Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, UK.
Johnson Matthey Technology Centre, Blount's Court, Sonning Common, Reading RG4 9NH, UK.
Nat Commun. 2014 Dec 19;5:5787. doi: 10.1038/ncomms6787.
Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.
包含醋酸铅和喹啉改性碳酸钙的钯/碳酸钙 Lindlar 催化剂在工业上被广泛用于炔烃的部分氢化。然而，由于铅的毒性极强，及其从催化剂表面浸出的风险，其用途受到限制，特别是在食品、化妆品和药品制造方面。此外，在许多情况下，这些催化剂的选择性也很差。在这里，我们报告了一种非表面修饰的钯，它产生了一种超选择性的纳米催化剂。硼原子被发现存在于钯的间隙晶格位中，具有良好的化学和热稳定性。这是由于当负载钯纳米粒子用硼烷四氢呋喃溶液处理时，存在很强的主客体电子相互作用。钯的吸附性能被亚表面的硼原子修饰，并在一些具有挑战性的炔烃氢化反应中表现出超选择性，其性能优于 Lindlar 催化剂。
