Yifan Tang

Electrocatalytic Activity of Nitrogen-Doped Carbon Nanotube Cups

The electrochemical activity of stacked nitrogen-doped carbon nanotube cups (NCNCs) has been explored in comparison to commercial Pt-decorated carbon nanotubes. The nanocup catalyst has demonstrated comparable performance to that of Pt catalyst in oxygen reduction reaction. In addition to effectively catalyzing O(2) reduction, the NCNC electrodes have been used for H(2)O(2) oxidation and consequently for glucose detection when NCNCs were functionalized with glucose oxidase (GOx). Creating the catalysts entirely free of precious metals is of great importance for low-cost fuel cells and biosensors.

Chemical Sensing with Polyaniline Coated Single‐Walled Carbon Nanotubes

Single-walled carbon nanotube/polyaniline (SWNT/PAni) nanocomposite with controlled core/shell morphology was synthesized by a noncovalent functionalization approach. Unique electron interactions between the SWNT core and the PAni shell were studied electrochemically and spectroscopically, and superior sensor performance to chemical gases and vapors was demonstrated.

Understanding Interfaces in Metal-Graphitic Hybrid Nanostructures.

Metal-graphitic interfaces formed between metal nanoparticles (MNPs) and carbon nanotubes (CNTs) or graphene play an important role in the properties of such hybrid nanostructures. This Perspective summarizes different types of interfaces that exist within the metal-carbon nanoassemblies and discusses current efforts on understanding and modeling the interfacial conditions and interactions. Characterization of the metal-graphitic interfaces is described here, including microscopy, spectroscopy, electrochemical techniques, and electrical measurements. Recent studies on these nanohybrids have shown that the metal-graphitic interfaces play critical roles in both controlled assembly of nanoparticles and practical applications of nanohybrids in chemical sensors and fuel cells. Better understanding, design, and manipulation of metal-graphitic interfaces could therefore become the new frontier in the research of MNP/CNT or MNP/graphene hybrid systems.

Carbon Nanotube Chemiresistor for Wireless pH Sensing

The ability to accurately measure real-time pH fluctuations in-vivo could be highly advantageous. Early detection and potential prevention of bacteria colonization of surgical implants can be accomplished by monitoring associated acidosis. However, conventional glass membrane or ion-selective field-effect transistor (ISFET) pH sensing technologies both require a reference electrode which may suffer from leakage of electrolytes and potential contamination. Herein, we describe a solid-state sensor based on oxidized single-walled carbon nanotubes (ox-SWNTs) functionalized with the conductive polymer poly(1-aminoanthracene) (PAA). This device had a Nernstian response over a wide pH range (2–12) and retained sensitivity over 120 days. The sensor was also attached to a passively-powered radio-frequency identification (RFID) tag which transmits pH data through simulated skin. This battery-less, reference electrode free, wirelessly transmitting sensor platform shows potential for biomedical applications as an implantable sensor, adjacent to surgical implants detecting for infection.

Nano-gold corking and enzymatic uncorking of carbon nanotube cups

Because of their unique stacked, cup-shaped, hollow compartments, nitrogen-doped carbon nanotube cups (NCNCs) have promising potential as nanoscale containers. Individual NCNCs are isolated from their stacked structure through acid oxidation and subsequent probe-tip sonication. The NCNCs are then effectively corked with gold nanoparticles (GNPs) by sodium citrate reduction with chloroauric acid, forming graphitic nanocapsules with significant surface-enhanced Raman signature. Mechanistically, the growth of the GNP corks starts from the nucleation and welding of gold seeds on the open rims of NCNCs enriched with nitrogen functionalities, as confirmed by density functional theory calculations. A potent oxidizing enzyme of neutrophils, myeloperoxidase (MPO), can effectively open the corked NCNCs through GNP detachment, with subsequent complete enzymatic degradation of the graphitic shells. This controlled opening and degradation was further carried out in vitro with human neutrophils. Furthermore, the GNP-corked NCNCs were demonstrated to function as novel drug delivery carriers, capable of effective (i) delivery of paclitaxel to tumor-associated myeloid-derived suppressor cells (MDSC), (ii) MPO-regulated release, and (iii) blockade of MDSC immunosuppressive potential.

Corking carbon nanotube cups with gold nanoparticles.

Nitrogen doping of carbon nanotubes during chemical vapor deposition synthesis can create unique stacked cup-shaped structures termed as nitrogen-doped carbon nanotube cups (NCNCs). These cups have semielliptical hollow cavities and elevated reactivity which could lead to various applications. In this work, by applying intense ultrasonication to the as-synthesized NCNCs, we demonstrated an effective mechanical method to isolate the individual cups with opened cavities from their stacks. The graphitic structures of the isolated cups and their inherent nitrogen functionalities were characterized by comprehensive microscopic and spectroscopic methods. In particular, we quantitatively determined the existence of amine functionalities on NCNCs and found that they were preferentially distributed at the open edges of the cups, providing localized reactive sites. Further, by thiolating the amine groups with 3-mercapto-propionic acid, we were able to effectively cork the isolated cups by gold nanoparticles with commensurate diameters. These cup-shaped carbon nanomaterials with controlled inner volumes and gold nanoparticle corks could find potential applications as nanoscale reaction containers or drug delivery vehicles.

