Strategic Growth Area: Economical and Sustainable Materials (ESM)
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Browsing Strategic Growth Area: Economical and Sustainable Materials (ESM) by Department "Chemical Engineering"
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- Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotentialWang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng (Springer Nature, 2018-05-15)Electrochemical reduction of N2 to NH3 provides an alternative to the Haber−Bosch process for sustainable, distributed production of NH3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N2 reduction. Here we report efficient electroreduction of N2 to NH3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH3 yield rate of ~4.5 μg mg−1Pd h−1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N2 hydrogenation to *N2H, the rate-limiting step for NH3 electrosynthesis.
- Amphiphilic hydroxyalkyl cellulose derivatives for amorphous solid dispersion prepared by olefin cross-metathesisDong, Yifan; Mosquera-Giraldo, Laura I.; Troutman, Jacob; Skogstad, Brittny; Taylor, Lynne S.; Edgar, Kevin J. (Royal Society of Chemistry, 2016-07-07)Olefin cross-metathesis (CM) has enabled design and synthesis of diverse, amphiphilic cellulose ether derivatives (e.g. of ethyl and methyl cellulose). In this paper, hydroxyalkyl cellulose was selected as a hydrophilic starting material, with the additional advantage that it has DS (OH) 3.0 that allows targeting of a full range of DS of selected functional groups. Hydroxypropyl cellulose (HPC) was first etherified with 5-bromopent-1-ene to attach olefin “handles” for metathesis, whereby control of molar ratios of sodium hydride and 5-bromopent-1-ene permits full DS control of appended olefin. These olefin-terminated HPC ethers then were subjected to CM with acrylic acid and different acrylates, followed by diimide hydrogenation to reduce the resulting α,β-unsaturation. NMR and FT-IR spectroscopies were useful tools for following reaction progress. One of the product carboxyl-functionalized HPC derivatives, designated HPC-Pen106-AA-H, showed high promise as a crystallization inhibitor of the antiviral drug telaprevir. Its nucleation-induction inhibitory ability was compared to those of commercial controls, HPC and HPMCAS. All three polymers were very effective for inhibiting telaprevir crystallization, increasing induction time up to 8-fold. HPC did not effectively prevent amorphous particle growth, whereas the carboxyl-containing HPC-Pen106-AA-H and HPMCAS were able to prevent formation of agglomerates of amorphous drugs.
- Development of Recyclable and High-Performance In Situ Hybrid TLCP/Glass Fiber CompositesChen, Tianran; Kazerooni, Dana; Ju, Lin; Okonski, David A.; Baird, Donald G. (MDPI, 2020-08-24)By combining the concepts of in situ thermotropic liquid crystalline polymer (TLCP) composites and conventional fiber composites, a recyclable and high-performance in situ hybrid polypropylene-based composite was successfully developed. The recycled hybrid composite was prepared by injection molding and grinding processes. Rheological and thermal analyses were utilized to optimize the processing temperature of the injection molding process to reduce the melt viscosity and minimize the degradation of polypropylene. The ideal temperature for blending the hybrid composite was found to be 305 °C. The influence of mechanical recycling on the different combinations of TLCP and glass fiber composites was analyzed. When the weight fraction ratio of TLCP to glass fiber was 2 to 1, the hybrid composite exhibited better processability, improved tensile performance, lower mechanical anisotropy, and greater recyclability compared to the polypropylene reinforced by either glass fiber or TLCP alone.
- Femtosecond Laser Pulse Driven Melting in Gold Nanorod Aqueous Colloidal Suspension: Identification of a Transition from Stretched to Exponential KineticsLi, Yuelin; Lin, Xiao-Min; Wen, Haidan; Walko, Donald A.; Deshmukh, Sanket A.; Subbaraman, Ram; Sankaranarayanan, Subramanian K. R. S.; Gray, Stephen K.; Ho, Phay (Nature, 2015-01-30)Many potential industrial, medical, and environmental applications of metal nanorods rely on the physics and resultant kinetics and dynamics of the interaction of these particles with light. We report a surprising kinetics transition in the global melting of femtosecond laser-driven gold nanorod aqueous colloidal suspension. At low laser intensity, the melting exhibits a stretched exponential kinetics, which abruptly transforms into a compressed exponential kinetics when the laser intensity is raised. It is found the relative formation and reduction rate of intermediate shapes play a key role in the transition. Supported by both molecular dynamics simulations and a kinetic model, the behavior is traced back to the persistent heterogeneous nature of the shape dependence of the energy uptake, dissipation and melting of individual nanoparticles. These results could have significant implications for various applications such as water purification and electrolytes for energy storage that involve heat transport between metal nanorod ensembles and surrounding solvents.
