2015

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

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E. Braun, J. J. Chen, S. K. Schnell, L.-C. Lin, J. A. Reimer, and B. Smit, Nanoporous Materials Can Tune the Critical Point of a Pure Substance Angew. Chem. Int. Ed., n/a (2015) http://dx.doi.org/10.1002/anie.201506865


Abstract Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. …

Systematic tuning and multi-functionalization of covalent organic polymers for enhanced carbon capture

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Z. Xiang, R. Mercado, J. M. Huck, H. Wang, Z. Guo, W. Wang, D. Cao, M. Haranczyk, and B. Smit, Systematic tuning and multi-functionalization of covalent organic polymers for enhanced carbon capture J. Am. Chem. Soc. 137 (41), 13301  (2015) http://dx.doi.org/10.1021/jacs.5b06266


Abstract: Porous covalent polymers are attracting increasing interest in the fields of gas adsorption, gas separation, and catalysis due to their fertile synthetic polymer chemistry, large internal surface areas, and ultrahigh hydrothermal stabilities. While precisely manipulating the porosities of porous organic materials for targeted applications remains challenging, we show how a large degree of diversity can be achieved in covalent organic polymers by incorporating multiple functionalities into a single framework, as is done for crystalline porous materials. …

Computer-aided search for materials to store natural gas for vehicles

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C. M. Simon, J. Kim, D. A. Gomez-Gualdron, Y. G. Chung, R. L. Martin, R. Mercado, M. W. Deem, D. Gunter, M. Haranczyk, R. Q. Snurr, and B. Smit, Computer-aided search for materials to store natural gas for vehicles Front. Young Minds 3 (11), 1 (2015) http://dx.doi.org/10.3389/frym.2015.00011


Abstract: Most cars use gasoline as a fuel. But cars can run on other fuels, such as natural gas (NG), the same gas that is used for cooking and for heating our homes. NG is cheaper and possibly better for the environment than gasoline. However, gasoline is much more dense than NG since gasoline is a liquid and NG is a gas. So, to run a car on NG, we need to increase its density so that we can fit enough NG in the fuel tank to drive a similar distance as with a tank of gasoline. …

Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2

Z. Hulvey, B. Vlaisavljevich, J. A. Mason, E. Tsivion, T. P. Dougherty, E. D. Bloch, M. Head-Gordon, B. Smit, J. R. Long, and C. M. Brown, Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2 J. Am. Chem. Soc.  137 (33), 10816 (2015) http://dx.doi.org/10.1021/jacs.5b06657


Thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal-organic framework Cu3(btc)2 (btc3– = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analog Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. …

Carbon Capture Turned Upside Down: High-Temperature Adsorption & Low-Temperature Desorption (HALD)

L. Joos, K. Lejaeghere, J. M. Huck, V. Van Speybroeck, and B. Smit, Carbon Capture Turned Upside Down: High-Temperature Adsorption & Low-Temperature Desorption (HALD) Energy Environ. Sci. 8 (8), 2480 (2015) http://dx.doi.org/10.1039/C5EE01690H


Abstract Carbon Capture & Sequestration (CCS) could reduce CO2 emissions from large fossil-fuel power plants in the short term, but the high energy penalty of the process hinders its industrial deployment. Moreover, the utility of nanoporous materials, known to be selective for the CO2/N2 separation, is drastically reduced due to the competitive adsorption with H2O. Taking advantage of the power plant's waste heat to perform CCS while at the same time surmounting the negative effect of H2O is therefore an attractive idea. …

CO2 induced phase transitions in diamine-appended metal organic frameworks

B. Vlaisavljevich, S. O. Odoh, S. Schnell, A. L. Dzubak, K. Lee, N. Planas, J. Neaton, L. Gagliardi, and B. Smit, CO2 induced phase transitions in diamine-appended metal organic frameworks Chem. Sci. 6 (9), 5177 (2015) http://dx.doi.org/10.1039/C5SC01828E



Abstract: Using a combination of density functional theory and lattice models, we study the effect of CO2 adsorption in an amine functionalized metal organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. …

Energypolis: Chemistry for Energy

2015_05

B. Smit, Energypolis: Chemistry for Energy Chimia 69 (5) (2015)



Editorial for a special issue of Chimia about the energy research in Sion, Valais.


