23 research outputs found
Olsalazine-Based Metal–Organic Frameworks as Biocompatible Platforms for H_2 Adsorption and Drug Delivery
The drug olsalazine (H_4olz) was employed as a ligand to synthesize a new series of mesoporous metal–organic frameworks that are expanded analogues of the well-known M_2(dobdc) materials (dobdc^4– = 2,5-dioxido-1,4-benzenedicarboxylate; M-MOF-74). The M_2(olz) frameworks (M = Mg, Fe, Co, Ni, and Zn) exhibit high surface areas with large hexagonal pore apertures that are approximately 27 Å in diameter. Variable temperature H_2 adsorption isotherms revealed strong adsorption at the open metal sites, and in situ infrared spectroscopy experiments on Mg_2(olz) and Ni_2(olz) were used to determine site-specific H_2 binding enthalpies. In addition to its capabilities for gas sorption, the highly biocompatible Mg_2(olz) framework was also evaluated as a platform for the delivery of olsalazine and other encapsulated therapeutics. The Mg_2(olz) material (86 wt % olsalazine) was shown to release the therapeutic linker through dissolution of the framework under simulated physiological conditions. Furthermore, Mg_2(olz) was used to encapsulate phenethylamine (PEA), a model drug for a broad class of bioactive compounds. Under simulated physiological conditions, Mg_2(olz)(PEA)_2 disassembled to release PEA from the pores and olsalazine from the framework itself, demonstrating that multiple therapeutic components can be delivered together at different rates. The low toxicity, high surface areas, and coordinatively unsaturated metal sites make these M_2(olz) materials promising for a range of potential applications, including drug delivery in the treatment of gastrointestinal diseases
Olsalazine-Based Metal–Organic Frameworks as Biocompatible Platforms for H_2 Adsorption and Drug Delivery
The drug olsalazine (H_4olz) was employed as a ligand to synthesize a new series of mesoporous metal–organic frameworks that are expanded analogues of the well-known M_2(dobdc) materials (dobdc^4– = 2,5-dioxido-1,4-benzenedicarboxylate; M-MOF-74). The M_2(olz) frameworks (M = Mg, Fe, Co, Ni, and Zn) exhibit high surface areas with large hexagonal pore apertures that are approximately 27 Å in diameter. Variable temperature H_2 adsorption isotherms revealed strong adsorption at the open metal sites, and in situ infrared spectroscopy experiments on Mg_2(olz) and Ni_2(olz) were used to determine site-specific H_2 binding enthalpies. In addition to its capabilities for gas sorption, the highly biocompatible Mg_2(olz) framework was also evaluated as a platform for the delivery of olsalazine and other encapsulated therapeutics. The Mg_2(olz) material (86 wt % olsalazine) was shown to release the therapeutic linker through dissolution of the framework under simulated physiological conditions. Furthermore, Mg_2(olz) was used to encapsulate phenethylamine (PEA), a model drug for a broad class of bioactive compounds. Under simulated physiological conditions, Mg_2(olz)(PEA)_2 disassembled to release PEA from the pores and olsalazine from the framework itself, demonstrating that multiple therapeutic components can be delivered together at different rates. The low toxicity, high surface areas, and coordinatively unsaturated metal sites make these M_2(olz) materials promising for a range of potential applications, including drug delivery in the treatment of gastrointestinal diseases
M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites
The well-known frameworks of the type M2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) have numerous potential applications in gas storage and separations, owing to their exceptionally high concentration of coordinatively unsaturated metal surface sites, which can interact strongly with small gas molecules such as H2. Employing a related meta-functionalized linker that is readily obtained from resorcinol, we now report a family of structural isomers of this framework, M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni; m-dobdc4– = 4,6-dioxido-1,3-benzenedicarboxylate), featuring exposed M2+ cation sites with a higher apparent charge density. The regioisomeric linker alters the symmetry of the ligand field at the metal sites, leading to increases of 0.4–1.5 kJ/mol in the H2 binding enthalpies relative to M2(dobdc). A variety of techniques, including powder X-ray and neutron diffraction, inelastic neutron scattering, infrared spectroscopy, and first-principles electronic structure calculations, are applied in elucidating how these subtle structural and electronic differences give rise to such increases. Importantly, similar enhancements can be anticipated for the gas storage and separation properties of this new family of robust and potentially inexpensive metal–organic frameworks
M<sub>2</sub>(<i>m</i>‑dobdc) (M = Mn, Fe, Co, Ni) Metal–Organic Frameworks as Highly Selective, High-Capacity Adsorbents for Olefin/Paraffin Separations
The metal–organic
frameworks M<sub>2</sub>(<i>m</i>-dobdc) (M = Mn, Fe, Co,
Ni; <i>m</i>-dobdc<sup>4–</sup> = 4,6-dioxido-1,3-benzeneÂdicarboxylate)
were evaluated as
adsorbents for separating olefins from paraffins. Using single-component
and multicomponent equilibrium gas adsorption measurements, we show
that the coordinatively unsaturated M<sup>2+</sup> sites in these
materials lead to superior performance for the physisorptive separation
of ethylene from ethane and propylene from propane relative to any
known adsorbent, including <i>para</i>-functionalized structural
isomers of the type M<sub>2</sub>(<i>p</i>-dobdc) (<i>p</i>-dobdc<sup>4–</sup> = 2,5-dioxido-1,4-benzeneÂdicarboxylate).
