Insights into the hydrogenation mechanism of nitrobenzene to aniline on Pd₃/Pt(111): a density functional theory study

Abstract

The hydrogenation mechanism of nitrobenzene to aniline on Pd3/Pt(111) surface preferentially follows the direct route and fits best the Jackson reaction mechanism (mechanism B).

Insights into the mechanism of nitrobenzene reduction to aniline over Pt catalyst and the significance of the adsorption of phenyl group on kinetics

“…This is, in fact, consistent with the adsorption of benzene on Pt(111) [21,22]. It was worth noticing that our result is different from that in ref [32], where the phenyl group of nitrobenzene adsorbed vertically on the surface during the reaction.…”

“…Only a few pioneering works have been made in the study of these large molecules [21,22,[26][27][28][29][30][31][32]. Saeys et al calculated benzene adsorption and hydrogenation to cyclohexane on Pt(111) [21,22].…”

“…To model the mechanism of nitrobenzene reduction, there are two significant problems to overcome. The first challenge is associated with the large size of nitrobenzene molecule, because a larger molecule would considerably increase the number of possible adsorption configurations [21][22][23][24][25][26][27][28][29][30][31][32], therefore, a significantly more adsorption configurations should be carefully tested in the calculations of nitrobenzene, in contrast to the much fewer adsorption configurations of other smaller organic molecules such as formic acid or methanol. In addition, an increase in adsorption configurations would also lead to an increase in the numbers of possible transition states, which again makes the calculations more complicated and time-consuming [21,22].…”

Controlled nitridation of tantalum (oxy)nitride nanoparticles towards optimized metal-support interactions with gold nanocatalysts

“…44,45 According to the Balandin-type volcano plots, the moderate adsorption on metals is demanded for efficient catalytic conversion because a weak adsorption cannot effectively activate substrates and a strong adsorption precludes product desorption. 7b) would promote the adsorption of polar -N δ+ -O δbonds in NB, 42,46,47 as compared with the neutral Au on Ta 2 O 5 , which presents optimized activity and selectivity (Scheme 2). XPS in Fig.…”

Insight into the Role of Additives in Catalytic Synthesis of Cyclohexylamine from Nitrobenzene

“…The first step involves the reduction of the nitro group to aniline (AN). According to previous researches, [5][6][7][8][9] there are two possible reaction pathways in this step, i.e., the direct route (upside pathway in Scheme 1) and condensation route (bottom pathway in Scheme 1). In general, the reaction rate for the condensation route is slower than that for the direct one, and no selectivity issue occurs in this step.…”