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

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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.

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Fig. 1: Real-time molecular picture of microenvironment formation probed by in situ nano-FTIR and SERS.
Fig. 2: In situ nano-FTIR setup and determination of initial binding configuration of ligands on Ag NPs.
Fig. 3: Spatially resolved bidentate-to-monodentate transformation and structural dynamics.
Fig. 4: Bias-induced second-bond cleavage towards formation of the catalytic interlayer.

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All data are available from the authors on reasonable request.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, & Biosciences Division, of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231 and FWP CH030201 (Catalysis Research Program). This research used resources of the Advanced Light Source, a DOE Office of Science User Facility under the same contract number. Nano-FTIR was performed at beamlines 2.4 and 5.4 in ALS. XPS, SEM and STEM/energy-dispersive X-Ray were performed at the Molecular Foundry, supported by the Office of Science, Office of Basic Energy Sciences of DOE under contract number DE-AC02-05CH11231. Y.S. acknowledges fellowship from University of Chinese Academy of Sciences. X.Z. is supported by an NSF-BSF grant (no. 1906014). J.Q. is supported by the Laboratory Directed Research and Development Program of Lawrence Berkeley National Laboratory through contract no. DE-AC02-05CH11231, and by the Gas Phase Chemical Physics Program of the US DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, through contract no. DE-AC02-05CH11231. A.J. is supported by an Early Career Award in the Condensed Phase and Interfacial Molecular Science Program, in the Chemical Sciences Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the United States DoE under contract no. DE-AC02-05CH11231, and also by the Gas Phase Chemical Physics Program of the US DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, through contract no. DE-AC02-05CH11231. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US DOE, under contract no. DE-AC02-05CH11231, using NERSC award no. BES-ERCAP0020767. H.C. is supported by the Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, of the US DOE under contract nos. DE-AC02-05CH11231 and FWP CH030201 (Catalysis Research Program). We also thank J. Jin for the informative discussions.

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Author notes

  1. These authors contributed equally: Yu Shan, Xiao Zhao, Maria Fonseca Guzman.

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California at Berkeley, Berkeley, CA, USA

    Yu Shan, Xiao Zhao, Shouping Chen, Sunmoon Yu, Miquel B. Salmeron & Peidong Yang

  2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Yu Shan, Maria Fonseca Guzman, Asmita Jana, Shouping Chen, Sunmoon Yu, Inwhan Roh, Hao Chen, Jin Qian, Miquel B. Salmeron & Peidong Yang

  3. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Xiao Zhao, Ka Chon Ng & Miquel B. Salmeron

  4. Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA

    Maria Fonseca Guzman, Inwhan Roh & Peidong Yang

  5. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Asmita Jana, Stephanie N. Gilbert Corder & Hans A. Bechtel

  6. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Virginia Altoe

  7. Kavli Energy NanoScience Institute, Berkeley, CA, USA

    Peidong Yang

Authors
  1. Yu Shan
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Contributions

Y.S., X.Z. and M.F.G. designed this project under the guidance of M.B.S. and P.Y. Y.S. synthesized materials and conducted electrochemical and electron microscopy characterization, with the help of S.C., S.Y., I.R., H.C. and V.A. Y.S. and X.Z. performed the nano-FTIR experiment and analysed data, assisted by S.N.G.C. and H.A.B. M.F.G. conducted Raman measurements. A.J. and J.Q. performed DFT calculations. SFG measurements were conducted by K.C.N. and X.Z. All authors contributed to discussion of the experimental results and manuscript preparation.

Corresponding authors

Correspondence to Miquel B. Salmeron or Peidong Yang.

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Peer review information

Nature Catalysis thanks John Flake, Sangheon Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–7, methods, Figs. 1–21, Tables 1–7 and references.

Supplementary Data 1

Atomic coordinates of optimized bidentate structure.

Supplementary Data 2

Atomic coordinates of optimized monodentate structure.

Supplementary Data 3

Atomic coordinates of optimized free ligand structure.

Supplementary Video 1

The video shows the motion of vibrational mode with a wavenumber of 899 cm−1.

Supplementary Video 2

The video shows the motion of vibrational mode with a wavenumber of 969 cm−1.

Supplementary Video 3

The video shows the motion of vibrational mode with a wavenumber of 998 cm−1.

Supplementary Video 4

The video shows the motion of vibrational mode with a wavenumber of 1,006 cm−1.

Supplementary Video 5

The video shows the motion of vibrational mode with a wavenumber of 1,018 cm−1.

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Shan, Y., Zhao, X., Fonseca Guzman, M. et al. Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface. Nat Catal (2024). https://ift.tt/1bhZQWV

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