Functional Nanomaterials: Functional Low-Dimensional (0D, 1D, 2D) Materials 2022: On-Demand Oral Presentations
Sponsored by: TMS Functional Materials Division, TMS: Nanomaterials Committee
Program Organizers: Michael Cai Wang, University of South Florida; Yong Lin Kong, University of Utah; Sarah Ying Zhong, University of South Florida; Surojit Gupta, University of North Dakota; Nasrin Hooshmand, Georgia Institute of Technology; Woochul Lee, University of Hawaii at Manoa; Min-Kyu Song, Washington State University; Simona Hunyadi Murph, Savannah River National Laboratory; Hagar Labouta, University of Manitoba; Max Anikovskiy, University of Calgary; Patrick Ward, Savannah River National Laboratory

Monday 8:00 AM
March 14, 2022
Room: Nanostructured Materials
Location: On-Demand Room

Mickey Mouse on NanoCaffeine: Belinda Heyne1; 1University of Calgary
    As one of the most versatile reactive oxygen species, singlet oxygen, is at the forefront of a vast window of applications. In a medical context, production of singlet oxygen has been widely used in photodynamic therapy to kill cancerous tumors and microbial pathogens. Recently, growing attention has emerged on photodynamic inactivation (PDI) of bacteria. To allow a broad application of PDI, strategies to maximise singlet oxygen production remains to be developed. Nanoplasmonic materials offer one of the most promising strategies to improve the performances of current PDI by using light and metal nanoparticles, exploiting a phenomenon called “plasmon enhancement effect”. The overall goal of our research consists of building a fundamental knowledge concerning this effect by designing nanoscale model systems to kill bacteria. Herein, we present how the morphology and composition of plasmonic nanoparticles affects the extent of metal enhanced singlet oxygen production in a PDI of bacteria framework.

Processing of Nanocrystalline Diamond Coatings for Biomedical Applications: Roger Narayan1; 1University of North Carolina
     Diamond thin films such as nanocrytalline diamond and ultrananocrystalline diamond thin films are finding greater use in prostheses and other biomedical devices. Diamond thin films exhibit exceptional biomedical properties, including chemical inertness and wear resistance. In addition, the conductivity of diamond thin films can be altered through the incorporation of nitrogen. Ultrananocrystalline diamond-coated microneedles have been evaluated for electrochemical sensing, and nanoporous membranes have been examined for neural interface applications. We have previously demonstrated electrochemical detection of uric acid and dopamine under in vitro conditions with unmodified N-UNCD microneedles. We have also previously created free-standing nanoporous ultrananocrystalline diamond membranes with pore sizes of 100 nm by growing ultrananocrystalline diamond thin films on nanoporous silicon nitride membranes and reactive ion etching; the attachment of SK-N-SH cells on the membrane features was demonstrated. Our results suggest that diamond thin films exhibit many unique attributes that many enhance the function of medical devices.

Crumpling and Assembling of 1D/2D Nanomaterials into 3D Functional Structures: Baoxing Xu1; 1University of Virginia
    Assembly of nanomaterials such as graphene into functional structures has drawn tremendous attention for their potential widespread applications in a bulk form in the rational design of multifunctional structures and devices, yet this is challenging in manufacturing. I will start with the introduction of a capillary crumpling approach that helps create a new platform for attaining bulk quantities of nanomaterials meanwhile minimizing the simple restacking in assembly through local deformation, thus allowing to keep the large specific surface area and versatile surface functions of nanomaterials in their bulk forms. I will then present the development of both quantitative theory and coarse-grained computational models to reveal crumpling and self-assembly mechanism in parallel with comparison with available experiments. After that, the properties of assembled 3D architectural structures by graphene and graphene/CNTs will be demonstrated in terms of accessible area and mechanical strength.

Engineered Nanoclays in Bone Tissue Engineering and Bone Metastasis of Cancer: Kalpana Katti1; Haneesh Jasuja1; Dinesh Katti1; 1North Dakota State University
    Nanoclays are unique nanomaterial systems that are altered with small molecules called as ‘modifiers’ to result in ‘engineered nanoclays’ that are the primary components of polymer-clay-nanocomposites. These nanocomposites have a variety of applications as structural composites, diffusion barrier coatings and biomedical. We report a simulations-based design of novel polymer-clay-nanocomposites with varying modifier molecules especially suited for as scaffolds for bone tissue engineering. The complex hierarchical structure of the bone-mimetic collagen fibrils is created using the nanoclay platform. Besides the applications in regenerative medicine, we use these engineered bone structures as testbeds for evaluation of breast and prostate cancer bone metastasis. The novel metastatic cancer testbeds are used to screen novel drugs and develop new metastasis biomarkers such as nanomechanical, IR and RAMAN spectroscopic. Both the mechanical properties as well as biological response of human mesenchymal-stem-cells and human cancer cells is tailored and impacted with the use of engineered nanoclays.

