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Larese Group Featured Cover on J. Chem. Phys. C

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The Larese Group’s research Adsorption of Pentane and Hexane Thin Films on the Surface of Graphite(0001) was featured on the cover of The Journal of Physical Chemistry C.

Surface adsorption plays an important role in a variety of industrial and technological processes, especially in energy conversion, storage, and transformation. As a result, there is a growing need for advancing the current understanding of fundamental interactions that govern these types of processes. 

This research characterizes the interaction of n-pentane and n-hexane with graphite using high-resolution volumetric adsorption isotherms along with molecular dynamic simulations. The thermodynamics of adsorption were obtained for n-pentane and n-hexane adsorbed on the basal plane of graphite in the temperature ranges 190–235 and 230–280 K, respectively, using high-resolution volumetric adsorption isotherms. These linear molecules exhibit a van der Waals interaction with the surface of graphite(0001) and yield an overall greater binding than on boron nitride and MgO(100).

The averaged areas per molecule calculated for the fluid monolayer phases were determined to be 52.03 and 61.35 Å2 for pentane and hexane, respectively, which are in agreement with previous diffraction measurements performed for the monolayer solid. MD simulations were performed in order to provide additional microscopic insight.

Density profiles normal to the graphite substrate revealed that the stabilization of the layer nearest to the surface by the fluid multilayer exists for linear alkanes as small as pentane, however to a much lesser extent than that observed previously for adsorption on boron nitride and MgO. Intermolecular radial distribution functions and diffusion coefficients derived from the molecular trajectories suggest that a liquid crystal phase exists in the layer nearest the surface at temperatures well above the bulk triple-point temperatures.

Dai Group Published in ACS Energy Letters

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The Dai group published their research “Surpassing the Organic Cathode Performance for Lithium-Ion Batteries with Robust Fluorinated Covalent Quinazoline Networks” in  ACS Energy Letters.

Organic electrode materials have promising application prospects in energy storage, but issues including rapid capacity fading and poor power capacity restrict their practical applications. Herein, nanoporous fluorinated covalent quinazoline networks (F-CQNs) were constructed by condensation of fluorinated aromatic aminonitrile precursors via an ionothermal pathway.

Precise control of the reaction parameters afforded F-CQN-1-600 material featuring high surface area, permanent porosity, high nitrogen content (23.49 wt %), extended π-conjugated architecture, layered structure, and bipolar combination of benzene and tricycloquinazoline. Synergy among these unique properties leads to a good performance as a cathode source for lithium-ion batteries (LIBs) in terms of high capacity (250 mA h g–1 at 0.1 A g–1), high rate capability (105 mA h g–1 at 5.0 A g–1), and impressive cycling stability (95.8% retention rate after 2000 cycles at 2.0 A g–1 together with a high Coulombic efficiency of 99.95%), surpassing most of the previous organic cathode counterparts

Dai Published in Chem

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In a collaborative piece, UT Chemistry’s Sheng Dai and Pasquale Fulvio from Texas A&M’s Department of Nuclear Engineering published their work “Porous Liquids: The Next Frontier” in Chem.

Porous liquids are a new class of molecular- and colloidal-size porous materials that combine permanent porosity of solid sorbents and fluid properties of liquids. Different from transient molecular clathrates, porous liquids have the potential to reinvent materials syntheses and unify homogeneous and heterogeneous separations and catalytic and energy-related processes, previously ascribed to liquids and porous solids, respectively.

Surface areas and pore volumes of the first examples of porous liquids based on porous molecular organic cages restricted their potential for technological applications. Recent advances in ionic liquid-based colloidal suspensions or covalently stabilized nanocomposites have improved the adsorption properties and increased our ability to tailor chemical composition and pore architecture. These hybrid porous liquids, however, still present challenges such as high melting temperatures, density, and viscosity.

This critical review discusses these challenges and presents opportunities for selected emerging applications based on analogous structure to that of traditional colloidal systems.

Darko Lab Published in Dalton Transactions

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The Darko Lab published their work “Tuning Rh(ii)-catalysed cyclopropanation with tethered thioether ligands” in Dalton Transactions. 

