An experimental and theoretical study of glycerol oxidation to 1,3‐dihydroxyacetone over bimetallic Pt‐Bi catalysts

It is important to utilize glycerol, the main by‐product of biodiesel, to manufacture value‐added chemicals such as 1,3‐dihydroxyacetone (DHA). In the present work, the performance of five different catalysts (Pt‐Bi/AC, Pt‐Bi/ZSM‐5, Pt/MCM‐41, Pt‐Bi/MCM‐41, and Pt/Bi‐doped‐MCM‐41) was investigated experimentally, where Pt‐Bi/MCM‐41 was found to exhibit the highest DHA yield. To better understand the experimental results and to obtain insight into the reaction mechanism, density functional theory (DFT) computations were conducted to provide energy barriers of elementary steps. Both experimental and calculated results show that for high DHA selectivity, Bi should be located in an adatom‐like configuration Pt, rather than inside Pt. A favorable pathway and catalytic cycle of DHA formation were proposed based on the DFT results. A cooperative effect, between Pt as the primary component and Bi as a promoter, was identified for DHA formation. Both experimental and theoretical considerations demonstrate that Pt‐Bi is efficient to convert glycerol to DHA selectively. © 2016 American Institute of Chemical Engineers AIChE J , 63: 705–715, 2017