The special volume can be found here.


Screening Materials Relevant for Energy Technologies

B. Smit, Screening Materials Relevant for Energy Technologies CHIMIA 69 (5), 248 (2015) http://dx.doi.org/10.2533/chimia.2015.248

Abstract: In this short review, some recent advances are discussed in the development of computational techniques to perform large-scale screening of materials for energy-related applications. We focus on carbon capture and methane storage in different classes of nanoporous materials. We show how these screening studies can identify whether economic targets for particular processes can be reached.

Understanding Small-Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

J. S. Lee, B. Vlaisavljevich, D. K. Britt, C. M. Brown, M. Haranczyk, J. B. Neaton, B. Smit, J. R. Long, and W. L. Queen, Understanding Small-Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory Adv. Mater., 27 (38), 5785 (2015) http://dx.doi.org/10.1002/adma.201500966



Abstract: Metal–organic frameworks (MOFs) have gained much attention as next-generation porous media for various applications, especially gas separation/storage, and catalysis. New MOFs are regularly reported; however, to develop better materials in a timely manner for specific applications, the interactions between guest molecules and the internal surface of the framework must first be understood. …

What are the best materials to separate a xenon/krypton mixture?

C. M. Simon, R. Mercado, S. K. Schnell, B. Smit, and M. Haranczyk, What are the best materials to separate a xenon/krypton mixture? Chem. Mat. 27 (12), 4459  (2015) http://dx.doi.org/10.1021/acs.chemmater.5b01475



Abstract: Accelerating progress in the discovery and deployment of advanced nanoporous materials relies on chemical insight and structure property relationships for rational design. Because of the complexity of this problem, trial-and-error is heavily involved in the laboratory today. A cost-effective route to aid experimental materials discovery is to construct structure models of nanoporous materials in silico and use molecular simulations to rapidly test them and elucidate data-driven guidelines for rational design. …

Adsorption Thermodynamics and Intrinsic Activation Parameters for Monomolecular Cracking of N-alkanes on Brønsted-acid Sites in Zeolites

A. L. Janda, B. Vlaisavljevich, L.-C. Li, S. Mallikarjun Sharada, B. Smit, M. Head-Gordon, and A. T. Bell, Adsorption Thermodynamics and Intrinsic Activation Parameters for Monomolecular Cracking of N-alkanes on Brønsted-acid Sites in Zeolites J Phys Chem C  19 (19), 10427 (2015) http://dx.doi.org/10.1021/acs.jpcc.5b01715



Abstract: Experimental measurements of the rate coefficient (kapp) and apparent enthalpies and entropies of activation (ΔHapp and ΔSapp) for alkane cracking catalyzed by acidic zeolites can be used to characterize the effects of zeolite structure and alkane size on the intrinsic enthalpy and entropy of activation, 〖"ΔH" 〗_"int" ^"‡" and 〖"ΔS" 〗_"int" ^"‡" . …

Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

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T. M. McDonald, J. A. Mason, X. Kong, E. D. Bloch, D. Gygi, A. Dani, V. Crocella, F. Giordanino, S. O. Odoh, W. S. Drisdell, B. Vlaisavljevich, A. L. Dzubak, R. Poloni, S. K. Schnell, N. Planas, K. Lee, T. Pascal, L. F. Wan, D. Prendergast, J. B. Neaton, B. Smit, J. B. Kortright, L. Gagliardi, S. Bordiga, J. A. Reimer, and J. R. Long, Cooperative insertion of CO2 in diamine-appended metal-organic frameworks Nature 519 (7543), 303 (2015) http://dx.doi.org/10.1038/nature14327


Abstract: 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. …

PSII-LHCII Supercomplex Organizations in Photosynthetic Membrane by Coarse-Grained Simulation

C.-K. Lee, C.-W. Pao, and B. Smit, PSII-LHCII Supercomplex Organizations in Photosynthetic Membrane by Coarse-Grained Simulation J Phys Chem B  119 (10), 3999 (2015) http://dx.doi.org/10.1021/jp511277c