Notably, the M<sub>2</sub>(<i>m</i>-dobdc) frameworks all
exhibit an increased affinity for olefins over paraffins relative
to their corresponding structural isomers, with the Fe, Co, and Ni
variants showing more than double the selectivity. Among these frameworks,
Fe<sub>2</sub>(<i>m</i>-dobdc) displays the highest ethylene/ethane
(>25) and propylene/propane (>55) selectivity under relevant
conditions,
together with olefin capacities exceeding 7 mmol/g. Differential enthalpy
calculations in conjunction with structural characterization of ethylene
binding in Co<sub>2</sub>(<i>m</i>-dobdc) and Co<sub>2</sub>(<i>p</i>-dobdc) <i>via in situ</i> single-crystal
X-ray diffraction reveal that the vast improvement in selectivity
arises from enhanced metal–olefin interactions induced by increased
charge density at the metal site. Moderate olefin binding enthalpies,
below 55 and 70 kJ/mol for ethylene and propylene, respectively, indicate
that these adsorbents maintain sufficient reversibility under mild
regeneration conditions. Additionally, transient adsorption experiments
show fast kinetics, with more than 90% of ethylene adsorption occurring
within 30 s after dosing. Breakthrough measurements further indicate
that Co<sub>2</sub>(<i>m</i>-dobdc) can produce high purity
olefins without a temperature swing, an important test of process
applicability. The excellent olefin/paraffin selectivity, high olefin
capacity, rapid adsorption kinetics, and low raw materials cost make
the M<sub>2</sub>(<i>m</i>-dobdc) frameworks the materials
of choice for adsorptive olefin/paraffin separations
Metal-organic frameworks for on-board storage of hydrogen and natural gas
This paper studies about metal-org. frameworks for on-board storage of hydrogen and natural gas. The paper studies on synthesis of thermally-robust, high-surface area materials with a high concn. of open metal coordination sites
Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal-Organic Frameworks
We present accurate force fields developed from density functional theory (DFT) calculations with periodic boundary conditions for use in molecular simulations involving M-2(dobdc) (M-MOF-74; dobdc(4-) = 2,5-dioxidobenzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Zn) and frameworks of similar topology. In these systems, conventional force fields fail to accurately model gas adsorption due to the strongly binding open-metal sites. The DFT-derived force fields predict the adsorption of CO2, H2O, and CH4 inside these frameworks much more accurately than other common force fields. We show that these force fields can also be used for M2(dobpdc) (dobpdc(4-) = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an extended version of MOF-74, and thus are a promising alternative to common force fields for studying materials similar to MOF-74 for carbon capture applications. Furthermore, it is anticipated that the approach can be applied to other metal organic framework topologies to obtain force fields for different systems. We have used this force field to study the effect of contaminants such as H2O and N-2 upon these materials' performance for the separation of CO2 from the emissions of natural gas reservoirs and coal-fired power plants. Specifically, mixture adsorption isotherms calculated with these DFT-derived force fields showed a significant reduction in the uptake of many gas components in the presence of even trace amounts of H2O vapor. The extent to which the various gases are affected by the concentration of H2O in the reservoir is quantitatively different for the different frameworks and is related to their heats of adsorption. Additionally, significant increases in CO2 selectivities over CH4 and N2 are observed as the temperature of the systems is lowered
Recommended from our members
Record High Hydrogen Storage Capacity in the Metal–Organic Framework Ni2(m‑dobdc) at Near-Ambient Temperatures
Hydrogen holds promise as a clean alternative automobile fuel, but its on-board storage presents significant challenges due to the low temperatures and/or high pressures required to achieve a sufficient energy density. The opportunity to significantly reduce the required pressure for high density H2 storage persists for metal-organic frameworks due to their modular structures and large internal surface areas. The measurement of H2 adsorption in such materials under conditions most relevant to on-board storage is crucial to understanding how these materials would perform in actual applications, although such data have to date been lacking. In the present work, the metal-organic frameworks M2(m-dobdc) (M = Co, Ni; m-dobdc4- = 4,6-dioxido-1,3-benzenedicarboxylate) and the isomeric frameworks M2(dobdc) (M = Co, Ni; dobdc4- = 1,4-dioxido-1,3-benzenedicarboxylate), which are known to have open metal cation sites that strongly interact with H2, were evaluated for their usable volumetric H2 storage capacities over a range of near-ambient temperatures relevant to on-board storage. Based upon adsorption isotherm data, Ni2(m-dobdc) was found to be the top-performing physisorptive storage material with a usable volumetric capacity between 100 and 5 bar of 11.0 g/L at 25 °C and 23.0 g/L with a temperature swing between -75 and 25 °C. Additional neutron diffraction and infrared spectroscopy experiments performed with in situ dosing of D2 or H2 were used to probe the hydrogen storage properties of these materials under the relevant conditions. The results provide benchmark characteristics for comparison with future attempts to achieve improved adsorbents for mobile hydrogen storage applications
M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) metal-organic frameworks exhibiting increased charge density and enhanced H2 binding at the open metal sites.
The well-known frameworks of the type M2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) have numerous potential applications in gas storage and separations, owing to their exceptionally high concentration of coordinatively unsaturated metal surface sites, which can interact strongly with small gas molecules such as H2. Employing a related meta-functionalized linker that is readily obtained from resorcinol, we now report a family of structural isomers of this framework, M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni; m-dobdc(4-) = 4,6-dioxido-1,3-benzenedicarboxylate), featuring exposed M(2+) cation sites with a higher apparent charge density. The regioisomeric linker alters the symmetry of the ligand field at the metal sites, leading to increases of 0.4-1.5 kJ/mol in the H2 binding enthalpies relative to M2(dobdc). A variety of techniques, including powder X-ray and neutron diffraction, inelastic neutron scattering, infrared spectroscopy, and first-principles electronic structure calculations, are applied in elucidating how these subtle structural and electronic differences give rise to such increases. Importantly, similar enhancements can be anticipated for the gas storage and separation properties of this new family of robust and potentially inexpensive metal-organic frameworks