Although harmful NO and SO2 in flue gas can be separately removed by the established technologies, such as selective catalytic reduction (SCR) or selective non-catalytic reduction(SNCR) and wet scrubbing process, integrated method for simultaneous desulfurization and denitrification is still in demand and attractive to improve energy efficiency and reduce investment and operation cost. Upon this, a novel sulfur-cycling integrated technology of simultaneous catalytic desulfurization and denitrification with H2S (H2S-SCDD) has been proposed and is considered to be a profitable solution to the flue gas treatment. However, the high operation temperature (over 600oC) was required in the H2S-SCDD process for the sulfur-cycling flue gas treatment as reported. To realize the H2S-SCDD process at low temperatures, different catalysts were prepared and tested, such as Al2O3-TiO2 (AT) loaded with transition metal oxides. The results show that, CeO2-loaded AT catalyst (Ce-AT) was the suitable catalyst to balance NO and SO2 removal by the H2S-SCDD process in the temperature range of 300−400℃. Increasing Ce loading on AT significantly increased the NO conversion but had a slightly negative effect on SO2 reduction. With 15% Ce loading on AT catalyst (Ce15-AT), the optimal temperature for the H2S-SCDD process was 240—280℃. While at 280℃, the SO2 and NO conversions were about 75% and 90%, respectively, implying the efficient and simultaneous reduction of NO and SO2. Upon this, the sulfur-cycling process is promising and attractive for flue gas treatment in industrial sectors.

The paper is focused on investigation of layered double hydroxides (LDH) functionalized with ionic liquid (IL) as novel catalytic / initiating system for ring opening polymerization (ROP) of ε-caprolactone. Firstly, the Ca2+/Al3+ LDH nanoparticles were synthesized via a co-precipitation method followed by the anion exchange using phosphonium IL with decanoate anions producing the modified LDH with interlayered IL-anions. Then, the progress of microwave-assisted polymerization in the presence of the modified LDH was studied showing the anionic mechanism of ROP initiated by the water molecules, which were adsorbed on the LDH surface and intercalated in the LDH galleries. The whole polymerization was significantly accelerated by microwave energy, which induced molecular rotations of the intercalated IL-anions leading to LDH delamination and exfoliation into individual nanosheets, which made the catalytic sites (IL-anions) easily accessible for the εCL molecules. The kinetics of microwave-assisted ROP thus showed a 4.6-fold increase of the reaction rate compared to the polymerization performed under conventional heating. Activation enthalpy and entropy were calculated for the microwave-assisted polymerizations initiated by the modified LDH. The use of microwave-active catalytic-initiating LDH nanoparticles enables to synthesize the organometallic catalyst-free PCL or, at higher LDH loadings, the highly-exfoliated PCL/LDH nanocomposites, which are highly desirable for e.g. packaging materials.

This work presented a microfluidic processing of zeolite film in a capillary microreactor and its potential application for biomass conversion. Uniform and continuous HZSM-5 zeolite film was fabricated under a continuous flow hydrothermal system in which the film thickness could be precisely tuned by flow rate and synthesis time. The catalytic performance of this acidic HZSM-5 film capillary microreactor was evaluated by continuous flow acetalisation reaction of glycerol with acetone, affording ~62.61% solketal yield under mild and solvent free conditions. No deactivation was observed even after 100 h, indicating the excellent stability of this HZSM-5 film capillary microreactor. This microfluidic processing strategy provided an extended applicability in the fabrication of zeolite films-based capillary microchannel with high length-to-diameter ratio or other chip-based microchannel devices.

D-(-)-pantolactone (D-PL) is the key chiral intermediate to synthesize calcium D-pantothenate. In previous study, a conjugated polyketone reductase (CduCPR) was discovered to efficiently catalyse ketopantolactone (KPL) to D-PL with a high stereoselectivity. Nevertheless, the method was limited due to the expensive coenzyme, nicotinamide adenine dinucleotide phosphate hydrate (NADPH), and the poor stability of substrate KPL in pure aqueous buffer. Here, to overcome these problems, we developed a whole-cell biotransformation process to produce D-PL in a biphasic reaction system. Recombinant CduCPR and glucose dehydrogenase (BsuGDH) were co-expressed in Escherichia coli to simultaneously achieve the synthesis of D-PL and the regeneration of NADPH. The biphasic reaction system contained 15% dichloromethane (v/v) significantly inhibited the undesirable hydrolysis of KPL. Approximate 2.8 % of 100 mM KPL was spontaneously hydrolysed to ketopantoic acid in the biphasic system, which was lower than 54% of pure aqueous buffer. The biphasic reaction system was optimized and scaled up to prepare D-PL. In a fed-batch biphasic reaction, the substrate KPL was continuously fed into the reactor after a batch reaction. The D-PL concentration reached 0.77 mol/L in the reaction mixture at 7 h, and its enantiomeric excess was 99%. The space time yield was calculated as 343.2 g·L-1·d-1. This study presented an alternative method to asymmetrically synthesize enantiopure D-PL for further industrial application.

