基于酸促进的单原子活性位点Ir-La-S/AC催化剂在甲醇羰基化中的应用

doi:10.1016/S1872-2067(18)63019-0

催化学报 ›› 2018, Vol. 39 ›› Issue (6): 1060-1069.DOI: 10.1016/S1872-2067(18)63019-0

基于酸促进的单原子活性位点Ir-La-S/AC催化剂在甲醇羰基化中的应用

任周^a,c, 吕元^a, 冯四全^a,c, 宋宪根^a, 丁云杰^a,b

a 中国科学院大连化学物理研究所洁净能源国家实验室, 辽宁大连 116023;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023;
c 中国科学院大学, 北京 100049

收稿日期:2018-01-19 修回日期:2018-03-02 出版日期:2018-06-18 发布日期:2018-05-16
通讯作者: 吕元, 丁云杰
基金资助:
国家重点研发计划（2017YFB0602203）.

Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites

Zhou Ren^a,c, Yuan Lyu^a, Siquan Feng^a,c, Xiangen Song^a, Yunjie Ding^a,b

a Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b State Key Laboratory of catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-01-19 Revised:2018-03-02 Online:2018-06-18 Published:2018-05-16
Contact: 10.1016/S1872-2067(18)63019-0
Supported by:
This work was supported by the National Key R&D Program of China (2017YFB0602203).

摘要/Abstract

摘要：

甲醇羰基化是世界上重要的均相催化反应之一.无论是Rh或者Ir体系，虽然碘甲烷的引入会带来腐蚀问题，但是绝大多数的甲醇羰基化反应过程都需要碘甲烷作为助催化剂才能有较好的活性.多年来人们在不断研究非均相羰基化过程（即均相多相化），以避免均相中间歇生产和产物分离的缺点.其中Ir体系的非均相羰基化报道很少，值得关注的是Eastman公司将Ir-La/AC体系成功地应用于非均相的甲醇羰基化过程.基于此，本文试图引入硫元素以提高Ir-La/AC催化剂的羰基化活性，即将含有La和Ir前驱体的硫酸溶液通过共浸渍法制备了高活性的Ir-La-S/AC催化剂，评价了该系列催化剂的性能，并进行了深入的表征.Ir-La-S/AC催化剂的TOF最高可达2760h^-1，远远高于Ir-La/AC催化剂1000h^-1.HAADF-STEM的结果表明，Ir-La-S/AC催化剂中Ir物种绝大多数处于单分散状态，而Ir-La/AC催化剂中的Ir物种为平均粒径为1.5nm的纳米颗粒状态，说明Ir-La-S/AC催化剂中Ir的使用效率要远远高于Ir-La/AC.其次，NH₃-TPD的结果显示在制备过程中硫酸的加入使催化剂的酸性位点大幅度增多，而酸性位可以加速Ir体系机理中CO插入这一决速步骤.目前普遍认为，Ir⁺物种为甲醇羰基化的活性中心，故通过TPR和原位XPS测试证实了Ir-La-S/AC催化剂比Ir-La/AC中的Ir物种在通过CO/H₂=10：1混合气活化后更容易还原到Ir⁺，而且这又说明在Ir-La-S/AC催化剂中更易发生Ir³⁺物种还原消除为Ir⁺物种且同时产生酰基碘（AcI）这一重要循环步骤.所以Ir-La-S/AC催化剂具有更多的酸促进位点，更高的Ir分散度和更多的Ir⁺活性物种.此外，Ir-La-S/AC催化剂的羰基化活性在66h之后才趋于稳定（1660h^-1），通过XRF测试发现该过程中有少量的硫流失，而大部分剩余的硫比较稳定的存在于催化剂表面，且通过ICP-MS结果显示Ir和La没有明显的流失，因此66h之前活性下降主要是由于部分S的流失，而不是金属物种Ir和La流失造成的.总之，我们成功地制备了一种硫促进的双功能Ir-La-S/AC催化剂，这种方法不仅减轻了由液体酸带来的环境污染和设备腐蚀，同时避免了液相铱体系催化剂的循环使用问题.

关键词: 非均相甲醇羰基化, Ir-La-S/AC催化剂, 双功能催化剂, 单分散活性位点, 共浸渍

Abstract:

Highly active Ir-La-S/AC catalyst was successfully prepared by co-impregnation of an activated carbon (AC) carrier with a sulfuric acid solution of Ir and La species and compared with a traditionally prepared Ir-La/AC catalyst. High angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM) measurement results show that most of the Ir species on Ir-La-S/AC exist as single atomic sites, while those on Ir-La/AC exist as nanoparticles with an average diameter of 1.5 nm. Evaluation of Ir-La-S/AC as a catalyst for heterogeneous carbonylation of methanol to acetyl gave a maximum TOF (turn-over-frequency) of 2760 h^-1, which was distinctly higher than that achieved by the Ir-La/AC catalyst (approximately 1000 h^-1). Temperature-programmed desorption of ammonia (NH₃-TPD) result shows that the addition of sulfuric acid during the preparation procedure results in significantly more acidic sites on Ir-La-S/AC than those on Ir-La/AC, which plays a key role in the enhancement of CO insertion as the rate-determining step. Temperature-programmed reduction (TPR) and in situ X-ray photoelectron spectroscopy reveal that Ir species are more reducible, and that more Ir⁺ might be formed by activation of Ir-La-S/AC than those on the Ir-La/AC catalyst, which is thought to be beneficial for reductive elimination of AcI from Ir³⁺ species as an essential step for CH₃I regeneration and acetyl formation.

Key words: Heterogeneous methanol carbonylation, Ir-La-S/AC catalyst, Bifunctional catalyst, Single-atomic active site, Co-impregnation

任周, 吕元, 冯四全, 宋宪根, 丁云杰. 基于酸促进的单原子活性位点Ir-La-S/AC催化剂在甲醇羰基化中的应用[J]. 催化学报, 2018, 39(6): 1060-1069.

Zhou Ren, Yuan Lyu, Siquan Feng, Xiangen Song, Yunjie Ding. Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites[J]. Chinese Journal of Catalysis, 2018, 39(6): 1060-1069.

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基于酸促进的单原子活性位点Ir-La-S/AC催化剂在甲醇羰基化中的应用

Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites

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