The selective amination of benzaldehyde (BZH) is one of the important industrial reactions for the production of fine chemicals. Herein, we synthesized a Ru/NiO nanocatalyst with an extremely low loading of noble metals (0.22%) via a facile ball-milling method efficient for the conversion of BZH to N-benzylidenebenzylamine (N-BDB). Compared with the benchmark im-Ru/NiO catalyst prepared via the traditional impregnation (im) method, the Ru/NiO catalyst exhibited the higher yield of N-BDB, with a full conversion of BZH and a 91.5% selectivity to N-BDB in 0.1 MPa NH3 and 2 MPa H2 pressure. After that, various parameters that influenced the catalytic performance and potential reaction pathway were investigated. In addition, the catalyst maintained high stability, which could be recycled even for five runs without obvious deactivation. Extensive characterizations verified that the H2 activation ability of Ru and the overall acidity of the Ru/NiO catalyst were improved, which should account for the superior catalytic performance. This work provides a facile strategy of catalyst synthesis for the selective production of fine chemicals.
In this work, the thermodynamics of molecular self-assembly for an anionic biosurfactant, sodium deoxycholate (NaDC) and their mixture with an oppositely charged surfactant, docecyltrimethylamonium bromide (DTAB) in aqueous solution was investigated by isothermal titration calorimeter (ITC), companied with turbidity and conductivity measurements. From the perspective of interaction energy, the results for single surfactant NaDC obtained from ITC provided a direct evidence for the stepwise association model to form the premicelles in the first step and the stable micelles in the second step. We obtained a series of thermodynamic parameters of premicellar and micellar formation, and thus discussed the thermodynamic mechanisms of molecular aggregation in these two processes. Furthermore, we investigated the thermodynamics of intermolecular interaction for the mixed systems composed of oppositely charged surfactants (DTAB/NaDC). The mixed critical micelle concentration (cmcmix) and the transition concentration between two micellar morphologies (CM) and their corresponding changes of enthalpy in the both processes were derived from ITC measurements in rich-NaDC and in rich-DTAB region, respectively. The results show that aggregation behaviors of DTAB/NaDC differ from single surfactant system or the normal mixed surfactants with charged head-and-tail, due to the asymmetry in molecular structures caused by the rigid steroid skeleton of NaDC composed of a hydrophilic and a hydrophobic surfaces. As a result, the occurrence of various aggregation processes in mixed solution can be controlled by the total concentrations of two surfactants and their molar ratio. Conclusively the process of mixed micellization is driven by entropy, and the transition between two kinds of micellar morphologies is driven jointly by entropy and enthalpy. Therefore, from the perspective of interaction themodynamics, this work gave a deep insight in understanding the themodynamics of molecular self- assembly and their phase behavior for mixed systems with bile salts and the positively charged surfactant.