TY - JOUR

T1 - Boosting hydrogen production from formic acid over Pd catalysts by deposition of N-Containing precursors on the carbon support

AU - Golub, Fedor S.

AU - Beloshapkin, Sergey

AU - Gusel'Nikov, Artem V.

AU - Bolotov, Vasily A.

AU - Parmon, Valentin N.

AU - Bulushev, Dmitri A.

PY - 2019/10/14

Y1 - 2019/10/14

N2 - 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), 2,20-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.

AB - 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), 2,20-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.

KW - Bipyridine

KW - Formic acid decomposition

KW - G-C3N4

KW - Hydrogen production

KW - Melamine

KW - N-doped carbon

KW - Pd/C

KW - Phenanthroline

KW - g-C3N4

KW - bipyridine

KW - NANOFIBERS

KW - formic acid decomposition

KW - DOPED CARBON

KW - CO2

KW - melamine

KW - NITRIDE

KW - hydrogen production

KW - phenanthroline

KW - HIGH-SURFACE-AREA

KW - TEMPERATURE

KW - SITES

KW - EFFICIENCY

UR - http://www.scopus.com/inward/record.url?scp=85074969213&partnerID=8YFLogxK

U2 - 10.3390/en12203885

DO - 10.3390/en12203885

M3 - Article

AN - SCOPUS:85074969213

VL - 12

JO - Energies

JF - Energies

SN - 1996-1073

IS - 20

M1 - 3885

ER -