In Situ Spectroscopic Characterization of the Electrode-electrolyte Interphase: Sang-Don Han1; 1National Renewable Energy Laboratory
    The electrode-electrolyte interphase remains a poorly understood topic in Li-ion battery (LiB) research due to its intrinsic properties—complexity, high reactivity and continuous evolution—and its detailed and real-time analysis is a great challenge. Vibrational spectroscopy is a powerful tool for understanding the interfacial chemical reactions and the structural changes in an electrode, so the technique is used extensively by the battery community in their ex situ form. Developing in situ variants of the technique, however, can provide new insight and help to elucidate the failure mechanism in battery systems. Recently, we have developed in situ vibrational spectroscopic methods that show reproducible and reliable performance over multiple cycles in terms of both electrochemistry and spectroscopy, which enables us to monitor the surface chemistry and structural changes on/in the electrode. This is critical to gaining a fundamental and mechanistic understanding of the electrochemical performance of LiBs.

LED Assisted Synthesis and Excitation of Silver Nanoparticles for Plasmon-enhanced Antibacterial Effects: Connor Bourgonje1; Juan C. Scaiano1; 1University of Ottawa
    In this work, we expand on a seed-mediated silver nanoparticle (AgNP) synthesis which utilizes LED illumination to control the morphology and optical properties of citrate capped AgNPs. This method eliminates the need for surfactants (such as CTAB) to control AgNP shape, allowing for wavelength-dependent growth of decahedral, spherical, or triangular AgNPs with tunable sizes and absorbance bands spanning the entire visible and NIR spectrum. Using this method, we were able to synthesize triangular AgNPs with strong plasmonic absorbance in the biological window, the region in the visible/NIR region where photons can best penetrate biological samples. Under illumination with NIR LEDs the antibacterial activity of these AgNPs increases by several orders of magnitude, requiring only minutes to achieve 8 Log reductions in bacterial CFU counts. These preliminary results show great promise in enhancing the effectiveness of AgNPs, showcasing their immense potential as antibacterial and phototherapeutic agents when paired with LED illumination.

Reticulated Structure of Sulfur/Nitrogen-doped Graphene Oxide for High Specific Energy Lithium/Sulfur cells: Yoon Hwa1; 1Arizona State University
     Graphene oxide (GO) has been regarded as an effective functional additive of the sulfur electrode because the sulfur-philic characteristic of GO can significantly suppress the lithium polysulfide (Li-PS) shuttle during cell operation. In this presentation, a sulfur-nitrogen doped GO (S–NrGO) nanocomposite electrode with a reticulated pore structure, referring to the interconnected ionic percolation channel will be introduced. Multifaceted approaches to develop the reticulated structure of the S–NrGO composites with the adequate surface area of NrGO by intentionally reducing the aggregation of all composite materials will be discussed. While improved lithium-ion percolation through the reticulated ionic channel of the S–NrGO composite promotes electrochemical reaction kinetics of the sulfur electrode, enhanced utilization of the highly sulfur-philic surface of NrGO effectively mitigate Li-PS shuttle, thereby leading to substantial improvement of electrochemical performance of Li/S cells with a high peak specific energy of 325 Wh/kg(calculated).

Photoabsorbers with 2D Layered Perovskites for Bendable Optoelectronics and Solar Cells: Anupama Kaul1; Mohin Sharma1; 1University of North Texas
    We discuss our efforts in studying the light-matter interactions in halide-grown monolayer and few-layer 2D semiconducting WSe2 to unveil multibody interactions towards quantum platforms. Heterostructures of 0D-2D ensembles also offer an intriguing prospect to enhance the light matter interactions in these systems to new levels. When sheets of graphene are physically confined into nanoscale dimensions, either as graphene nanoribbons or zero-dimensional (0D) structures, such as graphene quantum dots (GQDs), a band gap in such structures is induced due to quantum confinement. We discuss the integration of GQDs and 2D MoS2 for optoelectronic devices surpassing the limitations of MoS2 photodetectors where the GQDs extend the optical absorption into the near-UV regime. Finally, our additive manufacturing approaches with organo-halide 2D perovskites, specifically, butylamine methyl-ammonium lead triiodide, opens up possibilities to inkjet print these complex crystallites and their heterostructures for exceptional optical absorbers in photodetectors and photovoltaics applications.

