Zhang Nan, Shao Qi, Wang Pengtang, Zhu Xing, Huang Xiaoqing
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu, 215123, China.
Testing & Analysis Center, Soochow University, Jiangsu, 215123, China.
Small. 2018 May;14(19):e1704318. doi: 10.1002/smll.201704318. Epub 2018 Apr 15.
Although chemoselective hydrogenation of unsaturated aldehydes is the major route to highly valuable industrially demanded unsaturated alcohols, it is still challenging, as the production of saturated aldehydes is more favorable over unsaturated alcohols from the view of thermodynamics. By combining the structural features of porous nanowires (NWs) and metal-organic frameworks (MOFs), a unique class of porous Pt-Ni NWs in situ encapsuled by MOFs (Pt-Ni NWs@Ni/Fex-MOFs) is designed to enhance the unsaturated alcohols selectivity in the cinnamaldehyde (CAL) hydrogenation. A detailed catalytic study shows that the porous Pt-Ni NWs@Ni/Fe -MOFs exhibit volcano-type activity and selectivity in CAL hydrogenation as a function of Fe content. The optimized porous PtNi NWs@Ni/Fe -MOF is highly active and selective with 99.5% CAL conversion and 83.3% cinnamyl alcohol selectivity due to the confinement effect, appropriate thickness of MOF and its optimized electronic structure, and excellent durability with negligible activity and selectivity loss after five runs.
尽管不饱和醛的化学选择性氢化是生产具有高工业价值的不饱和醇的主要途径，但该过程仍具有挑战性，因为从热力学角度来看，生成饱和醛比生成不饱和醇更有利。通过结合多孔纳米线（NWs）和金属有机框架（MOFs）的结构特征，设计了一类独特的由MOF原位封装的多孔Pt-Ni NWs（Pt-Ni NWs@Ni/Fex-MOFs），以提高肉桂醛（CAL）氢化反应中不饱和醇的选择性。详细的催化研究表明，多孔Pt-Ni NWs@Ni/Fe-MOFs在CAL氢化反应中表现出随铁含量变化的火山型活性和选择性。优化后的多孔PtNi NWs@Ni/Fe-MOF具有高活性和选择性，CAL转化率为99.5%，肉桂醇选择性为83.3%，这归因于限域效应、MOF的合适厚度及其优化的电子结构，并且具有出色的耐久性，五次循环后活性和选择性损失可忽略不计。
