Carbon Dioxide Capture from Ambient Air Using Amine-Grafted Mesoporous Adsorbents

Anthropogenic emissions of carbon dioxide (CO2) have been identified as a major contributor to climate change. An attractive approach to tackle the increasing levels of CO2 in the atmosphere is direct extraction via absorption of CO2 from ambient air, to be subsequently desorbed and processed under controlled conditions. The feasibility of this approach depends on the sorbent material that should combine a long lifetime with nontoxicity, high selectivity for CO2, and favorable thermodynamic cycling properties. Adsorbents based on pore-expanded mesoporous silica grafted with amines have previously been found to combine high CO2 adsorption capacity at low partial pressures with operational stability under highly defined laboratory conditions. Here we examine the real potential and functionality of these materials by using more realistic conditions using both pure CO2, synthetic air, and, most importantly, ambient air. Through a combination of thermogravimetric analysis and Fourier transform infrared (TGA-FTIR) spectroscopy we address the primary functionality and by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy the observed degradation of the material on a molecular level

Fundamental promise of anthraquinone functionalized graphene based next generation battery electrodes: A DFT study

Organic batteries are promising alternatives to the present rechargeable battery technologies, mainly due to projected lower fabrication costs, less environmental impact, more versatility, and chemical and mechanical flexibility. In this study we investigate potential organic battery electrodes composed of an electronically conductive graphene monolayer functionalized with redox-active anthraquinone (AQ). The combination overcomes common drawbacks of organic batteries: (i) the solubility of the organic redox-active materials in the electrolyte is mitigated by anchoring onto graphene and (ii) the need for a large amount of conductive additives in the composite electrode is circumvented by the high conductivity of graphene. The electrodes are modelled by various density functional theory (DFT) based approaches and their fundamental promise as part of Li, Ca, and Al based batteries are outlined. We model the design of the electrodes, such as AQ attachment and loading, the thermodynamics of accepting mono to trivalent ideal charge carriers from the electrolyte, i.e. Li+, Ca2+, and Al3+, and the kinetics of ion diffusion at the electrode surface by assessment of the activation barriers. From the calculated multi-step electrode potential profiles, the theoretical electrode energy densities, with respect to the redox-active part, are 570 and 512 W h kg-1 for Li and Ca, respectively, which is quite comparable to the active materials of inorganic medium voltage lithium-ion battery electrodes. As the average potentials are in the range 0.5-1.2 V vs. Mn+/M0 these materials are either to be used as negative electrodes, combined with a high or medium potential positive electrode, or as positive electrodes vs. metal electrodes, for low voltage battery application

Review-Development of Huckel Type Anions: From Molecular Modeling to Industrial Commercialization. A Success Story

This paper reviews the battery electrolyte technologies involving Huckel-type salts as a major electrolyte component. The concept was initially proposed by M. Armand in 1995 and then explored by several research groups. In the present review studies on the optimization of the electrolyte composition starting from molecular modeling through enhancing the yield of the salt synthesis to structural characterization and electrochemical performance are described. Furthermore, the use of the optimized electrolytes in a variety of lithium-ion and post-lithium batteries is presented and discussed. Finally, the commercialization of the up to date technology by Arkema is discussed as well as the performance of the present Huckel anion based electrolytes as compared to other marketed electrolyte technologies

On the partial connection between random matrices and interacting particle systems

In the last decade there has been increasing interest in the fields of random matrices, interacting particle systems, stochastic growth models, and the connections between these areas. For instance, several objects appearing in the limit of large matrices arise also in the long time limit for interacting particles and growth models. Examples of these are the famous Tracy-Widom distribution functions and the Airy_2 process. The link is however sometimes fragile. For example, the connection between the eigenvalues in the Gaussian Orthogonal Ensembles (GOE) and growth on a flat substrate is restricted to one-point distribution, and the connection breaks down if we consider the joint distributions. In this paper we first discuss known relations between random matrices and the asymmetric exclusion process (and a 2+1 dimensional extension). Then, we show that the correlation functions of the eigenvalues of the matrix minors for beta=2 Dyson's Brownian motion have, when restricted to increasing times and decreasing matrix dimensions, the same correlation kernel as in the 2+1 dimensional interacting particle system under diffusion scaling limit. Finally, we analyze the analogous question for a diffusion on (complex) sample covariance matrices.Comment: 31 pages, LaTeX; Added a section concerning the Markov property on space-like path

Fluctuation properties of the TASEP with periodic initial configuration

We consider the joint distributions of particle positions for the continuous time totally asymmetric simple exclusion process (TASEP). They are expressed as Fredholm determinants with a kernel defining a signed determinantal point process. We then consider certain periodic initial conditions and determine the kernel in the scaling limit. This result has been announced first in a letter by one of us and here we provide a self-contained derivation. Connections to last passage directed percolation and random matrices are also briefly discussed.Comment: 33 pages, 4 figure, LaTeX; We added several references to the general framework and techniques use

Finite time corrections in KPZ growth models

We consider some models in the Kardar-Parisi-Zhang universality class, namely the polynuclear growth model and the totally/partially asymmetric simple exclusion process. For these models, in the limit of large time t, universality of fluctuations has been previously obtained. In this paper we consider the convergence to the limiting distributions and determine the (non-universal) first order corrections, which turn out to be a non-random shift of order t^{-1/3} (of order 1 in microscopic units). Subtracting this deterministic correction, the convergence is then of order t^{-2/3}. We also determine the strength of asymmetry in the exclusion process for which the shift is zero. Finally, we discuss to what extend the discreteness of the model has an effect on the fitting functions.Comment: 34 pages, 5 figures, LaTeX; Improved version including shift of PASEP height functio

Buffering of Segmental and Chromosomal Aneuploidies in Drosophila melanogaster

Chromosomal instability, which involves the deletion and duplication of chromosomes or chromosome parts, is a common feature of cancers, and deficiency screens are commonly used to detect genes involved in various biological pathways. However, despite their importance, the effects of deficiencies, duplications, and chromosome losses on the regulation of whole chromosomes and large chromosome domains are largely unknown. Therefore, to explore these effects, we examined expression patterns of genes in several Drosophila deficiency hemizygotes and a duplication hemizygote using microarrays. The results indicate that genes expressed in deficiency hemizygotes are significantly buffered, and that the buffering effect is general rather than being mainly mediated by feedback regulation of individual genes. In addition, differentially expressed genes in haploid condition appear to be generally more strongly buffered than ubiquitously expressed genes in haploid condition, but, among genes present in triploid condition, ubiquitously expressed genes are generally more strongly buffered than differentially expressed genes. Furthermore, we show that the 4th chromosome is compensated in response to dose differences. Our results suggest general mechanisms have evolved that stimulate or repress gene expression of aneuploid regions as appropriate, and on the 4th chromosome of Drosophila this compensation is mediated by Painting of Fourth (POF)