Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

A new software package, RASPA, for simulating adsorption and diffusion of molecules in flexible nanoporous materials is presented. The code implements the latest state-of-the-art algorithms for molecular dynamics and Monte Carlo (MC) in various ensembles including symplectic/measure-preserving integrators, Ewald summation, configurational-bias MC, continuous fractional component MC, reactive MC and Baker's minimisation. We show example applications of RASPA in computing coexistence properties, adsorption isotherms for single and multiple components, self-and collective diffusivities, reaction systems and visualisation. The software is released under the GNU General Public License.

Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

A scalable, reproducible method of synthesizing UiO-66- and UiO-67-type MOFs, entailing the addition of HCl to the reaction mixture, has been investigated. The new protocol requires a fraction of the time of previously reported procedures, yields exceptional porosities, and works with a range of linkers.

Metal-organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented -OH groups and large 1D mesopores and apertures.

Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

We have synthesized, characterized, and computationally simulated/validated the behavior of two new metal-organic framework (MOF) materials displaying the highest experimental Brunauer-Emmett-Teller (BET) surface areas of any porous materials reported to date (~7000 m(2)/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, is the use of a supercritical CO(2) activation technique. Additionally, we demonstrate computationally that by shifting from phenyl groups to "space efficient" acetylene moieties as linker expansion units, the hypothetical maximum surface area for a MOF material is substantially greater than previously envisioned (~14600 m(2)/g (or greater) versus ~10500 m(2)/g).

The development of new microporous materials for adsorption separation processes is a rapidly growing field because of potential applications such as carbon capture and sequestration (CCS) and purification of clean-burning natural gas. In particular, new metal-organic frameworks (MOFs) and other porous coordination polymers are being generated at a rapid and growing pace. Herein, we address the question of how this large number of materials can be quickly evaluated for their practical application in carbon dioxide separation processes. Five adsorbent evaluation criteria from the chemical engineering literature are described and used to assess over 40 MOFs for their potential in CO(2) separation processes for natural gas purification, landfill gas separation, and capture of CO(2) from power-plant flue gas. Comparisons with other materials such as zeolites are made, and the relationships between MOF properties and CO(2) separation potential are investigated from the large data set. In addition, strategies for tailoring and designing MOFs to enhance CO(2) adsorption are briefly reviewed.