- Mitigation of bidirectional solute flux in forward osmosis via membrane surface coating of zwitterion functionalized carbon nanotubesZou, Shiqiang; Smith, Ethan D.; Lin, Shihong; Martin, Stephen M.; He, Zhen (Elsevier, 2019-07-08)Forward osmosis (FO) has emerged as a promising membrane technology to yield high-quality reusable water from various water sources. A key challenge to be solved is the bidirectional solute flux (BSF), including reverse solute flux (RSF) and forward solute flux (FSF). Herein, zwitterion functionalized carbon nanotubes (Z-CNTs) have been coated onto a commercial thin film composite (TFC) membrane, resulting in BSF mitigation via both electrostatic repulsion forces induced by zwitterionic functional groups and steric interactions with CNTs. At a coating density of 0.97 gm⁻², a significantly reduced specific RSF was observed for multiple draw solutes, including NaCl (55.5% reduction), NH₄H₂PO₄(83.8%), (NH₄)₂HPO₄ (74.5%), NH₄Cl (70.8%), and NH₄HCO₃ (61.9%). When a synthetic wastewater was applied as the feed to investigate membrane rejection, FSF was notably reduced by using the coated membrane with fewer pollutants leaked to the draw solution, including NH₄⁺-N (46.3% reduction), NO₂⁻₋N (37.0%), NO₂⁻₋N (30.3%), K⁺ (56.1%), PO₄³⁻₋P (100%), and Mg²⁺ (100%). When fed with real wastewater, a consistent water flux was achieved during semi-continuous operation with enhanced fouling resistance. This study is among the earliest efforts to address BSF control via membrane modification, and the results will encourage further exploration of effective strategies to reduce BSF.
- Prediction of Young’s Modulus for Injection Molded Long Fiber Reinforced ThermoplasticsChen, Hongyu; Baird, Donald G. (MDPI, 2018-08-06)In this article, the elastic properties of long-fiber injection-molded thermoplastics (LFTs) are investigated by micro-mechanical approaches including the Halpin-Tsai (HT) model and the Mori-Tanaka model based on Eshelby’s equivalent inclusion (EMT). In the modeling, the elastic properties are calculated by the fiber content, fiber length, and fiber orientation. Several closure approximations for the fourth-order fiber orientation tensor are evaluated by comparing the as-calculated elastic stiffness with that from the original experimental fourth-order tensor. An empirical model was developed to correct the fibers’ aspect ratio in the computation for the actual as-formed LFTs with fiber bundles under high fiber content. After the correction, the analytical predictions had good agreement with the experimental stiffness values from tensile tests on the LFTs. Our analysis shows that it is essential to incorporate the effect of the presence of fiber bundles to accurately predict the composite properties. This work involved the use of experimental values of fiber orientation and serves as the basis for computing part stiffness as a function of mold filling conditions. The work also explains why the modulus tends to level off with fiber concentration.
- Stereoselective photoredox ring-opening polymerization of O-carboxyanhydridesFeng, Quanyou; Yang, Lei; Zhong, Yongliang; Guo, Dong; Liu, Guoliang; Xie, Linghai; Huang, Wei; Tong, Rong (Nature, 2018-04-19)Biodegradable polyesters with various tacticities have been synthesized by means of stereoselective ring-opening polymerization of racemic lactide and β-lactones but with limited side-chain groups. However, stereoselective synthesis of functional polyesters remains challenging from O-carboxyanhydrides that have abundant pendant side-chain functional groups. Herein we report a powerful strategy to synthesize stereoblock polyesters by stereoselective ring-opening polymerization of racemic O-carboxyanhydrides with the use of photoredox Ni/Ir catalysts and a selected Zn complex with an achiral ligand. The obtained stereoblock copolymers are highly isotactic with high molecular weights ( > 70 kDa) and narrow molecular weight distributions (Mw/Mn < 1.1), and they display distinct melting temperatures that are similar to their stereocomplex counterparts. Furthermore, in one-pot photoredox copolymerization of two different O-carboxyanhydrides, the use of such Zn complex mediates kinetic resolution of the comonomers during enchainment and shows a chirality preference that allows for the synthesis of gradient copolymers.