State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi, 030001, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Nat Commun. 2023 May 6;14(1):2627. doi: 10.1038/s41467-023-38336-5.
Direct conversion of CO to a single specific hydrocarbon with high selectivity is extremely attractive but very challenging. Herein, by employing an InZrO-Beta composite catalyst in the CO hydrogenation, a high selectivity of 53.4% to butane is achieved in hydrocarbons (CO free) under 315 °C and 3.0 MPa, at a CO conversion of 20.4%. Various characterizations and DFT calculation reveal that the generation of methanol-related intermediates by CO hydrogenation is closely related to the surface oxygen vacancies of InZrO, which can be tuned through modulating the preparation methods. In contrast, the three-dimensional 12-ring channels of H-Beta conduces to forming higher methylbenzenes and methylnaphthalenes containing isopropyl side-chain, which favors the transformation of methanol-related intermediates to butane through alkyl side-chain elimination and subsequent methylation and hydrogenation. Moreover, the catalytic stability of InZrO-Beta in the CO hydrogenation is considerably improved by a surface silica protection strategy which can effectively inhibit the indium migration.
将 CO 直接转化为具有高选择性的单一特定烃类化合物极具吸引力，但极具挑战性。在此，通过在 CO 加氢中使用 InZrO-Beta 复合催化剂，在 315°C 和 3.0 MPa 条件下，在 CO 转化率为 20.4%时，烃类（无 CO）中可获得 53.4%的正丁烷高选择性。各种表征和 DFT 计算表明，CO 加氢生成与甲醇相关的中间体与 InZrO 的表面氧空位密切相关，通过调节制备方法可以对其进行调变。相比之下，H-Beta 的三维 12 元环通道有利于形成含有异丙基侧链的较高甲基苯和甲基萘，这有利于通过烷基侧链消除以及随后的甲基化和加氢反应将与甲醇相关的中间体转化为正丁烷。此外，通过表面硅保护策略可以显著提高 InZrO-Beta 在 CO 加氢中的催化稳定性，该策略可以有效抑制铟的迁移。
