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Engineered metal nanoparticles (metal NPs) possess unique size -dependent optical and electronic properties that could enable new applications in biomedicine, energy generation, microelectronics, micro-optics, and catalysis. For metal NPs to make a mark in these fields, however, new synthetic strategies must be developed that permit NP synthesis on the kilogram scale, while maintaining precise control over NP physiochemical properties (size, shape, composition, and surface chemistry). Currently, NP batch syntheses produce product on the milligram scale and rely on synthetic strategies that are not readily amenable to scale-up. Flow reactor systems (including lab-on-a-chip devices) provide a synthesis platform that can circumvent many of the traditional limitations of batch-scale NP syntheses. These reactors provide more uniform reagent mixing, more uniform heat transfer, opportunities to interface  in situ  monitoring technology, and allow product yield to be scaled up simply by running multiple reactors in parallel. While many NP syntheses have been successfully transferred to  microfluidic  reactor systems, microfluidic reactor fabrication is time intensive and typically requires sophisticated lithography facilities. Consequently,  millifluidic  flow reactors (reactors with channel dimensions of 0.5–10.0 mm) are gaining popularity in NP synthesis. These millifluidic reactors provide many of the same synthetic advantages as microfluidic devices, but are simpler to construct, easier to reconfigure, and more straightforward to interface with  in situ  monitoring techniques. In this chapter, we will discuss the progress that has been made in developing millifluidic reactors for functionalized metal NP synthesis. First, we will review the basic wet-chemical strategies used to control metal NP size and shape in batch reactors. We will then survey some of the basic principles of millifluidic device design, construction, and operation. We will also discuss the potential for incorporating  in situ  monitoring for quality control during synthesis. We will conclude by highlighting some particularly relevant examples of millifluidic metal NP synthesis that have set new standards for metal NP size, shape, and surface chemistry control.

Size and shape control of metal nanoparticles in millifluidic reactors