stripping studies reveal the adsorption of CO on these PtNiRu DNSs is much weaker than on pure Pt. Meanwhile, the surface Ru sites can provide neighbouring -OH groups to facilitate the oxidati on and removal of the adsorbed in termediates (-CO) on the surface Pt sites, effectively improvi ng the CO tolera nee of the catalysts. The PtNiRu DNSs also show effectively boosted capacity for breaking the C-C bond in C2-alcohols, showing great potential for fuel-flexible fuel cell applications.

In situ surface-doped PtNiCoRh nanocrystals promote electrooxidation of C_(1) fuels

Heteroatom-doped Pt-based nanocrystals have generated considerable interest and hold great prospects in heterocatalysis. However, engineering the superficial atomic configurations of these nanocrystals via in situ surface doping remains exceedingly challenging. Herein, we propose a onepot, in situ surface doping chemical synthesis protocol to prepare quatermetallic Pt Ni Co Rh dendritic nanocrystals as versatile and active catalysts for the electrooxidation of C_(1) fuels. Leveraging the selective coordination effect between ascorbic acid and Rh^(3+)ions, the doping of trace Rh atoms can be guided specifically at the near-surface of Pt Ni Co Rh nanocatalysts. Electrocatalytic tests indicate that Pt_(67)Ni_(16)Co_(16)Rh_(1) nanocrystals with in situ trace Rh-doped surface exhibit substantially enhanced activity, durability, and CO tolerance for the electrooxidation of methanol, formaldehyde, and formic acid. In situ Fourier transform infrared spectroscopy provides molecular-level insight into the exceptional performance of these nanocatalysts. The surface incorporation of anticorrosive Rh atoms enables the transfer of CO intermediates from the atop Pt sites to the bridged Rh–Pt surface sites,thereby facilitating the elimination of these poisoning species from the catalyst surface. This study presents an effective in situ surface doping strategy which can enable the design of more atom-economic heterocatalysts.