Shuaiwei Jiang, Jiawei Xue, Tong Liu, Hui Huang, Airong Xu, Dong Liu, Qiquan Luo, Jun Bao, Xiaokang Liu, Tao Ding, Zheng Jiang, Tao Yao
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引用次数: 0
摘要
了解固/液电化学界面上的界面羟基(OH)特性对于解读协同催化作用至关重要。然而,在原子水平上阐明界面羟基和相邻反应物之间的空间距离对反应动力学的影响仍然具有挑战性。在此,我们利用原位红外纳米光谱和原位红外光谱技术,将异质双位点催化中依赖于距离的协同作用可视化。这些光谱技术可直接识别协同物种的空间分布,并揭示出羟基促进反应物的去质子化过程取决于双位催化剂中的位点距离。通过调节铱-钴对的距离,我们发现在 7.9 Å 的最佳距离上,OH 的生成和消耗之间的动态平衡产生了高效的协同作用;而在更远或更短的距离上,OH 与中间产物之间的空间不接触性和阻力会导致 OH 积累,从而削弱协同效应。因此,以甲酸氧化反应为探针反应,空间距离与质量活性之间形成了一条火山状曲线。这一概念也可扩展到亲氧化金属,如 Ir-Ru 对,其中的火山曲线和动态平衡进一步证明了空间距离的普遍意义。
Visualization of the Distance-Dependent Synergistic Interaction in Heterogeneous Dual-Site Catalysis.
Understanding the characteristics of interfacial hydroxyl (OH) at the solid/liquid electrochemical interface is crucial for deciphering synergistic catalysis. However, it remains challenging to elucidate the influences of spatial distance between interfacial OH and neighboring reactants on reaction kinetics at the atomic level. Herein, we visualize the distance-dependent synergistic interaction in heterogeneous dual-site catalysis by using ex-situ infrared nanospectroscopy and in situ infrared spectroscopy techniques. These spectroscopic techniques achieve direct identification of the spatial distribution of synergistic species and reveal that OH facilitates the reactant deprotonation process depending on site distances in dual-site catalysts. Via modulating Ir-Co pair distances, we find that the dynamic equilibrium between generation and consumption of OH accounts for high-efficiency synergism at the optimized distance of 7.9 Å. At farther or shorter distances, spatial inaccessibility and resistance of OH with intermediates lead to OH accumulation, thereby diminishing the synergistic effect. Hence, a volcano-shaped curve has been established between the spatial distance and mass activity using formic acid oxidation as the probe reaction. This notion could also be extended to oxophilic metals, like Ir-Ru pairs, where volcano curves and dynamic equilibrium further evidence the universal significance of spatial distances.
期刊介绍:
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