A miniature CSTR cascade for continuous flow of reactions containing solids

Continuous handling of solids creates challenges for realizing continuous production of pharmaceuticals and fine chemicals. We present a new miniature continuous stirred-tank reactor (CSTR) cascade to handle solid-forming reactions in flow. Single-phase residence time distribution (RTD) measurements of the CSTR cascade reveal nearly ideal CSTR mixing behavior of the individual units. Consistency of experimental and predicted conversions of a Diels–Alder reaction further confirms the CSTR performance. Two solid-forming reactions, (i) glyoxal reacting with cyclohexylamine to form N,N′-dicyclohexylethylenediimine, (ii) sulfonylation of 2-octanol with methanesulfonyl chloride, demonstrate the ability of the reactor cascade to transport solid particles continuously for hours without significant signs of clogging

High quality epitaxial ZnSe and the relationship between electron mobility and photoluminescence characteristics

High quality epitaxial layers of nominally undoped ZnSe have been grown by metalorganic chemical vapor deposition at low temperature (325 °C) and pressure (30 Torr), using dimethylzinc and hydrogen selenide. All layers were unintentionally doped n type with net carrier concentrations of 6.4×10^(14)–1.5×10^(16) cm^(−3) and exhibited very high mobility at room temperature (up to 500 cm2/V s) as well as at 77 K, where the measured value of 9250 cm^2/V s is the highest so far reported for vapor phase growth. Additional evidence for the high quality of the material is provided by photoluminescence. Experimental results indicate a correlation between the photoluminescence characteristics and the electrical properties that may be useful in assessing the quality of ZnSe films

Direct Observation of Early-stage Quantum Dot Growth Mechanisms with High-temperature Ab Initio Molecular Dynamics

Colloidal quantum dots (QDs) exhibit highly desirable size- and shape-dependent properties for applications from electronic devices to imaging. Indium phosphide QDs have emerged as a primary candidate to replace the more toxic CdSe QDs, but production of InP QDs with the desired properties lags behind other QD materials due to a poor understanding of how to tune the growth process. Using high-temperature ab initio molecular dynamics (AIMD) simulations, we report the first direct observation of the early stage intermediates and subsequent formation of an InP cluster from separated indium and phosphorus precursors. In our simulations, indium agglomeration precedes formation of In-P bonds. We observe a predominantly intercomplex pathway in which In-P bonds form between one set of precursor copies while the carboxylate ligand of a second indium precursor in the agglomerated indium abstracts a ligand from the phosphorus precursor. This process produces an indium-rich cluster with structural properties comparable to those in bulk zinc-blende InP crystals. Minimum energy pathway characterization of the AIMD-sampled reaction events confirms these observations and identifies that In-carboxylate dissociation energetics solely determine the barrier along the In-P bond formation pathway, which is lower for intercomplex (13 kcal/mol) than intracomplex (21 kcal/mol) mechanisms. The phosphorus precursor chemistry, on the other hand, controls the thermodynamics of the reaction. Our observations of the differing roles of precursors in controlling QD formation strongly suggests that the challenges thus far encountered in InP QD synthesis optimization may be attributed to an overlooked need for a cooperative tuning strategy that simultaneously addresses the chemistry of both indium and phosphorus precursors.Comment: 40 pages, 9 figures, submitted for publicatio

Oscillatory multiphase flow strategy for chemistry and biology

Continuous multiphase flow strategies are commonly employed for high-throughput parameter screening of physical, chemical, and biological processes as well as continuous preparation of a wide range of fine chemicals and micro/nano particles with processing times up to 10 min. The inter-dependency of mixing and residence times, and their direct correlation with reactor length have limited the adaptation of multiphase flow strategies for studies of processes with relatively long processing times (0.5–24 h). In this frontier article, we describe an oscillatory multiphase flow strategy to decouple mixing and residence times and enable investigation of longer timescale experiments than typically feasible with conventional continuous multiphase flow approaches. We review current oscillatory multiphase flow technologies, provide an overview of the advancements of this relatively new strategy in chemistry and biology, and close with a perspective on future opportunities.Natural Sciences and Engineering Research Council of Canada (Postgraduate Fellowship

The role of flow in green chemistry and engineering

Flow chemistry and continuous processing can offer many ways to make synthesis a more sustainable practice. These technologies help bridge the large gap between academic and industrial settings by often providing a more reproducible, scalable, safe and efficient option for performing chemical reactions. In this review, we use selected examples to demonstrate how continuous methods of synthesis can be greener than batch synthesis on a small and a large scale.Natural Sciences and Engineering Research Council of Canada (NSERC postdoctoral fellowship

Efficient kinetic experiments in continuous flow microreactors

Flow chemistry is an enabling technology that can offer an automated and robust approach for the generation of reaction kinetics data. Recent studies have taken advantage of transient flows to quickly generate concentration profiles with various online analytical tools. In this work, we demonstrate an improved method where temperature and flow are transient throughout the reaction. It was observed that only two orthogonal temperature ramp experiments under the same transient flow condition were sufficient to characterize a Paal-Knorr (one step bimolecular) reaction within our chosen reaction space. This method further shortens the time and decreases the materials needed to collect sufficient kinetic data and provides a framework with which more complex kinetic studies could be performed

Carbon incorporation in ZnSe grown by metalorganic chemical vapor deposition

Carbon incorporation in ZnSe films grown by metalorganic chemical vapor deposition is reported. Secondary‐ion mass spectrometry measurements in ZnSe films grown from methylallylselenide and dimethylzinc show an enhanced carbon accumulation at the interface between ZnSe and GaAs. The carbon incorporation in the bulk ZnSe increases with the VI/II ratio and for a value of VI/II=3–4, the amount of incorporated carbon abruptly jumps to concentrations of 10^(21) cm^(−3), whereupon the films become polycrystalline. A new shallow peak I^C at 2.7920 eV dominates the near‐band‐edge low‐temperature photoluminescence spectra of all carbon‐contaminated ZnSe films. The intensity and linewidth of I^C increase with the VI/II ratio in a similar manner to the carbon concentration. This peak is proposed to be due to the radiative decay of excitons bound to a complex defect, which is associated with the presence of carbon in the films

Nested potassium hydroxide etching and protective coatings for silicon-based microreactors

We have developed a multilayer, multichannel silicon-based microreactor that uses elemental fluorine as a reagent and generates hydrogen fluoride as a byproduct. Nested potassium hydroxide etching (using silicon nitride and silicon oxide as masking materials) was developed to create a large number of channels (60 reaction channels connected to individual gas and liquid distributors) of significantly different depths (50–650 µm) with sloped walls (54.7° with respect to the (1 0 0) wafer surface) and precise control over their geometry. The wetted areas were coated with thermally grown silicon oxide and electron-beam evaporated nickel films to protect them from the corrosive fluorination environment. Up to four Pyrex layers were anodically bonded to three silicon layers in a total of six bonding steps to cap the microchannels and stack the reaction layers. The average pinhole density in as-evaporated films was 3 holes cm[superscript −2]. Heating during anodic bonding (up to 350 °C for 4 min) did not significantly alter the film composition. Upon fluorine exposure, nickel films (160 nm thick) deposited on an adhesion layer of Cr (10 nm) over an oxidized silicon substrate (up to 500 nm thick SiO[subscript 2]) led to the formation of a nickel fluoride passivation layer. This microreactor was used to investigate direct fluorinations at room temperature over several hours without visible signs of film erosion.MIT Microchemical Systems Technology Cente