Amine-functionalized MIL-101(Cr) fibers for direct air capture at cold temperatures using rapid temperature vacuum swing adsorption

We combined targeted chemistry and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell volume (approximately 702,000 cubic angstroms), a hierarchy of extra-large pore sizes (approximately 30 to 34 angstroms), and a Langmuir surface area for N2 of approximately 5900 +/- 300 square meters per gram. Beside the usual properties of porous compounds, this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.

The increase in the global atmospheric CO2 concentration resulting from over a century of combustion of fossil fuels has been associated with significant global climate change. With the global population increase driving continued increases in fossil fuel use, humanity's primary reliance on fossil energy for the next several decades is assured. Traditional modes of carbon capture such as precombustion and postcombustion CO2 capture from large point sources can help slow the rate of increase of the atmospheric CO2 concentration, but only the direct removal of CO2 from the air, or "direct air capture" (DAC), can actually reduce the global atmospheric CO2 concentration. The past decade has seen a steep rise in the use of chemical sorbents that are cycled through sorption and desorption cycles for CO2 removal from ultradilute gases such as air. This Review provides a historical overview of the field of DAC, along with an exhaustive description of the use of chemical sorbents targeted at this application. Solvents and solid sorbents that interact strongly with CO2 are described, including basic solvents, supported amine and ammonium materials, and metal-organic frameworks (MOFs), as the primary classes of chemical sorbents. Hypothetical processes for the deployment of such sorbents are discussed, as well as the limited array of technoeconomic analyses published on DAC. Overall, it is concluded that there are many new materials that could play a role in emerging DAC technologies. However, these materials need to be further investigated and developed with a practical sorbent-air contacting process in mind if society is to make rapid progress in deploying DAC as a means of mitigating climate change.

The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped CO2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO2 from various gas mixtures, and yield insights into the conservation of Mg(2+) within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.