A series of gold nanoparticles in the 4–40 nm range were prepared, immobilized on activated carbon and further tested, at low base concentration, in the catalytic oxidation of 5‐hydroxymethyl furfural (HMF) to 2,5‐furandicarboxylic acid (FDCA). Gold particles size variation has no influence on HMF conversion but significantly affects product selectivity and carbon balance. This behavior is ascribed to the thermodynamically favorable oxygen reduction reaction on Au(100) faces. As the gold particle size decreases the Au(100)/Au(111) exposure ratio, estimated by using the van Hardeveld‐Hartog model, increases as well as the FDCA selectivity. The smaller the gold particle size the smaller the 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA) to FDCA ratio pointing to the gold size dependent behavior of the oxidation of the alcohol function of the HMF molecule.
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