Abstract: Green plant photosystem II (PSII) and light-harvesting complex II (LHCII) in the stacked grana regions of thylakoid membranes can self-organize into various PSII-LHCII supercomplexes with crystalline or fluid-like supramolecular structures to adjust themselves with external stimuli such as high/low light and temperatures, rendering tunable solar light absorption spectrum and photosynthesis efficiencies. However, the mechanisms controlling the PSII-LHCII supercomplex organizations remain elusive. …

The Materials Genome in Action: Identifying the Performance Limits for Methane Storage

C. Simon, J. Kim, D. Gomez-Gualdron, J. Camp, Y. G. Chung, R. L. Martin, R. Mercado, M. W. Deem, D. Gunter, M. Haranczyk, D. Sholl, R. Q. Snurr, and B. Smit, The Materials Genome in Action: Identifying the Performance Limits for Methane Storage Energy Environ. Sci. 8, 1190–1199 (2015) http://dx.doi.org/10.1039/C4EE03515A (see cover picture here)


Abstract: Analogous to the way the Human Genome Project advanced an array of biological sciences by mapping the human genome, the Materials Genome Initiative aims to enhance our understanding of the fundamentals of material science by providing the information we need to accelerate the development of new materials. This approach is particularly applicable to recently developed classes of nanoporous materials, such as metal-organic frameworks (MOFs), which are synthesized from a limited set of molecular building blocks that can be combined to generate a very large number of different structures. …

Small molecule adsorption in open-site metal-organic frameworks: a systematic density functional theory study for rational design

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K. Lee, J. D. Howe, L.-C. Lin, B. Smit, and J. B. Neaton, Small molecule adsorption in open-site metal-organic frameworks: a systematic density functional theory study for rational design Chem. Mat. 27 (3), 668 (2015) http://dx.doi.org/10.1021/cm502760q

Abstract: 

Using density functional theory, we systematically compute and investigate the binding enthalpies of 14 different small molecules in a series of isostructural metal-organic frameworks, M-MOF-74, with M = Mg, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. The small molecules we consider include major flue gas components, trace gases, and small hydrocarbons, i.e., H2, CO, CO2, H2O, H2S, N2, NH3, SO2, CH4, C2H2, C2H4, C2H6, C3H6, and C3H8. …

In Silico Discovery of High Deliverable Capacity Metal-Organic Frameworks

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Y. Bao, R. L. Martin, C. M. Simon, M. Haranczyk, B. Smit, and M. W. Deem, In Silico Discovery of High Deliverable Capacity Metal-Organic Frameworks J. Phys. Chem. C. 19 (1),186 (2015) http://dx.doi.org/10.1021/jp5123486

Abstract: Metal organic frameworks (MOFs) are actively being explored as potential adsorbed natural gas storage materials for small vehicles. Experimental exploration of potential materials is limited by the throughput of synthetic chemistry. We here describe a computational methodology to complement and guide these experimental efforts. The method uses known chemical transformations in silico to identify MOFs with high methane deliverable capacity. …

Water Adsorption in Metal-Organic Frameworks with Open-Metal Sites

X. Peng, L.-C. Lin, W. Sun, and B. Smit, Water Adsorption in Metal-Organic Frameworks with Open-Metal Sites AIChE J.  61 (2), 677 (2015) http://dx.doi.org/10.1002/aic.14707

Abstract In this study, we investigated H2O adsorptions inside porous materials, including silica zeolites, zeolite imidazolate frameworks (ZIFs), and metal-organic frameworks (MOFs) by using molecular simulations with different water models. Due to the existence of coordinately unsaturated metal sites, the predicted adsorption properties in M-MOF-74 (M=Mg, Ni, Co, and Zn) and Cu-BTC are found to be greatly sensitive to the adopted H2O models. Surprisingly, the analysis of the orientations of H2O minimum energy configuration in these materials show that three-site H2O models predict an unusual perpendicular angle of H2O plane with respect to the Metal-O4 plane, whereas those models with more than three sites give a more parallel angle that is in better agreement with the one obtained from density functional theory (DFT) calculations. …


© Berend Smit 2019