Facile synthesis of CoSi alloy with rich vacancy for base- and solvent-free aerobic oxidation of aromatic alcohols

Rational design and green synthesis of low-cost and robust catalysts efficient for the selective oxidation of various alcohols are full of challenges. Herein, we report a fast and solvent-free arc-melting (AM) method to controllably synthesize semimetal CoSi alloy (abbreviated as AM-CoSi) that is efficient for the base- and solvent-free oxidation of six types of aromatic alcohols. X-ray absorption fine structure (XAFS), electron paramagnetic resonance (EPR), and aberration corrected high angle annular dark field scanning transmission electron microscope (AC HAADF-STEM) confirmed the successful synthesis of AM-CoSi with rich Si vacancy (Siv). The as-prepared CoSi alloy catalysts exhibit an order of magnitude activity enhancement in the oxidation of model reactant benzyl alcohol (BAL) to benzyl benzoate (BBE) compared with its mono counterparts, whereas 70 highest yield to date. Experimental results and DFT calculations well verify that the CoSi alloy structure improves the BAL conversion and Si vacancy mainly contributes to the generation of BBE. After that, CoSi alloy maintains high stability and a potential pathway is rationally proposed. Besides, CoSi alloy also efficiently works for the selective oxidation of various alcohols with different groups. This work demonstrates for the first time that semimetal CoSi alloy is robust for the green oxidation of various alcohols and provides a vast opportunity for reasonable design and application of other semimetal alloy catalysts.