Block copolymer-templated nitrogen-enriched nanocarbons with morphology-dependent electrocatalytic activity for oxygen reduction

Binder-free films of nitrogen-enriched nanocarbons, prepared by the pyrolysis of polyacrylonitrile-block-poly(n-butyl acrylate) copolymer drop-casted on glassy carbon disk electrode, exhibited high electrocatalytic activity for the oxygen reduction reaction (ORR), matching that of Pt-based electrocatalyst. Dependence of the activity on pyrolysis temperature revealed that it is governed by the interplay of nitrogen content and electrical conductivity of the material. It was demonstrated that a nanocarbon formed by pyrolysis at 800 °C provided both large number of electrons transferred and high kinetic current density. ORR performance has been shown to critically depend on the presence of a nanoporous structure, suggesting that it facilitates high density and accessibility of catalytic sites, such as nitrogen-terminated edges of nanographitic domains.

Oxidative Unzipping of Stacked Nitrogen-Doped Carbon Nanotube Cups

We demonstrate a facile synthesis of different nanostructures by oxidative unzipping of stacked nitrogen-doped carbon nanotube cups (NCNCs). Depending on the initial number of stacked-cup segments, this method can yield graphene nanosheets (GNSs) or hybrid nanostructures comprised of graphene nanoribbons partially unzipped from a central nanotube core. Due to the stacked-cup structure of as-synthesized NCNCs, preventing complete exposure of graphitic planes, the unzipping mechanism is hindered, resulting in incomplete unzipping; however, individual, separated NCNCs are completely unzipped, yielding individual nitrogen-doped GNSs. Graphene-based materials have been employed as electrocatalysts for many important chemical reactions, and it has been proposed that increasing the reactive edges results in more efficient electrocatalysis. In this paper, we apply these graphene conjugates as electrocatalysts for the oxygen reduction reaction (ORR) to determine how the increase in reactive edges affects the electrocatalytic activity. This investigation introduces a new method for the improvement of ORR electrocatalysts by using nitrogen dopants more effectively, allowing for enhanced ORR performance with lower overall nitrogen content. Additionally, the GNSs were functionalized with gold nanoparticles (GNPs), resulting in a GNS/GNP hybrid, which shows efficient surface-enhanced Raman scattering and expands the scope of its application in advanced device fabrication and biosensing.

Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers

Nitrogen-doped carbon nanotubes consist of many cup-shaped graphitic compartments termed as nitrogen-doped carbon nanotube cups (NCNCs). These as-synthesized graphitic nanocups from chemical vapor deposition (CVD) method were stacked in a head-to-tail fashion held only through noncovalent interactions. Individual NCNCs can be isolated out of their stacking structure through a series of chemical and physical separation processes. First, as-synthesized NCNCs were oxidized in a mixture of strong acids to introduce oxygen-containing defects on the graphitic walls. The oxidized NCNCs were then processed using high-intensity probe-tip sonication which effectively separated the stacked NCNCs into individual graphitic nanocups. Owing to their abundant oxygen and nitrogen surface functionalities, the resulted individual NCNCs are highly hydrophilic and can be effectively functionalized with gold nanoparticles (GNPs), which preferentially fit in the opening of the cups as cork stoppers. These graphitic nanocups corked with GNPs may find promising applications as nanoscale containers and drug carriers.

Growth of Carbon Nanotubes on Copper Substrates Using a Nickel Thin Film Catalyst

Carbon nanotubes with their attractive properties, one-dimensional geometry, and their large aspect ratio are ideal candidates for a variety of applications including energy storage, sensing, nanoelectronics, among others. We have studied the growth of carbon nanotubes on copper substrates using a nickel thin film as a catalyst. The catalyst was sputtered in a chamber with a base pressure in the ultra-high-vacuum regime. By adjusting the sputtering parameters, the effects of the morphology and the thickness of the nickel catalyst on the growth of carbon nanotubes have also been investigated. Multiple hydrocarbon sources as carbon feedstock (methane, acetylene and m-xylene), corresponding catalyst precursors and varying temperature conditions were used during chemical vapor deposition (CVD) process to understand and determine the best conditions for growth of carbon nanotubes on copper. Correlation between the thickness of the thin film nickel catalyst and the carbon nanotube diameter is also presented in the study. Characterization techniques used to study the morphology of the CNTs grown on copper include SEM, TEM, HRTEM, Raman Spectroscopy. Results of these studies are outlined and discussed.