Novel energy-efficient tunable method for fabrication of nanomaterials: Biomedical and energy storage applications
First and second years funded by an anonymous donor.
From January 2025 the project is funded and administered by the Higher Education and Science Committee of Armenia.
Principal Investigator: Prof. Alexander Mukasyan
University: University of Notre Dame
Research Group: Aram Manukyan, Khachatur Kirakosyan, Armine Ginoyan, Vardges Avakyan Harutyun Gyulasaryan, Armenuhi Sargsyan, Davit Hambardzumyan
Contributing Researchers: Astghik Kuzanyan
Duration: 2023-2027
Hosting partner: Institute for Physical Research of National Academy of Sciences of Armenia (IPR-NAS, ASHTARAK, ARMENIA)
Project Importance
Nanocomposites represent а class of materials, which due to their unique properties, found applications in different industries, including energy, aerospace, and automotive. The global nanocomposites market is rapidly growing, with the forecast of total investments up to $14.34 billion by 2027. Among various compounds, the metal-carbon nanocomposites have received great attention due to the unique combination of properties such as excellent flexibility, environmental friendliness, chemical durability, light weight, excellent mechanical properties, biocompatibility and unique electrical and magnetic capabilities. Such nanocomposites have various applications, including in biomedicine, energy conversion and storage, catalysis, agriculture, etc.
Several methods are known for the fabrication of the metal-carbon nanocomposites, including arc-discharge, RF plasma torch, magnetron, and ion beam co-sputtering, high-temperature annealing of the mixtures of carbon-based materials and metal-containing powders, pyrolysis of organometallic compounds and catalytic carbonization process. All these approaches have advantages and drawbacks. Among them, pyrolysis synthesis (PS: the thermal decomposition of a substance in a non-reactive atmosphere at high temperatures to produce a valuable solid product) is considered a promising approach since it possesses attractive flexibility for scale-up. It is important that the research team from the Institute for Physical Research of the National Academy of Sciences of Armenia (IPR-NAS, ASHTARAK, ARMENIA) has long-term experience in PS of carbon-based nanocomposites. The Armenian scientific group has developed solid-phase pyrolysis of metal-organic compounds. Several metal-carbon nanostructures have been synthesized using this method, and their structure, morphology, and magnetic properties have been investigated. The following drawbacks of the PS can be outlined: (a) the use of an external energy source, (b) relatively long heat treatment duration (10-600 min). It means that PS is an energy-consuming process. Also, the agglomeration of the fabricated particles during a relatively long-term high-temperature treatment is an issue that does not allow to reach the desired properties. Thus, developing an energy-efficient method, which permits the rapid formation of nanomaterials, is a critical fundamental task.
Solution combustion synthesis (SCS) is an exciting phenomenon that involves self-sustained exothermic reactions using aqueous solutions or sol-gel media. This process allows for the synthesis of a variety of nanoscale materials, including oxides, metals, alloys, and sulfides, as well as carbon (graphene)- metal/metal oxides composites. We can define SCS as a complex self-sustained chemical process. After initiation, SCS starts with rapid dehydration and thermal decomposition of the homogeneous solution and involves several thermally coupled exothermic reactions, which result in the formation of desired solid compounds. The characteristic time of the process is about seconds. The SPS temperatures are comparable with those for PS; however, essentially, all energy is provided by the exothermic self-sustained reactions. It is critical that SCS allows fine control of the morphology of the synthesized nanomaterials. The International Principal Investigator (IPI) has 40 years of experience working in the field of combustion synthesis and is the world-recognized leader in this field.
The fundamental task of the project is to combine the advantages of the PS and SCS approaches and to develop a novel energy-efficient template-assisted synthesis method to produce multifunctional nanocomposites with tuned microstructure and superior properties. It is essential that the project, with its general concept, intersect with several global problems, such as cancer therapy and energy storage. Specifically, we plan to synthesize: (a) high-efficient functional nano-materials for magnetic hyperthermia of tumors; (b) carbon encapsulated nanoparticles for the usage as anode material in high-performance supercapacitors.
Expected Results and Impact
The project aims to develop a highly stable biocompatible magnetic core-shell nanocomposite with adjustable magnetic characteristics for drug delivery and disease diagnostics. Several types of compositions are planned to be investigated. For example, the "core-shell" architecture with Fe-core and shell - Fe3O4 or Fe3C as well as with an external graphite/graphene carbon shell will be synthesized by a novel TASP method. The Armenian team has experience for the PS fabrication of such materials. The main quantitative parameter that characterizes the suitability of nanoparticles for magnetic hyperthermia is SAR (Specific Absorption Rate). It represents the energy of the electromagnetic field absorbed per second by nanoparticles in body tissues, and in general, it determines the heating speed of the surrounding environment. The exact value of coefficient SAR strongly depends on the nanoparticle's size, shape, composition, concentration, magnetic interaction, and the frequency and amplitude of the applied magnetic field. We are confident that TASP allows the fabrication of such composite particles of much smaller size and narrow particle size distribution and also tunes up its magnetic properties. The other core-shell (Me@C; Me=Co, Ni, Fe, and their alloys) nanoparticles will be fabricated by TASP and tested in vitro and in vivo.
We expect to fabricate the magnetic core-shell biocompatible nanocomposite with average sizes of 3, 5, 10, and 20 nm and superparamagnetic-ferromagnetic transition temperature in the range of 40-50 °C. The magnetic properties of fabricated nanocomposites will be investigated at IPR-NAS using a sample magnetometer. The magnetic heating properties of the nanocomposites water liquids under the influence of an external magnetic field will be measured at the IPR-NAS using a generator with a power of 10 kW, with an amplitude of 50-1800 Oe and a frequency of 100-400 kHz. In vivo studies on mice will be accomplished in the Notre Dame Integrated Imaging Facility of the University of Notre Dame (USA) by using advanced CT and optical diagnostics. The particle with the optimized characteristic will be recommended for the further certifications.
For supercapacitor application, we will work on several composite carbon-based nano-materials. Among the supercapacitors, pseudo-capacitors that rely on surface rapid redox reactions for energy storage possess significantly higher energy densities as compared to conventional electrochemical double-layer capacitors. Currently, the pseudo-capacitors mostly use transition-metal oxides (TMOs), primarily due to their high theoretical specific capacitance. However, TMOs exhibit limited electronic conductivity, which impedes their usage in practical devices. By contrast, transition metal carbides (TMCs) have high electronic conductivity and mechanical stability besides being corrosion resistant. The possibility of using TMCs in electrochemical energy storage has been explored widely both at theoretical and experimental levels, suggesting their profound potential in energy storage.
Specifically, we will challenge to enhance the properties of the Fe/Fe3C nanoparticles encapsulated with graphitic layers, i.e. to achieve record-high specific capacitance above 250 F g−1. We will also study the Me@C (Me: Ni, Co) compositions. The Armenian team has experience in PS of such nanocomposites that showed encouraging results. By using TASP, we are confident that we can enhance the properties of such nanocomposites, which can be tested as electrodes for the supercapacitor with the H2SO4 electrolyte. Cyclic voltammogram (CV) and galvanostatic charge/discharge (GCD) tests will be performed at IPR-NAS.
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