Microenvironment and electronic state modulation of Pd nanoparticles within MOFs for enhancing low-temperature activity towards DCPD hydrogenation

IF 15.7 1区 化学 Q1 CHEMISTRY, APPLIED
Zhiyuan Liu , Changan Wang , Ping Yang , Wei Wang , Hongyi Gao , Guoqing An , Siqi Liu , Juan Chen , Tingting Guo , Xinmeng Xu , Ge Wang
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Abstract

Precise control of the local environment and electronic state of the guest is an important method of controlling catalytic activity and reaction pathways. In this paper, guest Pd NPs were introduced into a series of host UiO-67 MOFs with different functional ligands and metal nodes, the microenvironment and local electronic structure of Pd is modulated by introducing bipyridine groups and changing metal nodes (Ce6O6 or Zr6O6). The bipyridine groups not only promoted the dispersion Pd NPs, but also facilitated electron transfer between Pd and UiO-67 MOFs through the formation of Pd-N bridges. Compared with Zr6 clusters, the tunability and orbital hybridisation of the 4f electronic structure in the Ce6 clusters modulate the electronic structure of Pd through the construction of the Ce-O-Pd interfaces. The optimal catalyst Pd/UiO-67(Ce)-bpy presented excellent low-temperature activity towards dicyclopentadiene hydrogenation with a conversion of > 99% and a selectivity of > 99% (50 °C, 10 bar). The results show that the synergy of Ce-O-Pd and Pd-N promotes the formation of active Pdδ+, which not only enhances the adsorption of H2 and electron-rich C=C bonds, but also contributes to the reduction of proton migration distance and improves proton utilization efficiency. These results provide valuable insights for investigating the regulatory role of the host MOFs, the nature of host-guest interactions, and their correlation with catalytic performance.

利用 MOFs 内 Pd 纳米粒子的微环境和电子态调制提高二氯二苯并[DCPD]氢化的低温活性
精确控制客体的局部环境和电子状态是控制催化活性和反应途径的重要方法。本文将客体 Pd NPs 引入一系列具有不同功能配体和金属节点的宿主 UiO-67 MOFs 中,通过引入联吡啶基团和改变金属节点(Ce6O6 或 Zr6O6)来调控 Pd 的微环境和局部电子结构。联吡啶基团不仅促进了 Pd NPs 的分散,还通过形成 Pd-N 桥促进了 Pd 和 UiO-67 MOFs 之间的电子转移。与 Zr6 团簇相比,Ce6 团簇中 4f 电子结构的可调谐性和轨道杂化可通过构建 Ce-O-Pd 界面来调节 Pd 的电子结构。最佳催化剂 Pd/UiO-67(Ce)-bpy 在二环戊二烯加氢反应中表现出优异的低温活性,转化率达 99%,选择性达 99%(50 °C,10 巴)。结果表明,Ce-O-Pd 和 Pd-N 的协同作用促进了活性 Pdδ+ 的形成,这不仅增强了对 H2 和富电子 C=C 键的吸附,还有助于减少质子迁移距离,提高质子利用效率。这些结果为研究宿主 MOFs 的调控作用、宿主-客体相互作用的性质及其与催化性能的相关性提供了宝贵的见解。
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来源期刊
Chinese Journal of Catalysis
Chinese Journal of Catalysis 工程技术-工程:化工
CiteScore
25.80
自引率
10.30%
发文量
235
审稿时长
1.2 months
期刊介绍: The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.
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