Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon, Republic of Korea.
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea.
Nature. 2020 Sep;585(7824):221-224. doi: 10.1038/s41586-020-2671-4. Epub 2020 Sep 9.
Platinum is a much used catalyst that, in petrochemical processes, is often alloyed with other metals to improve catalytic activity, selectivity and longevity. Such catalysts are usually prepared in the form of metallic nanoparticles supported on porous solids, and their production involves reducing metal precursor compounds under a H flow at high temperatures. The method works well when using easily reducible late transition metals, but Pt alloy formation with rare-earth elements through the H reduction route is almost impossible owing to the low chemical potential of rare-earth element oxides. Here we use as support a mesoporous zeolite that has pore walls with surface framework defects (called 'silanol nests') and show that the zeolite enables alloy formation between Pt and rare-earth elements. We find that the silanol nests enable the rare-earth elements to exist as single atomic species with a substantially higher chemical potential compared with that of the bulk oxide, making it possible for them to diffuse onto Pt. High-resolution transmission electron microscopy and hydrogen chemisorption measurements indicate that the resultant bimetallic nanoparticles supported on the mesoporous zeolite are intermetallic compounds, which we find to be stable, highly active and selective catalysts for the propane dehydrogenation reaction. When used with late transition metals, the same preparation strategy produces Pt alloy catalysts that incorporate an unusually large amount of the second metal and, in the case of the PtCo alloy, show high catalytic activity and selectivity in the preferential oxidation of carbon monoxide in H.
铂是一种广泛使用的催化剂,在石油化工过程中,通常与其他金属合金化以提高催化活性、选择性和寿命。此类催化剂通常以负载在多孔固体上的金属纳米粒子的形式制备,其制备过程涉及在 H 流下于高温下还原金属前体化合物。该方法在使用易还原的后过渡金属时效果很好,但通过 H 还原途径将 Pt 与稀土元素形成合金几乎是不可能的,因为稀土元素氧化物的化学势较低。在这里,我们使用具有表面骨架缺陷(称为“硅醇窝”)的中孔沸石作为载体,并表明沸石能够在 Pt 和稀土元素之间形成合金。我们发现,硅醇窝使稀土元素以单个原子物种存在,其化学势与体氧化物相比大大提高,从而使它们能够扩散到 Pt 上。高分辨率透射电子显微镜和氢气化学吸附测量表明,负载在中孔沸石上的双金属纳米粒子是金属间化合物,我们发现它们是丙烷脱氢反应的稳定、高活性和选择性催化剂。当与后过渡金属一起使用时,相同的制备策略可制备出 Pt 合金催化剂,其中包含异常大量的第二种金属,并且在 PtCo 合金的情况下,在 H 中一氧化碳的优先氧化中表现出高催化活性和选择性。