Xu Shuaiwen, Wang Lei, Tian Pengfei, Zhou Shenghu
Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology 130 Meilong Road Shanghai 200237 P. R. China
Key Laboratory of Pressure Systems and Safety, Ministry of Education, School of Mechanical and Power Engineering, East China University of Science and Technology 130 Meilong Road Shanghai 200237 P. R. China.
RSC Adv. 2025 Mar 3;15(9):6847-6853. doi: 10.1039/d5ra00302d. eCollection 2025 Feb 26.
In this work, we report alumina-supported metal-metalloid alloy nanoparticles (PdB/AlO) as highly efficient alkyne semi-hydrogenation catalysts. The mentioned catalysts contain orthorhombically distorted PdB nanoparticles and were prepared by transformation of Pd/AlO with borane dimethylamine complex by a solvothermal method. The synthesized PdB/AlO demonstrated greatly enhanced semi-hydrogenation performance. Under reaction conditions of 30 °C, 0.1 MPa of H and a substrate/Pd molar ratio of 1000/1, the conversions of 3-hexyne-1-ol could reach 99.8% in 15 min with a yield of -3-hexen-1-ol of 93.3%. Importantly, the alkene and to -alkene selectivity only slightly decreases with an extended reaction time, showing the inhibition of deep hydrogenation. Experimental studies and density functional theory calculations indicate that the catalytic enhancement is originated from the formation of PdB alloy, which alters the electronic and geometric properties of surface species, thus suppressing the deep hydrogenation with the enhanced alkene selectivity.
在本工作中，我们报道了氧化铝负载的金属-类金属合金纳米颗粒（PdB/AlO）作为高效的炔烃半加氢催化剂。上述催化剂包含正交畸变的PdB纳米颗粒，通过溶剂热法用硼烷二甲胺络合物对Pd/AlO进行转化制备而成。合成的PdB/AlO表现出大大增强的半加氢性能。在30℃、0.1MPa氢气以及底物与钯摩尔比为1000/1的反应条件下，3-己炔-1-醇在15分钟内的转化率可达99.8%，-3-己烯-1-醇的产率为93.3%。重要的是，随着反应时间延长，烯烃向-烯烃的选择性仅略有下降，表明抑制了深度加氢。实验研究和密度泛函理论计算表明，催化性能的增强源于PdB合金的形成，这改变了表面物种的电子和几何性质，从而在提高烯烃选择性的同时抑制了深度加氢。
