Abstract:
The time- and temperature-dependent adsorption on N2O, CO, and CH4 on
CVD-grown graphene has been investigated by MIR reflection−absorption spectroscopy to
gain information about the adsorption kinetics, notably the rate constants k and activation
energies Ea on the adsorption step. The gas adsorption is followed by determining the change
of the reflected beam intensity with time by taking difference spectra, i.e., subtracting the
baseline signal (reflectivity of graphene at the respective gas excitation line) from the
measurement with added gas. The experiments yield adsorption activation energies Ea of
−19.6 ± 1.1 (N2O), −12.1 ± 0.2 (CO), and −9.5 ± 1.7 kJ/mol (CH4). The obtained Ea
values are in excellent agreement with the literature results from theory, thereby confrming
these studies. The Ea values indicate physisorption, i.e., no strong bonding of the gas
molecules to graphene. The analyzed adsorption rate constants k are reported for the frst
time and are on the order of 1011 to 1012 molecules·s−1·cm−2 with N2O showing the highest
value and CH4 the lowest value. The adsorption rate constants follow the series N2O > CO
> CH4, in line with the charge transfer abilities of the molecules. This work can be easily extended to kinetic studies of other gases
hazardous to the environment and adsorption studies with other 2D materials using versatile MIR reflection−absorption
spectroscopy.