Biporous Metal-Organic Framework with Tunable CO2/CH4 Separation Performance Facilitated by Intrinsic Flexibility.

In this work, we report the synthesis of SION-8, a novel metal-organic framework (MOF) based on Ca(II) and a tetracarboxylate ligand TBAPy4- endowed with two chemically distinct types of pores characterized by their hydrophobic and hydrophilic properties. By altering the activation conditions, we gained access to two bulk materials: the fully activated SION-8F and the partially activated SION-8P with exclusively the hydrophobic pores activated. SION-8P shows high affinity for both CO2 ( Qst = 28.4 kJ/mol) and CH4 ( Qst = 21.4 kJ/mol), while upon full activation, the difference in affinity for CO2 ( Qst = 23.4 kJ/mol) and CH4 ( Qst = 16.0 kJ/mol) is more pronounced. The intrinsic flexibility of both materials results in complex adsorption behavior and greater adsorption of gas molecules than if the materials were rigid. Their CO2/CH4 separation performance was tested in fixed-bed breakthrough experiments using binary gas mixtures of different compositions and rationalized in terms of molecular interactions. SION-8F showed a 40-160% increase (depending on the temperature and the gas mixture composition probed) of the CO2/CH4 dynamic breakthrough selectivity compared to SION-8P, demonstrating the possibility to rationally tune the separation performance of a single MOF by manipulating the stepwise activation made possible by the MOF's biporous nature

Achievable Secrecy Rates of an Energy Harvesting Device

The secrecy rate represents the amount of information per unit time that can be securely sent on a communication link. In this work, we investigate the achievable secrecy rates in an energy harvesting communication system composed of a transmitter, a receiver and a malicious eavesdropper. In particular, because of the energy constraints and the channel conditions, it is important to understand when a device should transmit and to optimize how much power should be used in order to improve security. Both full knowledge and partial knowledge of the channel are considered under a Nakagami fading scenario. We show that high secrecy rates can be obtained only with power and coding rate adaptation. Moreover, we highlight the importance of optimally dividing the transmission power in the frequency domain, and note that the optimal scheme provides high gains in secrecy rate over the uniform power splitting case. Analytically, we explain how to find the optimal policy and prove some of its properties. In our numerical evaluation, we discuss how the maximum achievable secrecy rate changes according to the various system parameters. Furthermore, we discuss the effects of a finite battery on the system performance and note that, in order to achieve high secrecy rates, it is not necessary to use very large batteries.Comment: Accepted for publication in IEEE Journal on Selected Areas in Communications (Mar. 2016

Modern Coding Theory: The Statistical Mechanics and Computer Science Point of View

These are the notes for a set of lectures delivered by the two authors at the Les Houches Summer School on `Complex Systems' in July 2006. They provide an introduction to the basic concepts in modern (probabilistic) coding theory, highlighting connections with statistical mechanics. We also stress common concepts with other disciplines dealing with similar problems that can be generically referred to as `large graphical models'. While most of the lectures are devoted to the classical channel coding problem over simple memoryless channels, we present a discussion of more complex channel models. We conclude with an overview of the main open challenges in the field.Comment: Lectures at Les Houches Summer School on `Complex Systems', July 2006, 44 pages, 25 ps figure

Infrared Spectroscopy of Trapped Gases in Metal-Organic Frameworks

There are a range of environmental and industrial applications to capturing carbon dioxide from gas mixtures. Currently, materials being used in these applications bind carbon dioxide too strongly for practical purposes, such that they require large amounts of energy to be regenerated for reuse. Highly porous materials called metal-organic frameworks (MOFs) could serve much more effectively as carbon-capturing materials, as they suck up large amounts of carbon dioxide gas at pressures and temperatures that are nearly ideal for carbon-capture applications. Moreover, they require much less energy than current materials to release the carbon dioxide and be regenerated. Additionally, many different structures can be created fairly easily, so scientists are on the hunt for the ideal carbon-capturing MOF. In this thesis we study Mg-MOF-74, a particularly promising metal-organic framework material for separating carbon dioxide from gas mixtures. We use infrared spectroscopy to probe the interactions between the Mg-MOF-74 host and both carbon dioxide and methane. By shining infrared radiation on Mg-MOF-74 with gases trapped in it and looking at which frequencies of radiation are absorbed by the bound gases, we can learn about the binding nature of the framework. This in turn helps us to better understand the properties are are preferable in metal organic frameworks, and will aid chemists in fabricating new structures that are ideal for carbon-capture and other applications

Exploring the flexibility of MIL-47(V)-type materials using force field molecular dynamics simulations

The flexibility of three MIL-47(V)-type materials (MIL-47, COMOC-2, and COMOC-3) has been explored by constructing the pressure versus volume and free energy versus volume profiles at various temperatures ranging from 100 to 400 K This is done with first-principles-based force fields using the recently proposed QuickFF parametrization protocol. Specific terms were added for the materials at hand to describe the asymmetry of the one-dimensional vanadium oxide chain and to account for the flexibility of the organic linkers. The force fields are used in a series of molecular dynamics simulations at fixed volumes but varying unit cell shapes. The three materials show a distinct pressure-volume behavior, which underlines the ability to tune the mechanical properties by varying the linkers toward different applications such as nanosprings, dampers, and shock absorbers