Talshyn Begildayeva1, Ahreum Ahn2, Shreyanka Shankar Naik1, Seung Jun Lee1, Jayaraman Theerthagiri1, Tae Ho Kim1, Myong Yong Choi3. 1. Core-Facility Center for Photochemistry & Nanomaterials, Department of Chemistry (BK21 FOUR), Research Institute of Natural Sciences, Gyeongsang National University, Jinju, 52828, Republic of Korea. 2. Center for Supercomputing Applications, Korea Institute of Science and Technology Information, 245 Daehak-ro, Daejeon, 34141, Republic of Korea. 3. Core-Facility Center for Photochemistry & Nanomaterials, Department of Chemistry (BK21 FOUR), Research Institute of Natural Sciences, Gyeongsang National University, Jinju, 52828, Republic of Korea. mychoi@gnu.ac.kr.
Abstract
Binding energies of different nitrile solvents and their utilization for CuCN formation were investigated through quantum chemical calculations. A pulsed laser ablation in liquid (PLAL) method for CuCN synthesis was developed herein. Initially, the interaction between the pulsed laser and the Cu-target generated Cu-ions and electrons at the point of contact. The laser beam also exhibited sufficient energy to dissociate the bonds of the respective solvents. In the case of acetonitrile, the oxidized Cu-ions bonded with CN- to produce CuCN with a cube-like surface structure. Other nitrile solvents generated spherically-shaped Cu@graphitic carbon (Cu@GC) nanoparticles. Thus, the production of CuCN was favorable only in acetonitrile due to the availability of the cyano group immediately after the fragmentation of acetonitrile (CH3+ and CN-) under PLAL. Conversely, propionitrile and butyronitrile released large amounts of hydrocarbons, which deposited on Cu NPs surface to form GC layers. Following the encapsulation of Cu NPs with carbon shells, further interaction with the cyano group was not possible. Subsequently, theoretical study on the binding energies of nitrile solvents was confirmed by highly correlated basic sets of B3LYP and MP2 which results were consistent with the experimental outcomes. The findings obtained herein could be utilized for the development of novel metal-polymer materials.
Binding energies of different nitrile solvents and then class="Gene">ir utilization for CuCN formation were investigated through quantum chemical calculations. A pulsed laser ablation in liquid (PLAL) method for CuCN synthesis was developed herein. Initially, the interaction between the pulsed laser and the Cu-target generated Cu-ions and electrons at the point of contact. The laser beam also exhibited sufficient energy to dissociate the bonds of the respective solvents. In the case of acetonitrile, the oxidized Cu-ions bonded with CN- to produce CuCN with a cube-like surface structure. Other nitrile solvents generated spherically-shaped Cu@graphitic carbon (Cu@GC) nanoparticles. Thus, the production of CuCN was favorable only in acetonitrile due to the availability of the cyano group immediately after the fragmentation of acetonitrile (CH3+ and CN-) under PLAL. Conversely, propionitrile and butyronitrile released large amounts of hydrocarbons, which deposited on CuNPs surface to form GC layers. Following the encapsulation of CuNPs with carbon shells, further interaction with the cyano group was not possible. Subsequently, theoretical study on the binding energies of nitrile solvents was confirmed by highly correlated basic sets of B3LYP and MP2 which results were consistent with the experimental outcomes. The findings obtained herein could be utilized for the development of novel metal-polymer materials.