Controlled Synthesis, Processing, and Applications of Structural and Functional Nanomaterials: Energy Applications
Sponsored by: ACerS Basic Science Division, ACerS Electronics Division, ACerS Engineering Ceramics Division
Program Organizers: Haitao Zhang, University of North Carolina at Charlotte; Gurpreet Singh, Kansas State University; Kathy Lu, University of Alabama Birmingham; Edward Gorzkowski, Naval Research Laboratory; Jian Shi, Rensselear Polytechnich University; Michael Naguib, Tulane University; Sanjay Mathur, University of Cologne
Wednesday 8:00 AM
October 12, 2022
Room: 320
Location: David L. Lawrence Convention Center
Session Chair: Gurpreet Singh, Kansas State University; Michael Naguib, Tulane University
8:00 AM Invited
An Axially Continuous Graphene-Copper Wire for Multifunctional Applications: Wonmo Kang1; Hamzeh Kashani1; Chunghwan Kim1; Christopher Rudolf2; Keith Perkins2; 1Arizona State University; 2Naval Research Laboratory
With the increasing use of modern electric power systems in uniquely challenging situations, excellent electrical properties of conductors with environmental stability are becoming increasingly relevant. In this presentation, we demonstrate significantly enhanced electrical properties (i.e., a 450-% increase in the current density breakdown limit) and superb thermal stability compared to pure copper by synthesizing axially continuous-graphene layers on microscale-diameter copper wires. Our experiments combined with theoretical analysis reveal that the continuous graphene layers on a fine copper wire considerably improve (1) surface heat dissipation (224% increase), (2) electrical conductivity (41% increase), and (3) thermal stability (41.2% lower resistivity after thermal cycles up to 450oC) compared to pure copper wires. Our promising results and fundamental understanding of the underlying mechanisms may bring technical paradigm shift in designing high-performance, axially bi-continuous graphene-metal composites for high power transmission applications in aerospace, advanced electronics, electric vehicles, and power transportation systems.
8:30 AM Invited
Controlled Synthesis of Robust Reusable Nanostructures for Thermal Management and Energy Efficiency: Sharmila Mukhopadhyay1; 1University of Maine
As electronic devices shrink in size, efficient dissipation of waste heat generated at junctions become more challenging. One approach of rapidly transporting heat away from localized hot-spots is use of carbon nanotubes (CNT) that combine ultra-high thermal conductivity along axial direction with chemical stability and mechanical strength. CNTs, often used as coatings, fiber, film or aggregated paper, have shown significant promise in efficient heat-dissipation. However, the major limitation of most current designs is reusability and safety, because the nanotubes can disintegrate easily. This limitation is addressed by our design where CNT carpets/arrays are covalently bonded to larger substrates and act like built-in nano-radiators. This carpet not only provides heat dissipation, but also water repellency and EMI shielding. In-depth thermal investigation of these materials will be presented and current efforts in optimizing them for efficient thermo-electric conversion will be discussed.
9:00 AM
Synthesis of the Titanium Carbonitride MXenes and their Applications in Energy Storage: Anika Tabassum1; Kun Liang1; Ahmad Majed1; Kaitlyn Prenger1; Michael Naguib1; 1Tulane University
MXenes are a large family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides, with a composition of Mn+ 1 XnTx, where M is an early transition metal, X is C and/or N, n =1–4, and Tx denotes the surface terminations. They are electrically conductive and promising materials for electrochemical energy storage and conversion. Among the +45 synthesized MXenes, very few carbonitrides have been reported, despite the distinct properties of the first reported carbonitride (Ti3CNTx) compared to its carbide counterpart. This is in part due to the difficulty of synthesizing carbonitride. Herein, we report on the synthesis and applications of a new titanium carbonitride MXene (Ti2C0.5N0.5Tx) which exhibited the highest specific capacity among all reported MXene electrodes for sodium-ion batteries. In addition, we will discuss the performance of Ti3CNTx as electrocatalyst for hydrogen evolution reaction with an onset potential of 56 mV which is significantly lower than that of Ti3C2Tx.