Architecting 3D Lithium-ion Batteries: Corie Cobb1; 1University of Washington
    Technology progressions in portable electronics and electric vehicles have motivated a shift in Lithium-ion (Li-ion) batteries to accommodate rapid charge, long cycle life, higher power and energy materials with more efficient packaging. An emerging trend to address this technology shift is the use of additive manufacturing (AM) techniques to rapidly pattern and manufacture batteries with customized three-dimensional (3D) geometries on a micron to millimeter scale, changing the way we fundamentally create energy storage devices today. 3D battery architectures enhance ion transport in existing battery materials, thereby increasing useable energy and power densities relative to conventional planar geometry batteries. This talk will highlight promising design and material concepts for high-performance 3D Li-ion batteries from our research group, with a focus on AM material compatibility and manufacturing methods that are key components for more broadly enabling novel fabrication routes for functional materials and advanced device applications.

Dynamic Vessel-on-a-chip Model: Bringing Bio-relevance to In Vitro Evaluation of Quantum Dots: Hagar Labouta1; 1University of Manitoba
    Microfluidics, manipulation of fluids at the sub-millimetre scale, has given rise to platforms for controlled synthesis of nanomaterials as well as to biomimetic systems called organ-on-a-chip to evaluate nanoparticles under conditions mimicking in vivo scenarios. My talk will focus on our research on synthesizing nanoparticles under controlled flow conditions and examining their interaction with cells exposed to shear stress due to flow. We have developed a vessel-on-a-chip model using vascular endothelial cells (HUVEC) subjected to shear stress within the physiological range, 1 dyne/cm2. Using this model, we examined the effect of wall shear stress on the interaction of quantum dots with the endothelium in regards to cell viability, cell internalization of quantum dots, as well as their effect on the cell transcriptome using microarray analysis. The results of this work will direct future studies towards the use of in vitro approaches for improving in vitro-in vivo correlation.

In Situ Chemo-mechanical Characterization of the Formation and Oxidation of Redox Reaction Products at Nanoscale For Li-O2 Batteries: Omer Ozgur Capraz1; Hannah Dykes1; 1Oklahoma State University
    The theoretical energy density of lithium-oxygen batteries is by far the closest competitor to gasoline compared to other battery configurations. The sluggish oxygen evolution kinetics are typically more severe and cause the slow oxidation of lithium peroxide. It is crucial to elucidate how the nucleation of discharge products on the cathode surface affects the electrochemical performance in order to design new electrolytes and cathodes for lithium-oxygen batteries. In this study, we investigate the impact of the electrolyte salt on nanoscale dynamic changes on the surface of thin Au film cathode (1-D) during charge / discharge of Li-O2 batteries. In situ curvature evolution on the cathode is monitored during discharge and charge cycle via galvanostatic and cycling voltammetry. We will present the impact of the electrolyte salt on the potential-dependent surface stress generation during the formation and oxidation of electrochemical redox reaction products at nanoscale on the Au thin film cathode.

In-situ Investigation of the Interface Formation between Si-terminated Diamond and a Nb2O5 Electron Acceptor Layer for Electronic Applications: Gabrielle Abad1; Stephen McDonnell1; 1University of Virginia
    Diamond, an ultra-wide band gap semiconductor, has shown promise in high power, frequency, and temperature electronics; however, issues with impurity doping has limited its use. Instead, surface transfer doping has been used to induce a two-dimensional hole gas at the diamond surface increasing its conductivity. The established method to do this is to hydrogen-terminate diamond prior to the addition of an electron acceptor layer. Alternatively, we investigate silicon-terminated diamond with a Nb2O5 electron acceptor layer. In ultra-high vacuum, Si is deposited onto diamond substrates via electron beam (e-beam) deposition. The formation of Nb2O5 is accomplished by either sequentially e-beam depositing Nb in an oxygen partial pressure or exposing Nb to oxygen post-deposition. To observe how surface structure. interfacial chemistry, electronic structure, and band alignment evolves with Nb2O5 thickness, in-situ low energy electron diffraction (LEED), x-ray photoemission spectroscopy (XPS), ultraviolet photoelectron (UPS) spectroscopy, and angle-resolved photoemission (ARPES) spectroscopy are used.

