Bimetallic nanoparticles often show properties superior to their single-component counterparts. However, the large parameter space, including size, structure, composition, and spatial arrangement, impedes the discovery of the best nanoparticles for a given application. High-throughput methods that can control the composition and spatial arrangement of the nanoparticles are desirable for accelerated materials discovery. Herein, we report a methodology for synthesizing bimetallic alloy nanoparticle arrays with precise control over their composition and spatial arrangement. A dual-channel nanopipet is used, and nanofluidic control in the nanopipet further enables precise tuning of the electrodeposition rate of each element, which determines the final composition of the nanoparticle. The composition control is validated by finite element simulation as well as electrochemical and elemental analyses. The scope of the particles demonstrated includes Cu–Ag, Cu–Pt, Au–Pt, Cu–Pb, and Co–Ni. We further demonstrate surface patterning using Cu–Ag alloys with precise control of the location and composition of each pixel. Additionally, combining the nanoparticle alloy synthesis method with scanning electrochemical cell microscopy (SECCM) allows for fast screening of electrocatalysts. The method is generally applicable for synthesizing metal nanoparticles that can be electrodeposited, which is important toward developing automated synthesis and screening systems for accelerated material discovery in electrocatalysis.
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On-Demand Electrochemical Fabrication of Ordered Nanoparticle Arrays using Scanning Electrochemical Cell Microscopy
Well-ordered nanoparticle arrays are attractive platforms for a variety of analytical applications, but the fabrication of such arrays is generally challenging. Here, it is demonstrated that scanning electrochemical cell microscopy (SECCM) can be used as a powerful, instantly reconfigurable tool for the fabrication of ordered nanoparticle arrays. Using SECCM, Ag nanoparticle arrays were straightforwardly fabricated via electrodeposition at the interface between a substrate electrode and an electrolyte-filled pipet. By dynamically monitoring the currents flowing in an SECCM cell, individual nucleation and growth events could be detected and controlled to yield individual nanoparticles of controlled size. Characterization of the resulting arrays demonstrate that this SECCM-based approach enables spatial control of nanoparticle location comparable with the terminal diameter of the pipet employed and straightforward control over the volume of material deposited at each site within an array. These results provide further evidence for the utility of probe-based electrochemical techniques such as SECCM as tools for surface modification in addition to analysis.
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- NSF-PAR ID:
- 10383450
- Date Published:
- Journal Name:
- ACS Nano
- ISSN:
- 1936-0851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Hydrogels have emerged as prototypical stimuli‐responsive materials with potential applications in soft robotics, microfluidics, tissue engineering, and adaptive optics. To leverage the full potential of these materials, fabrication techniques capable of simultaneous control of microstructure, device architecture, and interfacial stability, that is, adhesion of hydrogel components to support substrates, are needed. A universal strategy for the microfabrication of hydrogel‐based devices with robust substrate adhesion amenable to use in liquid environments would enable numerous applications. This manuscript reports a general approach for the facile production of covalently attached, ordered arrays of microscale hydrogels (microgels) on silicone supports. Specifically, silicone‐based templates are used to: i) drive mechanical assembly of prepolymer droplets into well‐defined geometries and morphologies, and ii) present appropriate conjugation moieties to fix gels in place during photoinitiated crosslinking via a “graft from” polymerization scheme. Automated processing enabled rapid microgel array production for characterization, testing, and application. Furthermore, the stimuli‐responsive microlensing properties of these arrays, via contractile modulated refractive index, are demonstrated. This process is directly applicable to the fabrication of adaptive optofluidic systems and can be further applied to advanced functional systems such as soft actuators and robotics, and 3D cell culture technologies.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsnano.2c09336
