Trace 1300

The HMF hydrogenation reactions were carried out in a 100 mL stainless steel autoclave equipped with a mechanical stirrer and a thermocouple. In a typical experiment, 0.1550 g of HMF (Sigma-Aldrich, 99%) were dissolved in 15 mL of 2-butanol (Sigma-Aldrich, 99%). The solution was placed into a glass inlet with the appropriate amount of activated catalyst (Ru:HMF molar ratio of 1:100). The system was then sealed and purged with N₂ first and then H₂, which pressurized the reactor to the desired pressure (20 bar). The autoclave was heated up to 150 °C and the solution was stirred at 1000 rpm. Samplings were carried out by stopping the stirring and quenching of the reaction of the samples in an ice bath. A sample of the reaction solution (ca. 500 µL) was withdrawn and centrifuged in order to separate the catalyst from the solution. The filtrate was diluted with a solution of an external standard (dodecanol, Sigma-Aldrich, >98%) for GC measurement. Product analysis was carried out with a GC-MS (Thermo Scientific, Waltham, MA, USA, ISQ QD equipped with an Agilent VF-5ms column) and the resulting fragmentation peaks were compared with standards present in the software database. Product quantification was carried out through a GC-FID equipped with a non-polar column (Thermo Scientific, TRACE 1300 equipped with an Agilent HP-5 column).

The reference catalysts (1% Pd/GNP) were tested in the hydrogenation of both benzaldehyde (ReagentPlus^®, ≥99% Sigma-Aldrich) and octanal (for synthesis, Sigma-Aldrich).
The reactions were carried out in a 100 mL stainless steel autoclave. We used 10 mL of a 0.3 M solution of substrate (benzaldehyde or octanal) in the solvent (p-xylene or dodecane, anhydrous, ≥99% Sigma-aldrich) and an amount of catalyst to reach a reactant-to-metal molar ratio of 1000:1. The reaction occurred at 50 °C and 2 bar of H₂ pressure. Samplings were carried out by stopping the stirrer and quenching the reaction under cold water. In order to separate the catalyst, 200 µL of reaction mixture were withdrawn and centrifuged. Then, 100 µL of the supernatant solution was diluted with a solution of 1-dodecanol in p-xylene (external standard) for GC measurement.
Product analysis was carried out with a GC-MS (Thermo Scientific, Waltham, MA, USA, ISQ QD equipped with an Agilent VF-5 ms column, Santa Clara, California, USA) and the resulting fragmentation peaks were compared with standards present in the software database. Product quantification was carried out through a GC-FID equipped with a non-polar column (Thermo Scientific, TRACE 1300 equipped with an Agilent HP-5 column).