9:20 AM
Role of Pre-Intercalation on the Electrochemical Performance of Ti3C2Tx MXene in Aqueous and Room Temperature Ionic Liquid Electrolyte (RTIL) Supercapacitors and in Sodium Ion Capacitors: Kaitlyn Prenger1; Kun Liang1; Alexander Brady2; Michael Naguib1; Robert Sacci2; Hsiu-Wen Wang2; 1Tulane University; 2Oak Ridge National Laboratory
MXenes, a large family of 2D transition metal carbides/nitrides, have demonstrated high electrical conductivity and an ability to host ions, making them attractive electrode materials for electrochemical energy storage (EES). Pre-intercalation can be used to tune MXene properties and behavior. Here we demonstrate three pre-intercalated Ti3C2Tx systems and their utilization for EES. 1-Pre-intercalating MXene with small amounts of alkyl metal cations can lead to multilayer K-Ti3C2Tx achieving outstanding areal capacitance of up to 5.7F/cm2 in aqueous electrolyte. 2-Pre-intercalation of different chain length alkylammonium (AA) cations opened MXene interlayer spacing for use in room temperature ionic liquids. At an interlayer spacing ≈2.2nm AA-Ti3C2Tx delivered a capacitance of 257F/g in neat EMIMTFSI (>3V window), achieving high energy and power densities. 3-Finally, we pre-intercalated Ti3C2Tx with 2Na equivalents for direct use in sodium-ion capacitors without the usual need for an electrochemical sodiation step of MXene cathodes in half-cell before utilizing it in full-cell.
9:40 AM Invited
Designing Atomically Precise Nanocatalysts for CO2 Electrochemical Reduction: Giannis Mpourmpakis1; 1University of Pittsburgh
Atomically precise Au nanoclusters, stabilized by organic ligands, exhibit well-defined structure (size/shape), but the accessibility of reactants to the metal is limited by the ligands. Experiments show that these nanoclusters are active for CO2 electroreduction, but the catalytic active sites are elusive. In this work, we apply first principles calculations to assess the CO2 reduction to CO on thiolate protected Au-based nanoclusters. We demonstrate that partial ligand loss from the nanocluster under electrochemical conditions generates active sites, significantly stabilizing the COOH intermediate. Interestingly, the reaction intermediates act as stabilizing ligands on the nanocluster. Importantly, heterometal doping can alter the electronic properties of the nanoclusters and tune the electrocatalytic activity and selectivity. This work highlights the importance of the electronic state of ligand-protected nanoclusters and the generation of catalytically active sites for CO2 electroreduction. Our computational findings rationalize experimental observations and demonstrate paths for designing active and tunable electrocatalysts.
10:10 AM Break
10:30 AM
Dopamine Assisted Phase Transformation and Electrochemical Charge Storage Properties of Vanadium Oxide/Carbon Composite Electrodes: Ryan Andris1; Timofey Averianov1; Ekaterina Pomerantseva1; 1Drexel University
Carbon containing nanocomposites are a class of materials capable of improving the electronic conductivity of metal oxides. In this work, chemically pre-intercalated dopamine (DOPA) molecules were used as both reducing agent and carbon precursor to prepare a variety of vanadium oxide/carbon composites via post-synthesis heat treatments. We found that the phase composition and morphology of the produced composites are influenced by the DOPA concentration used to synthesize the (DOPA)xV2O5 precursors. An increase of DOPA concentration led to more pronounced reduction of vanadium and a higher fraction of carbon in the composites’ structure. The electrochemical charge storage properties of the synthesized nanocomposites were evaluated in Li-ion cells. δ-V2O5∙nH2O/C, H2V3O8/C, VO2(B)/C, and V2O3/C electrodes delivered high initial capacities of 214, 252, 279, and 637 mAh·g-1, respectively. The insights provided by this investigation open the possibility of creating new nanocomposite oxide/carbon electrodes for a variety of applications that require redox activity.
