Submerged Membrane Photo Reactor (SMPR) with Simultaneous Photo Degradation and TiO2 Catalyst Recovery for Efficient Dyes Removal

In this study, a polyvinylidene difluoride (PVDF) hollow fiber membrane module incorporated with TiO2 was submerged into a photocatalytic reactor to create a hybrid photocatalysis with membrane separation process (a submerged membrane photoreactor, SMPR), for advanced dyes wastewater treatment. The SMPR performance was assessed by the degradation of single component Rhodamine B (RhB) and degradation of mixed dyes (RhB and Methyl orange (MO)) in a binary solution. Several operational parameters such as the amount of catalyst loading, permeate flux, and the effect of aeration were studied. Fouling tendency on the membrane was also investigated to determine the optimum operating conditions. The results show that the synergetic effect of the low catalyst loading and permeate flux creates the environment for optimum light penetration for high photocatalytic activity as the hybrid system with low catalyst loading (0.5 g/L) and 66 L/m2h of flux with aeration at 1.3 L/min has proven to increase the photocatalysis performance by 20% with additional catalyst recovery. In addition, applying the low catalyst loading and flux permeate with aeration brings minimal fouling problems.

Catalyst Recovery, Regeneration and Reuse during Large-Scale Disinfection of Water Using Photocatalysis

The deployment of photocatalysis for remediation of water has not yet been realized, although laboratory-scale studies have demonstrated promise. Accomplishing this requires the development of photocatalysis as a process, including studying its efficiencies in remedying water when high volumes of water are processed, and addressing the recovery, possible regeneration and reuse of the photocatalysts. To that end, this work is aimed at demonstrating the use of a custom-built mobile platform for disinfecting large quantities of water. The benchtop platform built is capable of processing 15.14 L (4 gallons) per minute of water, with possibility for further scale-up. Preliminary studies on the catalyst recovery, regeneration and reuse via gravity-assisted settling, centrifugation and air plasma treatment indicated that 77% of Aeroxide® P25 titania (TiO2) nanoparticle and 57% of porous TiO2 nanowire photocatalysts could be recovered and regenerated for further use. Overall, this study indicated that process improvements, including increasing the kinetics of the photocatalysis, and optimization of the efficacies of the catalyst recovery and regeneration processes will make it useful for water remediation on any scale. More importantly, the portable and flexible nature of the benchtop photocatalysis system makes it amenable for use in conjunction with existing technologies for remedying large quantities of water.

Synthesis of C3-Symmetric Cinchona-Based Organocatalysts and Their Applications in Asymmetric Michael and Friedel–Crafts Reactions

In this work, anchoring of cinchona derivatives to trifunctional cores (hub approach) was demonstrated to obtain size-enlarged organocatalysts. By modifying the cinchona skeleton in different positions, we prepared four C3-symmetric size-enlarged cinchona derivatives (hub-cinchonas), which were tested as organocatalysts and their catalytic activities were compared with the parent cinchona (hydroquinine) catalyst. We showed that in the hydroxyalkylation reaction of indole, hydroquinine provides good enantioselectivities (up to 73% ee), while the four new size-enlarged derivatives resulted in significantly lower values (up to 29% ee) in this reaction. Anchoring cinchonas to trifunctional cores was found to facilitate nanofiltration-supported catalyst recovery using the PolarClean alternative solvent. The C3-symmetric size-enlarged organocatalysts were completely rejected by all the applied membranes, whereas the separation of hydroquinine was found to be insufficient when using organic solvent nanofiltration. Furthermore, the asymmetric catalysis was successfully demonstrated in the case of the Michael reaction of 1,3-diketones and trans-β-nitrostyrene using Hub3-cinchona (up to 96% ee) as a result of the positive effect of the C3-symmetric structure using a bulkier substrate. This equates to an increased selectivity of the catalyst in comparison to hydroquinine in the latter Michael reaction.

Synthesis of C3-Symmetric Cinchona-Based Organocatalysts and Their Application in Asymmetric Michael and Friedel–Crafts Reactions

In this work, anchoring of cinchona derivatives to trifunctional cores (hub approach) was demonstrated to obtain size-enlarged organocatalysts. By modifying the cinchona skeleton in different positions, we prepared four C3-symmetric size-enlarged cinchona derivatives (hub-cinchonas), which were tested as organocatalysts and their catalytic activities were compared with the parent cinchona (hydroquinine) catalyst. We showed that in the hydroxyalkylation reaction of indole, hydroquinine provides good enantioselectivities (up to 73% ee), while the four new size-enlarged derivatives gave significantly lower values (up to 29% ee) in this reaction. Anchoring cinchonas to trifunctional cores was found to facilitate nanofiltration-supported catalyst recovery using PolarClean alternative solvent. The C3-symmetric size-enlarged organocatalysts were completely rejected by all the applied membranes, whereas the separation of hydroquinine was found to be insufficient using organic solvent nanofiltration. Furthermore, the asymmetric catalysis was successfully demonstrated in the case of Michael reaction of 1,3-diketones and trans-β-nitrostyrene using Hub3-cinchona (up to 96% ee) as a result of the positive effect of the C3-symmetric structure using a bulkier substrate. This means an increased selectivity of the catalyst in comparison to hydroquinine in the latter Michael reaction.

The Stabilizing Effect of Pre-Equilibria: A Trifluoromethyl Complex as CF2 Reservoir in Catalytic Olefin Difluorocarbenation

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF₃ as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF₂ in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF₂-recombination side-reactions.

The Stabilizing Effect of Pre-Equilibria: A Trifluoromethyl Complex as CF2 Reservoir in Catalytic Olefin Difluorocarbenation

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF₃ as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF₂ in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF₂-recombination side-reactions.