Semiconductors are intriguing due to their unique electrical properties, particularly the behavior of their electrons in the presence of different stimuli (e.g., electric field, magnetic field, light irradiation), which differ greatly from conducting (i.e., metals) and insulating materials. In insulators and semiconductors, the available electronic states are discontinuous, with the existence of a gap between the lower energy states, commonly referred to as the valence band (VB), and the higher energy states, known as the conduction band (CB). The distinguishing factor between these materials is the size of the energy difference between the highest energy state in the VB and the lowest energy state in the CB, called the band gap. In insulators, the band gap is very large, making it difficult, if not impossible, to cause an electron to move from the VB to the CB. By comparison, semiconductors possess narrow to moderate band gaps, implying that it is possible to introduce enough energy to an electron to cause it to move from the VB to the CB, enabling electron transfer, the use of high energy electrons, or the emission of energy (i.e., photons) when the electron returns from the CB to the VB. The wide range of industrial application-specific requirements demands versatility in the target characteristics of semiconductor materials (e.g., size, morphology, composition, band gap, emission wavelength), which are vastly different from those commonly used in thin-film transistors. Typically, the semiconductor materials synthesized for use in the above applications are particulate materials produced across a range of sizes spanning five orders of magnitude (from just a few nm to hundreds of µm), and can be divided into two overarching categories, nano-and microsized particulate materials. Nanosized semiconductor materials, due in large part to their miniscule dimensions, present a variety of intriguing characteristics not observed in microsized semiconductor particles. First and foremost, if the dimensions of the semiconductor material decrease below a certain threshold known as the Bohr radius, the absorption and emission energies become highly dependent on the particle size, a phenomenon known as quantum confinement. [28-30] Moreover, nanosized structures have significantly larger surface-to-volume ratios which increases the surface contribution to the total free energy of the semiconductor materials, making them highly soluble [29] and therefore much easier to process and handle. Thus far, nanosized semiconductor particles have been effectively utilized in sensors, [7] LEDs, [9] Controlled synthesis of semiconductor nano/microparticles has attracted sub stantial attention for use in numerous applications from photovoltaics to photo catalysis and bioimaging due to the breadth of available physicochemical and optoelectronic properties. Microfluidic material synthesis strategies have recently been demonstrated as an effective technique for rapid development, controlled synthesis, and continuous manufacturing of solutionpr...
Microfluidic devices and systems have entered many areas of chemical engineering, and the rate of their adoption is only increasing. As we approach and adapt to the critical global challenges we face in the near future, it is important to consider the capabilities of flow chemistry and its applications in next-generation technologies for sustainability, energy production, and tailor-made specialty chemicals. We present the introduction of microfluidics into the fundamental unit operations of chemical engineering. We discuss the traits and advantages of microfluidic approaches to different reactive systems, both well-established and emerging, with a focus on the integration of modular microfluidic devices into high-efficiency experimental platforms for accelerated process optimization and intensified continuous manufacturing. Finally, we discuss the current state and new horizons in self-driven experimentation in flow chemistry for both intelligent exploration through the chemical universe and distributed manufacturing. Expected final online publication date for the Annual Review of Chemical and Biomolecular Engineering, Volume 13 is October 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.
A microfluidic strategy is developed for continuous synthesis of monodisperse yolk−shell titania microspheres. The continuous flow synthesis of titania microparticles is achieved by decoupling the microdroplet formation and interfacial hydrolysis reaction steps by utilizing a polar aprotic solvent as the continuous phase in the microreactor. The decoupling of the precursor microdroplet formation and the hydrolysis reaction allows titania synthesis throughputs an order of magnitude higher than those previously reported in a single-channel flow reactor (∼0.1 g/h calcined microparticles), without affecting the microreactor lifetime due to clogging. Flow synthesis and dynamics across a broad range of precursor flow rates are examined, while effects of flow synthesis parameters, including the precursor to continuous phase flow rate ratio, precursor composition, and calcination temperature on the surface morphology, size, and composition of the resulting titania microparticles, are explored in detail. Titania microparticle size can be controlled by variation in the precursor to continuous phase flow rate ratio. The surface morphology and porosity of the in-flow synthesized titania microparticles can be varied by adjusting the precursor composition, while the crystalline phase can be tuned by varying the calcination temperature.
Macroporous microbeads are synthesized by microfluidic production of silica-loaded polymeric microdroplets followed by porogen removal via selective etching.
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