12 research outputs found
Molecular Dynamics Simulations on Gate Opening in ZIF-8: Identification of Factors for Ethane and Propane Separation
Gate opening of zeolitic imidazolate
frameworks (ZIFs) is an important
microscopic phenomenon in explaining the adsorption, diffusion, and
separation processes for large guest molecules. We present a force
field, with input from density functional theory (DFT) calculations,
for the molecular dynamics simulation on the gate opening in ZIF-8.
The computed self-diffusivities for sorbed C1 to C3 hydrocarbons were
in good agreement with the experimental values. The observed sharp
diffusion separation from C<sub>2</sub>H<sub>6</sub> to C<sub>3</sub>H<sub>8</sub> was elucidated by investigating the conformations of
the guest molecules integrated with the flexibility of the host framework
One-Pot Synthesis of <i>N</i>‑(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere
A facile
one-pot synthesis of <i>N</i>-(α-peroxy)Âindole and <i>N</i>-(α-peroxy)Âcarbazole has been developed using metal-free,
organo-acid-catalyzed three-component condensation reactions of indole/carbazole,
aldehyde, and peroxide. Based on the reaction discovered, a new synthetic
proposal for Fumitremorgin A and Verruculogen is introduced. Such
a protocol could be easily handled and scaled up in an open atmosphere
with a wide substrate scope, enabling the construction of a new molecule
library
Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN<sup>3</sup>–Pincer Ligand Containing a Phenanthroline Backbone
Selective catalytic hydrogenation
of aromatic compounds is extremely
challenging using transition-metal catalysts. Hydrogenation of arenols
to substituted tetrahydronaphthols or cyclohexanols has been reported
only with heterogeneous catalysts. Herein, we demonstrate the selective
hydrogenation of arenols to the corresponding tetrahydronaphthols
or cyclohexanols catalyzed by a phenanthroline-based PN<sup>3</sup>-ruthenium pincer catalyst
Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN<sup>3</sup>–Pincer Ligand Containing a Phenanthroline Backbone
Selective catalytic hydrogenation
of aromatic compounds is extremely
challenging using transition-metal catalysts. Hydrogenation of arenols
to substituted tetrahydronaphthols or cyclohexanols has been reported
only with heterogeneous catalysts. Herein, we demonstrate the selective
hydrogenation of arenols to the corresponding tetrahydronaphthols
or cyclohexanols catalyzed by a phenanthroline-based PN<sup>3</sup>-ruthenium pincer catalyst
Enhanced Reactivities toward Amines by Introducing an Imine Arm to the Pincer Ligand: Direct Coupling of Two Amines To Form an Imine Without Oxidant
Dehydrogenative homocoupling of primary alcohols to form
esters
and coupling of amines to form imines was accomplished using a class
of novel pincer ruthenium complexes. The reactivities of the ruthenium
pincer complexes for the direct coupling of amines to form imines
were enhanced by introducing an imine arm to the pincer ligand. Selective
oxidation of benzylamines to imines was achieved using aniline derivatives
as the substrate and solvent
Synthesis of Sub-10 nm Two-Dimensional Covalent Organic Thin Film with Sharp Molecular Sieving Nanofiltration
We
demonstrated here a novel and facile synthesis of two-dimensional
(2D) covalent organic thin film with pore size around 1.5 nm using
a planar, amphiphilic and substituted heptacyclic truxene based triamine
and a simple dialdehyde as building blocks by dynamic imine bond formation
at the air/water interface using Langmuir–Blodgett (LB) method.
Optical microscopy (OM), scanning electron microscopy (SEM), transmission
electron microscopy (TEM), and atomic force microscopy (AFM), all
unanimously showed the formation of large, molecularly thin and free-standing
membrane that can be easily transferred on different substrate surfaces.
The 2D membrane supported on a porous polysulfone showed a rejection
rate of 64 and 71% for NaCl and MgSO<sub>4</sub>, respectively, and
a clear molecular sieving at molecular size around 1.3 nm, which demonstrated
a great potential in the application of pretreatment of seawater desalination
and separation of organic molecules
Using UCST Ionic Liquid as a Draw Solute in Forward Osmosis to Treat High-Salinity Water
The concept of using a thermoresponsive
ionic liquid (IL) with
an upper critical solution temperature (UCST) as a draw solute in
forward osmosis (FO) was successfully demonstrated here experimentally.
