Costa Dolly Carolina, Soldati Analía Leticia, Bengoa José Fernando, Marchetti Sergio Gustavo, Vetere Virginia
Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco"-CINDECA (UNLP-CONICET-CICBA), Calle 47 N 257, 1900, La Plata, Bs. As, Argentina.
Grupo de Caracterización de Materiales, Centro Atómico Bariloche, CONICET. Av. Bustillo, 9500, San Carlos de Bariloche, Río Negro, Argentina.
Heliyon. 2019 Jun 3;5(6):e01859. doi: 10.1016/j.heliyon.2019.e01859. eCollection 2019 Jun.
Two catalysts were prepared using monodisperse pre-synthetized nanoparticles of metallic nickel and nickel phosphides with the same average diameter. Both nanoparticles species were deposited on the same support: mesoporous silica nano-spheres of MCM-41. This support is suitable to inhibit agglomeration and sintering processes during preparation steps. Therefore, two supported and activated catalysts with the same average nanoparticles diameter were obtained. They differ only in the nature of the active species: metallic nickel and nickel phosphides. The effect of the presence of a second element (phosphorus), more electronegative than nickel, on the activity and selectivity in the chemoselective hydrogenation of acetophenone was studied. The reaction conditions were: H pressure of 1 MPa, 80 °C using n-heptane as solvent. With the aim to understand the catalytic results, nanoparticles, support and catalysts were carefully characterized by X-ray diffraction, diffuse light scattering, transmission electron microcopy, high resolution transmission electron microcopy, selected area electron diffraction, scanning electron microcopy, Fourier transformer infrared spectroscopy, N adsorption at -196 °C, atomic absorption, H and CO chemisorption and volumetric oxidation. Considering these results and geometric and electronic characteristics of the surface of both active species, a change in the adsorption intermediate state of acetophenone in presence of phosphorus is proposed to explain the hydrogenation chemoselectivity of nickel phospides.
使用具有相同平均直径的单分散预合成金属镍纳米颗粒和磷化镍纳米颗粒制备了两种催化剂。这两种纳米颗粒都沉积在相同的载体上:MCM-41介孔二氧化硅纳米球。这种载体适用于在制备步骤中抑制团聚和烧结过程。因此,获得了两种具有相同平均纳米颗粒直径的负载型和活化催化剂。它们仅在活性物种的性质上有所不同:金属镍和磷化镍。研究了比镍电负性更强的第二种元素(磷)的存在对苯乙酮化学选择性氢化反应活性和选择性的影响。反应条件为:氢气压力1 MPa,80℃,使用正庚烷作为溶剂。为了理解催化结果,通过X射线衍射、漫散射光、透射电子显微镜、高分辨率透射电子显微镜、选区电子衍射、扫描电子显微镜、傅里叶变换红外光谱、-196℃下的氮气吸附、原子吸收、氢气和一氧化碳化学吸附以及体积氧化对纳米颗粒、载体和催化剂进行了仔细表征。考虑到这些结果以及两种活性物种表面的几何和电子特性,提出了在磷存在下苯乙酮吸附中间态的变化来解释磷化镍的氢化化学选择性。