Nakaya Yuki, Hayashida Eigo, Asakura Hiroyuki, Takakusagi Satoru, Yasumura Shunsaku, Shimizu Ken-Ichi, Furukawa Shinya
Institute for Catalysis, Hokkaido University, N-21, W-10, Kita-ku, Sapporo001-0021, Japan.
Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Nishikyo-ku, Kyoto615-8520, Japan.
J Am Chem Soc. 2022 Sep 7;144(35):15944-15953. doi: 10.1021/jacs.2c01200. Epub 2022 Aug 19.
Propane dehydrogenation has been a promising propylene production process that can compensate for the increasing global demand for propylene. However, Pt-based catalysts with high stability at ≥600 °C have barely been reported because the catalysts typically result in short catalyst life owing to side reactions and coke formation. Herein, we report a new class of heterogeneous catalysts using high-entropy intermetallics (HEIs). Pt-Pt ensembles, which cause side reactions, are entirely diluted by the component inert metals in PtGe-type HEIs. The resultant HEI (PtCoCu) (GeGaSn)/Ca-SiO exhibited an outstandingly high catalytic stability, even at 600 °C ( = τ = 4146 = 173 d), and almost no deactivation of the catalyst was observed for 2 months for the first time. Detailed experimental studies and theoretical calculations demonstrated that the combination of the site-isolation and entropy effects upon multi-metallization of PtGe drastically enhanced the desorption of propylene and the thermal stability, eventually suppressing the side reactions even at high reaction temperatures.
丙烷脱氢一直是一种很有前景的丙烯生产工艺,能够满足全球对丙烯日益增长的需求。然而,几乎没有报道过在≥600°C时具有高稳定性的铂基催化剂,因为这类催化剂通常会因副反应和积炭导致催化剂寿命较短。在此,我们报道了一类使用高熵金属间化合物(HEIs)的新型多相催化剂。在PtGe型高熵金属间化合物中,引发副反应的Pt-Pt原子簇被组分中的惰性金属完全稀释。所得的高熵金属间化合物(PtCoCu)(GeGaSn)/Ca-SiO即使在600°C时也表现出极高的催化稳定性(τ = 4146 h = 173天),并且首次在两个月内几乎未观察到催化剂失活。详细的实验研究和理论计算表明,PtGe多金属化过程中的位点隔离和熵效应相结合,极大地增强了丙烯的脱附以及热稳定性,最终即使在高反应温度下也能抑制副反应。