Methylamine decomposition on nickel surfaces: A density functional theory study

Direct n-octanol amination by ammonia on supported Ni and Pd catalysts: activity is enhanced by “spectator” ammonia adsorbates

“…However, this reaction has attracted attention as a major step of the nitrile hydrogenation reaction network and as an intermediate in the decomposition of amines. 21,22,23 In this reaction, the hydrogenation of the nitrogen belonging to the imine appears to be more difficult than the hydrogenation of the carbon over most metals. Furthermore, to the best of our knowledge, the effect of co-adsorbed species on this reaction has never been addressed.…”

Hydrogen generation from methylamine using silicon carbide nanotubes as a dehydrogenation catalyst: A density functional theory study

“…In the configuration A, which is the most stable mode, CH 3 NH 2 is adsorbed on the SiCNT surface through its nitrogen lone pair electrons in a top configuration with an adsorption energy of -45.6 kcal/mol. The Si-N bond length is about 1.94 Å, which is shorter than the corresponding interaction on Ni surface[15]. The C-N bond length of CH 3 NH 2 is about 1.48 Å, a little longer than that of the isolated molecule (1.46 Å), suggesting that adsorption process weakens the C-N bond.…”

“…Furthermore, CH 3 NH 2 liquefies at normal conditions, thus it can be handled and stored more easily than hydrogen. Up to now, it is wellknown that methylamine can be adsorbed through the nitrogen lone pair electrons on metal surfaces [14][15][16][17][18][19][20][21], and the C-H, N-H or C-N bond can be activated at an enough high temperature. Several fundamental studies indicated that CH 3 NH 2 is able to release hydrogen via a room temperature dehydrogenation reaction in the presence of a suitable catalyst [22,23].…”

Decomposition mechanism of methylamine to hydrogen cyanide on Pt(111): selectivity of the C–H, N–H and C–N bond scissions

“…This indicates that there is no signicant activation of CH 3 NH 2 when adsorbed on Pt(111), similar to previous DFT studies about CH 3 NH 2 absorbed on Ni(100) and Ni(111). 24 CH 2 NH 2 prefers to absorb at the bridge site with h 1 (N)-h 1 (C) conguration, in which both CH 2 and NH 2 fragments locate at the top sites. The corresponding adsorption energy is 2.35 eV, and the C-N bond length is 1.480 Å with the C-N axis almost parallel to the surface.…”

“…Theoretical investigations are of great help for understanding the reaction mechanisms, especially for DFT investigations applied to reveal the microscopic adsorption structures, decomposition congurations, reaction pathways, and reaction kinetics and thermodynamics. [21][22][23] Lv et al 24 carried out DFT modelling to understand the initial CH 3 NH 2 decomposition on Ni(111) and Ni(100), and found that CH 3 NH 2 scission sequence took place with the order of C-H > N-H > C-N. Moreover, they investigated CH 3 NH 2 decomposition on Mo(100) 25,26 and Pd(111), 27 and the results showed that the most likely decomposition pathway was CH 28 and Co(111), 29 and found that the reaction mechanism of the hydrogenation pathway on both surfaces was HCN / CNH 2 + HCNH / CH 2 NH / CH 2 NH 2 + CH 2 NH / CH 3 NH 2 .…”