Dirhodium(II) paddlewheel complexes have high utility in diazo-mediated cyclopropanation reactions and ethyl diazoacetate is one of the most commonly used diazo compounds in this reaction. In this study, the lab reports efforts to use tethered thioether ligands to tune the reactivity of RhII-carbene mediated cyclopropanation of olefins with ethyl diazoacetate.

Microwave methods enabled the synthesis of a family of RhII complexes in which tethered thioether moieties were coordinated to axial sites of the complex. Different tether lengths and thioether substituents were screened to optimise cyclopropane yields and minimise side product formation.

Good yields were obtained when equimolar diazo and olefin were used. Structural and spectroscopic investigation revealed that tethered thioethers changed the electronic structure of the rhodium core, which was instrumental in the performance of the catalysts. Computational modelling of the catalysts provided further support that the tethered thioethers were responsible for increased yields.

Vogiatzis Group Published in JCTC

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Electronic structure theory describes the motions of electrons in atoms or molecules, and provides a versatile framework for the calculation of molecular geometries, chemical bonding, electronic and spectroscopic properties, reaction barriers, intermolecular interactions, and more. Wave function theory-based methods such as coupled-cluster methods, provide accurate results in a systematic manner, but they typically carry a significant computational cost.

The Vogiatzis group uses machine learning, the field of study allowing computers to learn without explicit programming, to provide novel approaches on the learning of the underlying electronic structure while subverting a significant portion of the computational expense. In a recent article published in the Journal of Chemical Theory and Computation, Jacob Townsend, under the supervision of Kostas Vogiatzis, presents a new efficient methodology that explores the local nature of the correlated motion of electrons which offers scalability and transferability between different chemical systems.

The novel approach provides coupled-cluster quality electronic energies at the cost of second-order perturbation theory (MP2), a computationally more affordable method. As a result, the authors were able to predict energies of a large molecular database, known as the GDB-9 dataset, at high accuracy at a fraction of the cost. Additionally, it was shown that the introduced method could be used to accurately predict energies of large chemical systems based on models trained on smaller ones.

Townsend recently received his PhD in the chemistry doctoral program at UT.

Dai 2020 Highly Cited Researcher

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Each year, Clarivate™ identifies the world’s most influential researchers ─ the select few who have been most frequently cited by their peers over the last decade. In 2020, fewer than 6,200, or about 0.1%, of the world’s researchers, in 21 research fields and across multiple fields, have earned this exclusive distinction.
Sheng Dai Sheng Dai is among this elite group recognized for exceptional research influence, demonstrated by the production of multiple highly-cited papers that rank in the top 1% by citations for field and year in the Web of Science™.

Musfeldt Group Published in Nature Communications

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The Musfeldt group published their work “Site-specific spectroscopic measurement of spin and charge in (LuFeO3)m/(LuFe2O4)1 multiferroic superlattices” in a collaborative piece in Nature Communications.

Interface materials offer a means to achieve electrical control of ferrimagnetism at room temperature as was recently demonstrated in (LuFeO3)m/(LuFe2O4)1 superlattices. A challenge to understanding the inner workings of these complex magnetoelectric multiferroics is the multitude of distinct Fe centres and their associated environments. This is because macroscopic techniques characterize average responses rather than the role of individual iron centres.

In this article, researchers combine optical absorption, magnetic circular dichroism and first-principles calculations to uncover the origin of high-temperature magnetism in these superlattices and the charge-ordering pattern in the m = 3 member. In a significant conceptual advance, interface spectra establish how Lu-layer distortion selectively enhances the Fe2+ →  Fe3+ charge-transfer contribution in the spin-up channel, strengthens the exchange interactions and increases the Curie temperature.

Comparison of predicted and measured spectra also identifies a non-polar charge ordering arrangement in the LuFe2O4 layer. This site-specific spectroscopic approach opens the door to understanding engineered materials with multiple metal centres and strong entanglement.

Dai Group Published in Advanced Energy & Sustainability Research

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The Dai Group published their work “Organic Cathode Materials for Lithium‐Ion Batteries: Past, Present, and Future” in Advanced Energy & Sustainability Research.

