Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates.

Dehydration of methyl lactate to acrylic acid and methyl acrylate was experimentally evaluated over a Na-FAU zeolite catalyst impregnated with multifunctional diamines. 1,2-Bis(4-pyridyl)ethane (12BPE) and 4,4'-trimethylenedipyridine (44TMDP), at a nominal loading of 40 wt % or two molecules per Na-FAU supercage, afforded a dehydration selectivity of 96 ± 3% over 2000 min time on stream. Although 12BPE and 44TMDP have van der Waals diameters approximately 90% of the Na-FAU window opening diameter, both flexible diamines interact with internal active sites of Na-FAU as characterized by infrared spectroscopy. During continuous reaction at 300 °C, the amine loadings in Na-FAU remained constant for 12BPE but decreased as much as 83% for 44TMDP. Tuning the weighted hourly space velocity (WHSV) from 0.9 to 0.2 h-1 afforded a yield as high as 92% at a selectivity of 96% with 44TMDP impregnated Na-FAU, resulting in the highest yield reported to date.

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this Chemical Reviews contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena. The Review highlights signature accomplishments across a broad research portfolio and is organized into four wide-ranging research themes that address the topic in a comprehensive manner: Feedstocks, Polymerization Processes and Techniques, Intended Use, and End of Use. We emphasize those successes that benefitted from collaborative engagements across disciplinary lines.

Catalysis-in-a-Box: Robotic Screening of Catalytic Materials in the Time of COVID-19 and Beyond.

This work describes the design and implementation of an automated device for catalytic materials testing by direct modifications to a gas chromatograph (GC). The setup can be operated as a plug-flow isothermal reactor and enables the control of relevant parameters such as reaction temperature and reactant partial pressures directly from the GC. High-quality kinetic data (including reaction rates, product distributions, and activation barriers) can be obtained at almost one-tenth of the fabrication cost of analogous commercial setups. With these key benefits including automation, low cost, and limited experimental equipment instrumentation, this implementation is intended as a high-throughput catalyst screening reactor that can be readily utilized by materials synthesis researchers to assess the catalytic properties of their synthesized structures in vapor-phase chemistries.

Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs.

Electrochemical studies of the reduction and oxidation reactions of five different organic nitroxyls have been performed across a wide pH range (0-13). The resulting Pourbaix diagrams illustrate structural effects on their various redox potentials and on the p Ka values of the corresponding hydroxylamine and hydroxylammonium ions. Evidence is also given for the reversible formation of a hydroxylamine N-oxide when nitroxyls are oxidized in alkaline media. Structural effects on the thermodynamics of this reaction are assessed.

Novel approaches to improve iris recognition system performance based on local quality evaluation and feature fusion.

For building a new iris template, this paper proposes a strategy to fuse different portions of iris based on machine learning method to evaluate local quality of iris. There are three novelties compared to previous work. Firstly, the normalized segmented iris is divided into multitracks and then each track is estimated individually to analyze the recognition accuracy rate (RAR). Secondly, six local quality evaluation parameters are adopted to analyze texture information of each track. Besides, particle swarm optimization (PSO) is employed to get the weights of these evaluation parameters and corresponding weighted coefficients of different tracks. Finally, all tracks' information is fused according to the weights of different tracks. The experimental results based on subsets of three public and one private iris image databases demonstrate three contributions of this paper. (1) Our experimental results prove that partial iris image cannot completely replace the entire iris image for iris recognition system in several ways. (2) The proposed quality evaluation algorithm is a self-adaptive algorithm, and it can automatically optimize the parameters according to iris image samples' own characteristics. (3) Our feature information fusion strategy can effectively improve the performance of iris recognition system.

Characterization of plasmonic hole arrays as transparent electrical contacts for organic photovoltaics using high-brightness Fourier transform methods.

We present a methodology for probing light-matter interactions in prototype photovoltaic devices consisting of an organic semiconductor active layer with a semitransparent metal electrical contact exhibiting surface plasmon-based enhanced optical transmission. We achieve high-spectral irradiance in a spot size of less than 100 µm using a high-brightness laser-driven light source and appropriate coupling optics. Spatially resolved Fourier transform photocurrent spectroscopy in the visible and near-infrared spectral regions allows us to measure external quantum efficiency with high sensitivity in small-area devices (<1 mm2). This allows for rapid fabrication of variable-pitch sub-wavelength hole arrays in metal films for use as transparent electrical contacts, and evaluation of the evanescent and propagating mode coupling to resonances in the active layer.