Example Project 1: Design of Innovative Active Polymers for Next-Generation Batteries
Foreign Advisor: Dr. David Mecerreyes
Lithium ion batteries are part of our modern life: mobile phones, tablets, computers, watches, sport accessories, electric cars. Next generation batteries will require the development of innovative polymers that help to improve their performance in terms of power density, cyclability, raw materials availability, low weight, printability, flexibility, sustainability and security. This project focuses on the development of innovative electronically, redox or ionically active polymers. This includes the development of binders for electrodes, polymer electrolytes and redox polymers used in batteries (Figure 2). Research Problem: Understanding redox behavior of polymers in next generation battery technologies such as metal-polymer, organic, polymer-air and redox-flow batteries. Role of Student in Research: Participate in the development of polymers for batteries by performing polymer synthesis reactions, molecular characterizations, and electrochemical tests. Equipment/Software Student will Use: Organic and polymer synthetic reactions and characterization tools: NMR, FTIR, and GPC. Electrochemistry equipment: cyclic voltammetry (CV), galvanostatic, glove box, battery cell assembly.
Example Project 2: Polymer Coatings as Corrosion Inhibitors
Foreign Advisor: Dr. Maria Forsyth
The deterioration of materials by corrosion is one of the biggest issues in our society, leading to major safety issues and economic losses. Corrosion can be seen in our daily life (e.g., food cans, pipelines, bridges, etc.). Chromate-free corrosion inhibitors will be investigated, in order to mitigate the economic loss caused by mild-steel corrosion. We will investigate metal-free organic inhibitors having free coumarate and other organic anions that can be used either as direct corrosion inhibitors or incorporated into polymer coatings (Figure 3). Ionic monomers and polymer coatings with different counterions will be investigated. Research Problem: Understanding corrosion protection on steel and other metals with polymeric inhibitors. Role of Student in Research: Synthesis of polymer coatings and corrosion inhibitors. Carry out metal surface characterization. Equipment/Software Student will Use: Organic chemistry reactions, UV-photopolymerization, SEM, Electrochemical Impedance Spectroscopy.
Example Project 3: Organocatalysts for Polymerization Reactions
Foreign Advisor: Dr. Haritz Sardon
Typical organic compounds need high catalyst loading and demonstrate poor thermal stability (leading to catalyst degradation in high temperature processes). This project will focus on the use of organocatalysis at elevated temperatures for polymerization reactions, which has been explored much less than traditional metal-based catalysts. The main attribute of organocatalysts compared to organometallic catalysts resides in its versatility, high selectivity and possibility of purification or recovery of the catalyst from the final polymer. Recently, our group found that the stability issue could be solved by preparing an acid-base mixture which is stable up to 400 ºC (Figure 4). Research Problem: Developing organocatalyzed polymerization reactions at high temperatures. Role of Student in Research: Participate in the synthesis of catalysts and perform polymerization reactions utilizing these catalysts, and characterize the resultant polymers. Equipment/Software Student will Use: Organic and polymer synthesis, solution and solid-state NMR, GPC/SEC.
Example Project 4: Crystallinity and Phase Behavior in Complex Polymers
Foreign Advisor: Dr. Alejandro Müller
This project will focus on understanding structure, morphology, functionality and properties of semi-crystalline multiphasic polymers. It will include a wide diversity of multiphasic materials by designing and compounding blends, nano-structured blends, nanocomposites and bionanocomposites. The research will focus on novel polymeric materials capable of providing insights on self-assembly and physical properties (Figure 5). Research Problem: Understanding crystallization and phase separation in complex polymer systems. Role of Student in Research: Participate in the characterization of polymer multiphasic materials via a variety of techniques. Prepare samples using requisite methods for each instrument. Equipment/Software Student will Use: differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), cone microcalorimetry, polarized optical microscopy (PLOM), atomic force microscopy (AFM), electron microscopy (SEM and TEM) and x-ray diffraction (XRD).
Example Project 5: Computational Screening of Polymer-bound Catalysts for N2 Reduction
Foreign Advisor: Dr. Fernando Ruipérez
This project will perform a computational screening of novel frustrated Lewis pairs (FLP) to evaluate their performance in the activation of N2 and the subsequent reduction to NH3. Thus, sets of Lewis acids and bases will be characterized to generate a library of FLPs that are promising for N2 activation. These FLPs will be designed in such a way that they can be incorporated into polymeric chains as a first step to producing new materials able to capture and transform N2. Quantum chemical simulations based on Density Functional Theory (DFT) will be performed. Research problem: Design and characterize novel frustrated Lewis pairs by means of computational chemistry. Generate a library of metal-free FLP catalysts to activate N2 and reduce it to NH3. Role of the student in the research: Perform DFT calculations to design and characterize Lewis acids and bases to generate FLPs able to activate N2. Equipment that will be used: The calculations will be performed in the Scientific Computing Service of UPV which provides high-performance computing resources and specialized technical support.
Example Project 6: Effect of Hybrid Block on Properties of Solid Block Copolymer Electrolytes
Foreign Advisor: Dr. Irune Villaluenga
Catastrophic failure of Li-ion batteries often begins with the electrolyte decomposition and combustion. This effect is minimized in the case of solid electrolytes due to limited solubility and slow diffusion. However, inorganic materials cannot serve as efficient electrolytes as they do not adhere to moving boundaries of the active particles in the battery. Research Problem: Attempts to overcome the limitations of inorganic and organic ion conductors have led to great interest in solid hybrid electrolytes (Figure 7). Two key parameters in the design of solid hybrid electrolytes based on block copolymers are morphology and mechanical properties. Different volume fractions of each block will allow us to tune the morphology and modify the ion transport properties. Optimization of polymer electrolyte mechanical properties are crucial to avoid lithium dendrite growth and battery failure. Role of Student in Research: The student will perform studies about the effect of volume fraction of the hybrid block on ion transport properties. Moreover, the relationship between the mechanical properties and the ion transport properties will be studied to optimize their design. Equipment/Software Student will Use: Multichannel potentiostat/galvanostat, rheometer and dynamic mechanical analysis (DMA). Ionic conductivity will be measured with electrochemical impedance (EIS). The electrochemical window will be measured by cyclic voltammetry (CV).
Example Project 7: Multifunctional Polymer-Biohybrids for Redox Enzymes in Electrochemistry
Foreign Advisors: Dr. Ana Beloqui & Dr. Marcelo Calderon
The project is focused on the development of multifunctional biohybrids composed of biomacromolecules (e.g., mainly enzymes and functional polymers) (Figure 8). The polymeric component not only provides stability to the biomacromolecule, but also imparts new features to the biological component. We aim to incorporate conductive polymers in several different applications: improve the utilization of redox enzymes in electrochemistry applications; fluorescent polymers for tracking the hybrids delivered in vitro; and apply catalytic polymers to design and fabricate hybrid high-performance catalytic bioreactors. Research Problem: Current materials used in medical applications are strongly limited, regarding their disease targeting capabilities and ‘on-demand’ therapeutic functions. Taking this into consideration, current work is focused on the development of polymer-based nanomaterials that are able to sense environmental triggers and respond to them at the site of action, providing novel therapeutic and diagnostic approaches. Role of Student in Research: The student will establish chemical methodologies for the development of thermoresponsive nanogels and polymer-drug/dye conjugates. Equipment/Software Student will Use: Polymer synthesis, diagnostic tools, UV-Vis, FT-IR, tumor ablation by hyperthermia, flow cytometry.