Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface

Shan, Yu; Zhao, Xiao; Fonseca Guzman, Maria; Jana, Asmita; Chen, Shouping; Yu, Sunmoon; Ng, Ka Chon; Roh, Inwhan; Chen, Hao; Altoe, Virginia; Gilbert Corder, Stephanie N.; Bechtel, Hans A.; Qian, Jin; Salmeron, Miquel B.; Yang, Peidong

doi:10.1038/s41929-024-01119-2

Title: Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface

Journal Article · 25 March 2024 · Nature Catalysis

DOI: https://doi.org/10.1038/s41929-024-01119-2 · OSTI ID:2426886

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University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

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, in this work, 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2426886

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 4 Vol. 7; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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