High-Throughput Screening of Anion-Pillared Metal–Organic Frameworks for the Separation of Light Hydrocarbons

Abstract

Separation of light hydrocarbons is a challenging and energy-intensive industrial process. Adsorptive separations using metal–organic frameworks (MOFs) have drawn attention because they offer a potential route to higher energy efficiency for these separations. In this work, we performed high-throughput screening for the separations of C1–C3 light hydrocarbons based on adsorption in our previously reported anion-pillared MOF database. We explored the relationships of selectivity in the dilute limit with physical parameters including the largest cavity diameter, surface area, and pore volume fraction of MOFs. On the basis of this screening, we assessed the selective adsorption of binary light hydrocarbon mixtures for some promising MOFs by GCMC simulations and compared the selectivities with those of previously reported sorbent materials. We observed a trade-off between two performance metrics in which MOFs with higher selectivity usually show lower working capacity. When the pore space is available to both components, the vdW interaction plays a dominant role in light hydrocarbon separations. However, if the pore sizes are too small, separation is possible based on molecular sieving. The comparisons with some reported porous materials indicate that SIFSIX-2-Ni-i, SIFSIX-6-Cd-i, InFFIVE-5-Zn-i, and GaFFIVE-5-Cd-i appear promising for C3H6/C3H8, C2H6/CH4, C3H6/C2H4, and C3H8/C2H4 separations, respectively.

Immunoaffinity-Induced Signal Depression of Cu-MOF-74 for Label-Free Electrochemical Detection of Cardiac Troponin I

“…Metal–organic frameworks (MOFs) are a type of porous nanocrystalline materials composed of metal ions and multidentate organic ligands, which have been widely used in many fields such as catalysis, adsorption, optics, electricity, magnetism, and separation . In recent years, the research of MOFs as electrochemical biosensing materials has attracted increasing interest due to their unique advantages of structure and physicochemical properties like large surface area, controllable pore size, and excellent electroactivity or electrocatalysis. − For example, Yang et al have synthesized functionalized MOF nanosheets containing plenty of Ru­(dcbpy) 3 2+ (4,4′-dicarboxylic acid-2,2′-bipyridyl) and employed MOF as an electrochemiluminescence (ECL) probe to construct a “signal-on” ECL immunosensor.…”

Identifying High-Performance Metal–Organic Frameworks for Low-Temperature Oxygen Recovery from Helium by Computational Screening

“…Van der Waals interaction between framework atoms and adsorbates was described by combining parameters from the UFF for MOF atoms and from the TraPPE force field for O 2 and helium using the Lorentz–Berthelot mixing rule . Force fields based on similar principles have been shown to give adsorption energies in good agreement with dispersion-corrected density functional theory (DFT) calculations in a wide variety of MOFs for adsorption of hydrocarbons and CO 2. All Lennard-Jones potentials were truncated at a cutoff of 12.8 Å with analytical tail correction terms.…”

“…These materials can be tuned to have a specific surface area, pore size, and chemical functionality based on a wide variety of both metal nodes and organic ligands. Although the thousands of MOFs that exist represent an intriguing opportunity to develop effective separations processes, the large number of these materials makes systematic experimental studies impractical. , Computational screening based on molecular simulations of adsorption has emerged as a useful complement to direct experimental studies. − Data from studies of this kind have also been used to generate machine learning models for the prediction of adsorption properties in large libraries of materials. − …”

Discovery of High‐Performing Metal–Organic Frameworks for On‐Board Methane Storage and Delivery via LNG–ANG Coupling: High‐Throughput Screening, Machine Learning, and Experimental Validation

“…[ 22 ] The combination of TraPPE and DREIDING‐UFF had been used extensively in the literature, as described in several computational screening studies. [ 9 , 10 , 23 ] To determine the LJ parameters for the interaction between different types of atoms, the Lorentz–Berthelot combining rule was used (Equations ( 2 ) and ( 3 )): …”

“…Computational high‐throughput screening is a powerful approach that can be used to rapidly evaluate the performance of a large number of materials for a given application. [ 5 , 9 ] Considering MOFs for NG storage, [ 23 ] high‐throughput screening of 650 000 structures including experimental and hypothetical structures of MOFs, zeolites, and porous polymer networks for ANG application indicated the difficulty in achieving the target metric of the working capacity (315 cm 3 (STP) cm −3 ) proposed by the Advanced Research Projects Agency‐Energy (ARPA‐E) of the US Department of Energy (DOE), rendering a controversial verdict on porous material‐based methane storage and delivery. [ 10 ]…”