MoS2 Thermoelectrics for Sustainable Energy: Amall Ramanathan1; 1The University of Jordan
    Thermoelectric (TE) energy harvesting is the new area of investigation for sustainable development and application of modern day nano-micro technologies. New and novel techniques for energy harvesting are required with miniaturizing of semiconductor devices, especially in wearable technologies and sensors for the internet of things (IOT). Over 60% of the energy supply is emitted back to the environment as waste ’heat’ primarily below 300C. The favorable band gap, absence of dangling bonds, the high crystalline layered structure, with the possibility easy low dimensional fabrication makes MoS2 a prime candidate for thermoelectrics. In fact, there have been several studies on monolayer, bilayer, nano-ribbons, and other nanostructures of MoS2 that have explored ways of enhancing the Seebeck coefficient S and energy conversion efficiency ZT. This work is the author’s perspective of the latest innovations and technologies to successfully use various forms of MoS2 as a TE generator (TEG) in different devices.

Nanostructured Materials: A Review on Its Application in Water Treatment: Ikhazuagbe Ifijen1; Esther Ikhuoria2; Muniratu Maliki3; Godfrey Otabor2; Areguamen Aigbodion1; 1Rubber Research Institute of Nigeria; 2University of Benin, Benin City, Edo State,Nigeria; 3Department of Industrial Chemistry, Edo University Iyamho, Edo State, Nigeria
    Nano-sized materials have been the subject of active research and advancement worldwide in recent years due to the extraordinary properties resulting from nano-size, such as enhanced catalysis and adsorption properties and high reactivity. Diverse investigations have revealed that nanomaterials can efficiently eliminate several pollutants in water and thus have been favourably applied in water and wastewater treatment. This review focused on some broadly investigated nanomaterials, carbon nanotubes, graphene-based nanomaterials, metal oxide-based nano-adsorbents and bimetal oxide magnetic nanomaterials. The numerous studies carried out on the adsorptive capability of nanostructured materials shows that they are very promising for water treatment.

Second NIR-absorbing Gelatin Stabilized Gold Nanorods with High Media and Photothermal Stability for Photothermal Cancer Therapy: Samuel Oluwafemi1; Thabang Lebepe1; 1University of Johannesburg
    The excellent photothermal properties of gold nanorods (Au-NRs) make them one of the most researched plasmonic photothermal nanomaterials. However, their biological applications have been hampered greatly due to surfactant-induced cytotoxicity. We herein report the synthesis of highly biocompatible gelatin stabilized Au-NRs (gelatin@Au-NRs) to address this issue. The as-synthesized gelatin@Au-NRs were highly crystalline and rod-like in shape with an average length and diameter of 66.2 2.3 nm and 10 1.6 nm, respectively. The as-synthesized gelatin@Au-NRs showed high stability in common biological media (phosphate buffer saline and Dulbecco’s Modified Eagle’s Medium) compared to CTAB capped Au-NRs. Similarly, the gelatin@Au-NRs showed an improved heat production and outstanding cell viability against two different cancer cell lines; KM-Luc/GFP (mouse fibroblast histiocytoma cell line) and FM3A-Luc (breast carcinoma cell line) compared to CTAB capped Au-NRs and PEG@Au-NRs. In vitro, a photothermal therapy study against KM-Luc/GFP demonstrated the gelatin@Au-NRs are effectively destroying the cancer cells.

Facile Synthesis of Novel Quaternary Zn-Cu-In-S/ZnS QDs- mTHPP Porphyrin Conjugate and Its Photodynamic Therapy of Cancer and Antibacterial Activities: Samuel Oluwafemi1; 1University of Johannesburg
    Photodynamic therapy (PDT) is a non-invasive treatment modality that uses photosensitizing drugs (PS) to generate reactive oxygen species for the destruction of abnormally growing cells or microorganisms. Porphyrins are the most widely used PS in PDT however, their clinical application is limited by poor water solubility, which often results in aggregation and their low quantum yield of ROS generation after light absorption in the near infra-red region (NIR. To overcome these limitations and improve PDT efficacy, we herein report the conjugation of Zn-Cu-In-S/ZnS (ZCIS/ZnS) quantum dots (QDs) to 5,10,15,20 meso (4-hydroxyphenyl) porphyrin (mTHPP) and evaluated its PDT efficiency against murine metastatic melanoma (B16 F10 Nex 2) cell line and its antibacterial potency against Escherichia coli (ATCC 25922). The results of this study show that the as-synthesized ZCIS/ZnS – mTHPP conjugate is a suitable and promising class of material for dual anti-cancer and antimicrobial PDT.