A 3.2 M solution of protonated betaine bisÂ(trifluoromethylsulfonyl)Âimide
([Hbet]Â[Tf2N]) was obtained by heating and maintaining the temperature
above 56 °C. This solution successfully drew water from high-salinity
water up to 3.0 M through FO. When the IL solution cooled to room
temperature, it spontaneously separated into a water-rich phase and
an IL-rich phase: the water-rich phase was the produced water that
contained a low IL concentration, and the IL-rich phase could be used
directly as the draw solution in the next cycle of the FO process.
The thermal stability, thermal-responsive solubility, and UV–vis
absorption spectra of the IL were also studied in detail
Hydrogenation of Esters Catalyzed by Ruthenium PN<sup>3</sup>‑Pincer Complexes Containing an Aminophosphine Arm
Hydrogenation
of esters under mild conditions was achieved using
air-stable ruthenium PN<sup>3</sup>-pincer complexes containing an
aminophosphine arm. High efficiency was achieved even in the presence
of water. DFT studies suggest a bimolecular proton shuttle mechanism
which allows H<sub>2</sub> to be activated by the relatively stable
catalyst with a reasonably low transition state barrier
Graphene-Coated Hollow Fiber Membrane as the Cathode in Anaerobic Electrochemical Membrane Bioreactors – Effect of Configuration and Applied Voltage on Performance and Membrane Fouling
Electrically
conductive, graphene-coated, hollow-fiber porous membranes
were used as cathodes in anaerobic electrochemical membrane bioreactors
(AnEMBRs) operated at different applied voltages (0.7 and 0.9 V) using
a new rectangular reactor configuration compared to a previous tubular
design (0.7 V). The onset of biofouling was delayed and minimized
in rectangular reactors operated at 0.9 V compared to those at 0.7
V due to higher rates of hydrogen production. Maximum transmembrane
pressures for the rectangular reactor were only 0.10 bar (0.7 V) or
0.05 bar (0.9 V) after 56 days of operation compared to 0.46 bar (0.7
V) for the tubular reactor after 52 days. The thickness of the membrane
biofouling layer was approximately 0.4 ÎĽm for rectangular reactors
and 4 ÎĽm for the tubular reactor. Higher permeate quality (TSS
= 0.05 mg/L) was achieved in the rectangular AnEMBR than that in the
tubular AnEMBR (TSS = 17 mg/L), likely due to higher current densities
that minimized the accumulation of cells in suspension. These results
show that the new rectangular reactor design, which had increased
rates of hydrogen production, successfully delayed the onset of cathode
biofouling and improved reactor performance
A Novel Anaerobic Electrochemical Membrane Bioreactor (AnEMBR) with Conductive Hollow-fiber Membrane for Treatment of Low-Organic Strength Solutions
A new
anaerobic treatment system that combined a microbial electrolysis
cell (MEC) with membrane filtration using electrically conductive,
porous, nickel-based hollow-fiber membranes (Ni-HFMs) was developed
to treat low organic strength solution and recover energy in the form
of biogas. This new system is called an anaerobic electrochemical
membrane bioreactor (AnEMBR). The Ni-HFM served the dual function
as the cathode for hydrogen evolution reaction (HER) and the membrane
for filtration of the effluent. The AnEMBR system was operated for
70 days with synthetic acetate solution having a chemical oxygen demand
(COD) of 320 mg/L. Removal of COD was >95% at all applied voltages
tested. Up to 71% of the substrate energy was recovered at an applied
voltage of 0.7 V as methane rich biogas (83% CH<sub>4</sub>; <
1% H<sub>2</sub>) due to biological conversion of the hydrogen evolved
at the cathode to methane. A combination of factors (hydrogen bubble
formation, low cathode potential and localized high pH at the cathode
surface) contributed to reduced membrane fouling in the AnEMBR compared
to the control reactor (open circuit voltage). The net energy required
to operate the AnEMBR system at an applied voltage of 0.7 V was significantly
less (0.27 kWh/m<sup>3</sup>) than that typically needed for wastewater
treatment using aerobic membrane bioreactors (1–2 kWh/m<sup>3</sup>)