Isq qd

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 A sample of the reaction solution (ca. 500 µL) was withdrawn and centrifuged in order to separate the catalyst from the solution.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 In order to separate the catalyst, 200 µL of reaction mixture were withdrawn and centrifuged.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).

The hydrogenation reactions were carried out in a 100 ml stainless steel autoclave equipped with a thermocouple, a mechanical stirrer, and a glass inlet to contain the reaction solution. In a typical experiment, 15 mL of 2-butanol (Sigma-Aldrich, Haverhill, MA, USA; >99%), 0.1550 g of HMF (Sigma-Aldrich, >99%) and an appropriate amount of activated catalyst (usually 1 mol% relative to HMF) were added into a 100 ml glass inlet and placed into the autoclave. The system was flushed several times with N₂ first and then with H₂ and pressurized before heating. The reactor was heated at the desired temperature, setting the stirring rate to 1000 rpm, and held for a specified amount of time before the reaction was quenched in an ice bath. The catalyst was then removed by centrifugation and the filtrate was diluted with a solution of an external standard (p-xylene, Sigma-Aldrich, >99%) for GC measurement. For the analysis of the products, a GC-MS (Thermo Scientific, Waltham, MA, USA; ISQ QD equipped with an Agilent VF-5ms column) was employed and the resulting fragmentation peaks were compared with the standards present in the software database, while, for the quantification of the amounts of reactants consumed and products generated, a GC-FID equipped with a non-polar column was employed (Agilent, Santa Clara, CA, USA; 7820A equipped with an Agilent CP-Sil 5 CB column).