Boosting Hydrogen Production from Formic Acid over Pd Catalysts by Deposition of N-Containing Precursors on the Carbon Support

• Main Authors: Fedor S. Golub, Sergey Beloshapkin, Artem V. Gusel’nikov, Vasily A. Bolotov, Valentin N. Parmon, Dmitri A. Bulushev
• Format: Article
• Language: English
• Published: MDPI AG 2019-10-01
• Series: Energies
• Subjects: hydrogen production; formic acid decomposition; pd/c; melamine; g-c₃n₄; bipyridine; phenanthroline; n-doped carbon
• Online Access: https://www.mdpi.com/1996-1073/12/20/3885

Formic acid is a promising liquid organic hydrogen carrier (LOHC) since it has relatively high hydrogen content (4.4 wt%), low inflammability, low toxicity and can be obtained from biomass or from CO₂. The aim of the present research was the creation of efficient 1 wt% Pd catalysts supported on mesoporous graphitic carbon (Sibunit) for the hydrogen production from gas-phase formic acid. For this purpose, the carbon support was modified by pyrolysis of deposited precursors containing pyridinic nitrogen such as melamine (Mel), 2,2′-bipyridine (Bpy) or 1,10-phenanthroline (Phen) at 673 K. The following activity trend of the catalysts Pd/Mel/C > Pd/C ~ Pd/Bpy/C > Pd/Phen/C was obtained. The activity of the Pd/Mel/C catalyst was by a factor of 4 higher than the activity of the Pd/C catalyst at about 373 K and the apparent activation energy was significantly lower than those for the other catalysts (32 vs. 42−46 kJ/mol). The high activity of the melamine-based samples was explained by a high dispersion of Pd nanoparticles (~2 nm, HRTEM) and their strong electron-deficient character (XPS) provided by interaction of Pd with pyridinic nitrogen species of the support. The presented results can be used for the development of supported Pd catalysts for hydrogen production from different liquid organic hydrogen carriers.