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1.
J Am Chem Soc ; 145(37): 20208-20213, 2023 Sep 20.
Article in English | MEDLINE | ID: mdl-37677089

ABSTRACT

Advances in electrocatalysis research rely heavily on building a thorough mechanistic understanding of catalyst active sites under realistic operating conditions. Only recently have techniques emerged that enable sensitive spectroscopic data collection to distinguish catalytically relevant surface sites from the underlying bulk material under applied potential in the presence of an electrolyte layer. Here, we demonstrate that operando high-energy-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) is a powerful spectroscopic method which offers critical surface chemistry insights in CO2 electroreduction with sub-electronvolt energy resolution using hard X-rays. Combined with the high surface area-to-volume ratio of 5 nm copper nanoparticles, operando HERFD-XAS allows us to observe with clear evidence the breaking of chemical bonds between the ligands and the Cu surface as part of the ligand desorption process occurring under electrochemical potentials relevant for the CO2 reduction reaction (CO2RR). In addition, the dynamic evolution of oxidation state and coordination number throughout the operation of the nanocatalyst was continuously tracked. With these results in hand, undercoordinated metallic copper nanograins are proposed to be the real active sites in the CO2RR. This work emphasizes the importance of HERFD-XAS compared to routine XAS in catalyst characterization and mechanism exploration, especially in the complicated electrochemical CO2RR.

2.
STAR Protoc ; 4(3): 102410, 2023 Sep 15.
Article in English | MEDLINE | ID: mdl-37393611

ABSTRACT

Plasmonic nanoparticles and nanocrystalline materials have broad applicability in catalysis, optoelectronics, sensing, and sustainability. Below, we detail a robust protocol for the synthesis of bimetallic Au-Sn nanoparticles in mild, aqueous conditions. This protocol describes the steps for synthesizing gold nanoparticle seeds, diffusing Sn into the seeds by chemical reduction, and the optical and structural analysis by UV-visible spectroscopy, X-ray diffraction, and electron microscopy. For complete details on the use and execution of this protocol, please refer to Fonseca Guzman et al.1.


Subject(s)
Metal Nanoparticles , Tin , Tin/chemistry , Gold/chemistry , Gold Alloys , Silver/chemistry , Metal Nanoparticles/chemistry
3.
Nature ; 614(7947): 262-269, 2023 02.
Article in English | MEDLINE | ID: mdl-36755171

ABSTRACT

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3-5. Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis before complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.

4.
Nanoscale ; 14(3): 602-611, 2022 Jan 20.
Article in English | MEDLINE | ID: mdl-34985484

ABSTRACT

Plasmonic materials are promising for applications in enhanced sensing, energy, and advanced optical communications. These applications, however, often require chemical and physical functionality that is suited and designed for the specific application. In particular, plasmonic materials need to access the wide spectral range from the ultraviolet to the mid-infrared in addition to having the requisite surface characteristics, temperature dependence, or structural features that are not intrinsic to or easily accessed by the noble metals. Herein, we describe current progress and identify promising strategies for further expanding the capabilities of plasmonic materials both across the electromagnetic spectrum and in functional areas that can enable new technology and opportunities.

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