Yu Shan, Xiao Zhao, Maria Fonseca Guzman, Asmita Jana, Shouping Chen, Sunmoon Yu, Ka Chon Ng, Inwhan Roh, Hao Chen, Virginia Altoe, Stephanie N. Gilbert Corder, Hans A. Bechtel, Jin Qian, Miquel B. Salmeron, Peidong Yang
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引用次数: 0
Abstract
The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO2-to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience. Nanoparticles are often stabilized by capping ligands but the specific role of such ligands during catalytic processes is often ignored. Now, in situ techniques including spatially resolved infrared nanospectroscopy reveal the ligand-assisted formation of a catalytic microenvironment on the surface of silver nanoparticles with nanoscale precision during CO2 electroreduction.
纳米粒子(NPs)表面配体对外界刺激的动态反应决定了 NP-配体系统的功能。例如,在电催化过程中,NP 表面配体的集体解离可导致 NP/配体间层的产生,这种微环境对 CO2 到 CO 的转化具有高度活性和选择性。然而,由于缺乏高空间分辨率的原位表征技术,阻碍了对夹层形成机理的分子层面的全面了解。在这里,我们利用原位红外纳米光谱学和表面增强拉曼光谱,揭示了电化学偏压诱导的表面配体连续键裂解机制,从而导致 NP/被缚配体夹层的形成。这种实时的分子洞察力可影响多种催化系统中封闭局部场的设计。此外,所展示的捕捉纳米分辨动态分子尺度事件的能力为利用受控局部分子行为实现纳米科学多个研究领域所需的功能带来了希望。
期刊介绍:
Nature Catalysis serves as a platform for researchers across chemistry and related fields, focusing on homogeneous catalysis, heterogeneous catalysis, and biocatalysts, encompassing both fundamental and applied studies. With a particular emphasis on advancing sustainable industries and processes, the journal provides comprehensive coverage of catalysis research, appealing to scientists, engineers, and researchers in academia and industry.
Maintaining the high standards of the Nature brand, Nature Catalysis boasts a dedicated team of professional editors, rigorous peer-review processes, and swift publication times, ensuring editorial independence and quality. The journal publishes work spanning heterogeneous catalysis, homogeneous catalysis, and biocatalysis, covering areas such as catalytic synthesis, mechanisms, characterization, computational studies, nanoparticle catalysis, electrocatalysis, photocatalysis, environmental catalysis, asymmetric catalysis, and various forms of organocatalysis.