With the rapid development of energy storage systems in power supplies and electrical vehicles, the search for sustainable cathode materials to enhance the energy density of lithium‐ion batteries (LIBs) has become the focus in both academic and industrial studies. Currently, the widely utilized inorganic cathode materials have suffered from drawbacks such as limited capacity, high energy consumption in production, potential safety hazards, and high‐cost raw materials. It is necessary to develop green and sustainable cathode materials with higher specific capacity, better safety property, and more abundant natural resources.

As alternatives, organic cathode materials possess the advantages of high theoretical capacity, environmental friendliness, flexible structure design, systemic safety, and natural abundance, making them a promising class of energy storage materials.

This research reviews the development history of the organic cathode materials and recent research developments, introducing several categories of typical organic compounds as cathode materials for LIBs, including conductive polymers, organosulfur compounds, organic radical compounds, organic carbonyl compounds, and organic imine compounds. The electrochemical performance, electrode reaction mechanism, and pros and cons of different organic cathode materials have been comparatively analyzed to identify their challenges to be addressed.

The future research and improvement directions of the organic cathode materials have also been proposed in this review.

Dai Group Published in I&EC

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The Dai Group published their work “Mechanochemical Synthesis of High-Purity Anhydrous Binary Alkali and Alkaline Earth Chloride Mixtures” in the Journal of Industrial and Engineering Chemistry (I&EC).

A direct synthesis route for high-purity, anhydrous binary salt mixtures has been developed. This atom efficient, solvent-free process is easily scalable, with the potential to produce salt mixtures that meet the purity standards required for industrial heat transfer and nuclear applications. The essence of the methodology lies in mechanochemical synthesis of carnallite precursors that can mitigate the hydrolysis of MgCl2·6H2O under direct heating. Each dehydrated salt carnallite was then analyzed for purity and oxide content through subsequent powder X-ray diffraction, and strong acid titration. This process presents a more effective alternative route compared to previous methods for obtaining low-oxide, high-purity chloride salt mixtures.

Phillip Halstenberg, graduate student, oversaw all experimentation and writing of this manuscript. Dmitry Maltsev was responsible for pXRD
measurements and data evaluation. Ellie Kim and Dianna
Nguyen performed titrations and calculations to quantify oxide
content as part of their undergraduate research. Sheng
Dai advised and oversaw all experimentation.

Campagna Lab Published in JNP

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The Campagna Lab published their work “Isoflurane anesthesia disrupts the cortical metabolome” in a collaborative piece in the Journal of Neurophysiology (JNP). 

Identifying similarities and differences in the brain metabolome during different states of consciousness has broad relevance for neuroscience and state-dependent autonomic function. This study focused on prefrontal cortex (PFC) as a brain region known to modulate states of consciousness.

Anesthesia was used as a tool to eliminate wakefulness. Untargeted metabolomic analyses were performed on microdialysis samples obtained from mouse PFC during wakefulness and during isoflurane anesthesia.

Analyses detected 2153 molecules, 91 of which could be identified. Analytes were grouped as detected during both wakefulness and anesthesia (n=61), and as unique to wakefulness (n=23) or anesthesia (n=7). Data were analyzed using univariate and multivariate approaches. Relative to wakefulness, during anesthesia there was a significant (q < 0.0001) four-fold change in 21 metabolites. During anesthesia 11 of these 21 molecules decreased and 10 increased.

The Kyoto Encyclopedia of Genes and Genomes database was used to relate behavioral state specific changes in the metabolome to metabolic pathways. Relative to wakefulness, most of the amino acids and analogs measured were significantly decreased during isoflurane anesthesia. Nucleosides and analogs were significantly increased during anesthesia. Molecules associated with carbohydrate metabolism, maintenance of lipid membranes, and normal cell functions were significantly decreased during anesthesia.

Significant state-specific changes also were discovered among molecules comprising lipids and fatty acids, monosaccharides, and organic acids. Considered together, these molecules regulate point to point transmission, volume conduction, and cellular metabolism. The results identify a novel ensemble of candidate molecules in PFC as putative modulators of wakefulness and the loss of wakefulness.