Atmospheric-Pressure Conversion of CO2 to Cyclic Carbonates over Constrained Dinuclear Iron Catalysts.

The conversion of CO2 and epoxides to cyclic carbonates over a silica-supported di-iron(III) complex having a reduced Robson macrocycle ligand system is shown to proceed at 1 atm and 80 °C, exclusively producing the cis-cyclohexene carbonate from cyclohexene oxide. We examine the effect of immobilization configuration to show that the complex grafted in a semirigid configuration catalytically outperforms the rigid, flexible configurations and even the homogeneous counterparts. Using the semirigid catalyst, we are able to obtain a TON of up to 800 and a TOF of up to 37 h-1 under 1 atm CO2. The catalyst is shown to be recyclable with only minor leaching and no change to product selectivity. We further examine a range of epoxides with varying electron-withdrawing/donating properties. This work highlights the benefit arising from the constraining effect of a solid surface, akin to the role of hydrogen bonds in enzyme catalysts, and the importance of correctly balancing it.

First-Principle Colloidal Gate for Controlling Liquid and Molecule Flow Using 2D Claylike Nanoparticles.

Herein, we exploit the natural tendency of two-dimensional (2D) clay nanoparticles to self-assemble and restrict water permeability in soils to fabricate a first of its kind synthetic, pH-activated, reversible, and tunable colloidal flow gate. To realize this, we studied the effect of the pH level of a suspension of claylike layered double hydroxide (LDH) nanoparticles on the LDH coagulation process. We then packed the LDH into a fixed-bed column and examined the effect of pH on mass transport through the column. We found that the 2D platelike LDH particles coagulate in an edge-to-edge configuration, which renders highly nonisotropic aggregates, pivotal for obstructing the transport of liquid and molecules therein. We showed that the coagulation and flow through the column may be regulated by imposing various pH levels as an external stimulus to affect LDH zeta potential. Hence, this work shows that the flow through a column comprising a 2D particle bed can be regulated in a reversible manner by simply alternating the pH of the wash solution, equilibration time, or gate dimensions. Furthermore, we show that, subject to pH treatment, we may open and close the colloidal gate for the transport of large molecules and provide selective transport thereof.

A rare 4-fold interpenetrated metal-organic framework constructed from an anionic indium-based node and a cationic dicopper linker.

A unique 4-fold interpenetrated metal-organic framework, TIF-1, was synthesized by combining an anionic indium node with a cationic linker. This framework shows a rare type of 4-fold interpenetrated dia network, constructed from tessellation of biangular and tetragonal type metal-organic micropores. The porosity of TIF-1 is moderate due to four-fold interpenetration and charge-balancing anions. The cationic feature of this MOF may give good efficiency for selective small anion exchange or separation. In addition, the thermal stability and moderate CO2 adsorption property of the complex were studied.