Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects

化学 沸石 硅醇 烧结 氧化剂 质子化 无机化学 化学工程 有机化学 催化作用 工程类 离子
作者
Stephen C. Purdy,Greg Collinge,Junyan Zhang,Shivangi N. Borate,Kinga A. Unocic,Qiyuan Wu,Evan C. Wegener,A. Jeremy Kropf,Nohor “River” Samad,Simuck F. Yuk,Difan Zhang,Susan E. Habas,Theodore R. Krause,James W. Harris,Mal‐Soon Lee,Vassiliki‐Alexandra Glezakou,Roger Rousseau,Andrew D. Sutton,Zhenglong Li
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:146 (12): 8280-8297 被引量:21
标识
DOI:10.1021/jacs.3c13302
摘要

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu–Zn–Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu2+ reduces to Cu1+ after catalyst pretreatment (270 °C, 101 kPa H2) and further to Cu0 nanoparticles under reaction conditions (270–350 °C, 7 kPa EtOH, 94 kPa H2) or accelerated aging (400–450 °C, 101 kPa H2). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. The capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.
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