Boosting the Activity of Ligand-on Atomically Precise Pd3Cl Cluster Catalyst by Metal-Support Interaction from Kinetic and Thermodynamic Aspects
Boosting the Activity of Ligand-on Atomically Precise Pd3Cl Cluster Catalyst by Metal-Support Interaction from Kinetic and Thermodynamic Aspects
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从动力学和热力学方面通过金属-载体相互作用提高原子级精确的 Pd3Cl 簇催化剂上的配体活性
DOI：
10.1002/adsc.201800603
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发表时间：
2018
影响因子：
5.4
通讯作者：
Zhu Manzhou
中科院分区：
文献类型：
--
作者：
Yun Yapei;Sheng Hongting;Yu Jie;Bao Linquan;Du Yuanxin;Xu Fengqing;Yu Haizhu;Li Peng;Zhu Manzhou
原子精确纳米团簇（APNC）作为理想的模型催化剂，在深入理解多相催化反应机制方面具有巨大的优势。在保持结构不变性的前提下，提高APNC的活性是最关键的问题。在此，利用金属支撑相互作用（MSI）策略，我们通过将惰性纳米团簇[Pd3Cl（PPh2）2（PPh3）3]+[SbF6]−（表示为Pd3Cl）与功能性钛酸盐纳米管（TNT）相结合，制备了一种优异且可回收的有氧氧化催化剂。有前途的 Pd3Cl/TNT 复合材料在 30°C 和氧气压力下无需任何添加剂即可实现优异的转化率，选择性为 100%。这一结果在无需高温煅烧的配体纳米簇催化剂中是前所未有的。 Pd3Cl/TNT 复合材料和新鲜 Pd3Cl 纳米团簇活性之间的明显差异可以通过 MSI 效应的存在来解释，这一点通过 X 射线光电子能谱 (XPS) 分析得到证实。进一步进行理论模拟以阐明催化机制，表明MSI效应在动力学和热力学方面促进了关键的β-H消除步骤。这项工作提供了在原子水平上理解 MSI 对促进 APNC 催化性能的影响的例子。
Atomically precise nanoclusters (APNCs), as ideal model catalysts, revealed great advantages to deep‐understand of reaction mechanisms in heterogeneous catalysis. Boosting the activity of APNCs is the most critical issue under the premise of maintaining structure invariance. Herein, utilizing Metal‐Support Interaction (MSI) strategy, we prepared an excellent and recyclable catalyst for aerobic oxidation by combination of an otherwise inert nanocluster [Pd3Cl(PPh2)2(PPh3)3]+[SbF6]−(denoted as Pd3Cl) with functional titanate nanotubes (TNT). The promising Pd3Cl/TNT composite gives rise to excellent conversion with 100% selectivity without any additives at 30 °C under an oxygen pressure. This result is unprecedented in ligand‐on nanocluster catalysts without high temperature calcination. The distinct difference between their activities of Pd3Cl/TNT composite and fresh Pd3Cl nanocluster is explained by the presence of the MSI effect, as confirmed using X‐ray photoelectron spectroscopy (XPS) analysis. Theoretical simulations are further carried out to elucidate the catalytic mechanism, indicating the MSI effect promotes the crucial β‐H elimination step in both kinetic and thermodynamic aspects. This work presents the example of atomic‐level understanding of the effect of MSI on facilitating the APNCs catalytic properties.