10:50 AM
Computation-aided Developments of Highly Durable and Active Photoanodes and Electrocatalysts: Heechae Choi1; 1University of Cologne
The state-of-art density functional theory (DFT) calculation methods have greatly contributed to mechanism investigations and efficient developments of various catalytic materials with the high accuracy in energy predictions. On the contrary to the catalytic materials having homogeneity and metallicity, the largely variable catalytic activities of semiconductors and heterogeneous nanomaterials have not been well understood so far. Therefore, it is very challenging to rationally design wide-gap oxide catalysts or heterogeneous catalysts having complex geometry. Recently, I have developed a new theoretical model to explain the large variations of photoelectrochemical and electrocatalytic activities of semiconductors with doping, defect equilibria, and metal particle decorations. In this talk, I will present how I took the effects of nanomaterials geometries, Fermi-level variations, and interface defects into accounts for highly active and durable catalysts designs. In addition, a new material design principle of metal-semiconductor junctioned systems for enhanced selectivity of target reactions will be presented.
11:10 AM
Towards the Synthesis of Semiconducting Materials for Photo(electro)catalysis in Energy Conversion: CO2 Reduction and CH4 Controlled Oxidation: Caue Ribeiro1; 1Brazilian Agricultural Research Corporation - EMBRAPA
The climate problems related to greenhouse gas emissions request strategies for decarbonizing the global economy. Recycling CO2 and CH4 emissions using renewable energies, such as solar, depends on developing electrochemical routes with high efficiency, good selectivity, and long-term use. Thus, the design of photo(electro)catalysts plays a fundamental role. Several semiconductors such as TiO2, BiVO2, ZnO, CuO, and Cu2O, among others, have been synthesized and characterized as photoanodes or photocathodes. Finally, the photo(electro)chemical cell concept is challenging, demanding substrates to support the catalysts (immobilization), membranes for ion separation, and adequate fluid dynamics. A review of the concepts of photoelectrocatalysis applied to an integrated approach of CO2 reforming (reduction), and CH4 reforming (controlled oxidation to liquid products) is proposed, comprising a comparison of photoelectrocatalytic systems against other alternatives (e.g., high-temperature reactions), along with the specific challenges (synthesis routes, catalyst discovery, system design, upscaling) emphasizing case studies from our research group.
11:30 AM
Synthesis of WO3-AgCl Thin Films for Application in Continuous Photocatalytic Microreactor: Priscila Hasse Palharim1; Carolina de Araújo Gusmão1; Bruno Ramos1; Antonio Carlos Silva Costa Teixeira1; 1Universidade de São Paulo
Heterogeneous photocatalysis has shown promising results for wastewater treatment. Among the semiconductors commonly studied, WO3 is a material with interesting properties: its narrow band gap (2.5–2.8 eV) render it active in the wide UV-visible range. Silver-based materials (Ag2S, Ag2WO4, AgCl etc.) can be coupled to WO3 to improve its photocatalytic activity at a low cost, while extending its absorption range into the visible spectrum. In addition to the photocatalytic material, the type of reactor is also important. Although batch reactors are commonly used to evaluate the efficiency of these materials, their use is mainly restricted to laboratory investigations. Continuous microreactors allow an initial evaluation of different photocatalysts at a reduced scale, and enable the study of scaling-up. In this work, thin films of WO3 coupled with AgCl were synthesized, and their photocatalytic performances were assessed in microreactors under simulated sunlight using acetaminophen as a model contaminant.
11:50 AM
Synthesis and Characterization of Copper Nanowire Array: Long Zhu1; Fei Ren1; 1Temple University
Copper nanowire arrays exhibit attractive electrical, thermal, and mechanical properties with potential applications in many engineering fields such as thermal interface and electrical contacts. The reliability of Cu nanowire array-based devices relies on robust bonding between the nanowires and the substrates. Therefore, it is of great significance to evaluate and improve the bonding strength of Cu nanowire on the substrate. In this work, Cu nanowire arrays were prepared by electrochemical deposition on Cu substrate using polymer membrane templates. The mechanical properties of the nano arrays, including the elastic modulus, were characterized by nanoindentation method. The bonding strength between the nanowire array and the substrate was examined by nanoscratch technique. In addition, the electrical, thermal, and anti-corrosion behavior were studied. Furthermore, polydopamine (PDA) coating was applied on the Cu nanowire arrays, and the effect of the coating on the abovementioned properties were studied and compared to the bare Cu material.