Defect Rich Structure Activated 3D Palladium Catalyst for Methanol Oxidation Reaction

Abstract

AbstractControlling the structure and properties of catalysts through atomic arrangement is the source of producing a new generation of advanced catalysts. A highly active and stable catalyst in catalytic reactions strongly depends on an ideal arrangement structure of metal atoms. We demonstrated that the introduction of the defect‐rich structures, low coordination number (CN), and tensile strain in three‐dimensional (3D) urchin‐like palladium nanoparticles through chlorine bonded with sp‐C in graphdiyne (Pd‐UNs/Cl‐GDY) can regulate the arrangement of metal atoms in the palladium nanoparticles to form a special structure. In situ Fourier infrared spectroscopy (FTIR) and theoretical calculation results show that Pd‐UNs/Cl‐GDY catalyst is beneficial to the oxidation and removal of CO intermediates. The Pd‐UNs/Cl‐GDY for methanol oxidation reaction (MOR) that display high current density (363.6 mA cm−2) and mass activity (3.6 A mgPd−1), 12.0 and 10.9 times higher than Pd nanoparticles, respectively. The Pd‐UNs/Cl‐GDY catalyst also exhibited robust stability with still retained 95 % activity after 2000 cycles. A defects libraries of the face‐centered cubic and hexagonal close‐packed crystal catalysts (FH‐NPs) were synthesized by introducing chlorine in graphdiyne. Such defect‐rich structures, low CN, and tensile strain tailoring methods have opened up a new way for the catalytic reaction of MOR.