Owing to the low boiling point, Tetrahydrofuran (THF) forms an economical choice of solvent in biorenewable processing. Multifold acceleration in reaction rates is experimentally observed for Br{\o}nsted acid catalyzed reactions in THF, as compared to that of water. Herein, utilizing ab-initio Car-Parrinello Molecular Dynamics (CPMD), classical Molecular Dynamics (MD) and Density Functional Theory (DFT) simulations, a systematic theoretical framework is presented to explain the significant differences in the reactivity of Br{\o}nsted acid protons in THF as compared to that of water. The probe reaction of choice is the dehydration of 4-hydroxy-6-methyl lactone (HML) obtained from a biomass-derived substrate. Classical MD simulations are elucidating the hydrogen bonding networks formed around the hydroxyl group of the reactant HML in presence of explicit solvation environment of water and THF. Activation free energy barrier for the water removal step is calculated using CPMD metadynamics simulations. In THF, the free energy barrier is 107 kJ/mol, which is observed to be lower by 26 kJ/mol, as compared to that of water. This significant difference in activation free energies for the dehydration step explains the difference in reactivity. Static DFT simulations further elaborated the effect of first solvation shell, around the hydroxyl substituent in describing the activation barriers of the dehydration reaction. While the solvent environment in DFT simulations is kept implicit in nature, few explicit molecules of THF and water are allowed to interact with the hydroxyl group and $\beta$-carbon of HML. Activation energies for the dehydration of HML are calculated to be 103 kJ/mol in the pure water environment. Akin to the difference in free energy barriers obtained from CPMD calculations, the activation energy calculated from DFT is observed to be 25 kJ/mol lower in THF as compared to that of water.

An automated, droplet-flow microfluidic system explores and optimizes Pd-catalyzed Suzuki-Miyaura cross-coupling reactions. A smart optimal DoE-based algorithm is implemented to increase the turnover number and yield of the catalytic system considering both discrete variables-palladacycle and ligand-and continuous variables-temperature, time, and loading-simultaneously. The use of feedback allows for experiments to be run with catalysts and under conditions more likely to produce an optimum; consequently complex reaction optimizations are completed within 96 experiments. Response surfaces predicting reaction performance near the optima are generated and validated. From the screening results, shared attributes of successful precatalysts are identified, leading to improved understanding of the influence of ligand selection upon transmetalation and oxidative addition in the reaction mechanism. Dialkylbiarylphosphine, trialkylphosphine, and bidentate ligands are assessed.

Today, the generation of kinetic models is still seen as a resource intensive and specialised activity. We report an efficient method of generating reaction profiles from transient flows using a state-of-the-art continuous-flow platform. Experimental data for multistep aromatic nucleophilic substitution reactions are collected from an automated linear gradient flow ramp with online HPLC at the reactor outlet. Using this approach, we generated 16 profiles, at 3 different inlet concentrations and 4 temperatures, in less than 3 hours run time. The kinetic parameters, 4 rate constants and 4 activation energies were fitted with less than 4% uncertainty. We derived an expression for the error in the observed rate constants due to dispersion and showed that such error is 5% or lower. The large range of operational conditions prevented the need to isolate individual reaction steps. Our approach enables early identification of the sensitivity of product quality to parameter changes and early use of unit operation models to identify optimal process-equipment combinations in silico, greatly reducing scale up risks.

A versatile multistep continuous flow setup is reported for the four-step conversion of anilines into pyrazole products. The synthesis machine incorporates the use of amine-redox chemistry through diazotization and a metal-free vitamin C mediated reduction. The machine can be used for the synthesis of an array of analogues or the scale up of an individual target.

An electrochemical cell coupled with a recycle loop through a transmission FTIR cell is employed in studies of two free radical organic reactions, the oxidation of allylic alcohols and the trifluoromethylation of heteroarenes. Rapid mixing through the recycle loop allows continuous monitoring of reaction progress. Electrochemical generation of free radicals allows their controlled mediation into the reaction mixture for more efficient reaction. Kinetic profiles provide mechanistic insight into reactions under electrochemical control.