Functionalized TiO2 Nanotube-Based Electrochemical Biosensor for Rapid Detection of SARS-CoV-2.

The COronaVIrus Disease (COVID-19) is a newly emerging viral disease caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Rapid increase in the number of COVID-19 cases worldwide led the WHO to declare a pandemic within a few months after the first case of infection. Due to the lack of a prophylactic measure to control the virus infection and spread, early diagnosis and quarantining of infected as well as the asymptomatic individuals are necessary for the containment of this pandemic. However, the current methods for SARS-CoV-2 diagnosis are expensive and time consuming, although some promising and inexpensive technologies are becoming available for emergency use. In this work, we report the synthesis of a cheap, yet highly sensitive, cobalt-functionalized TiO2 nanotubes (Co-TNTs)-based electrochemical sensor for rapid detection of SARS-CoV-2 through sensing the spike (receptor binding domain (RBD)) present on the surface of the virus. A simple, low-cost, and one-step electrochemical anodization route was used for synthesizing TNTs, followed by an incipient wetting method for cobalt functionalization of the TNTs platform, which was connected to a potentiostat for data collection. This sensor specifically detected the S-RBD protein of SARS-CoV-2 even at very low concentration (range of 14 to 1400 nM (nano molar)). Additionally, our sensor showed a linear response in the detection of viral protein over the concentration range. Thus, our Co-TNT sensor is highly effective in detecting SARS-CoV-2 S-RBD protein in approximately 30 s, which can be explored for developing a point of care diagnostics for rapid detection of SARS-CoV-2 in nasal secretions and saliva samples.

Detection of Four Distinct Volatile Indicators of Colorectal Cancer using Functionalized Titania Nanotubular Arrays.

Screening of colorectal cancer is crucial for early stage diagnosis and treatment. Detection of volatile organic compounds (VOCs) of the metabolome present in exhaled breath is a promising approach to screen colorectal cancer (CRC). Various forms of volatile organic compounds (VOCs) that show the definitive signature for the different diseases including cancers are present in exhale breathe. Among all the reported CRC VOCs, cyclohexane, methylcyclohexane, 1,3-dimethyl- benzene and decanal are identified as the prominent ones that can be used as the signature for CRC screening. In the present investigation, detection of the four prominent VOCs related to CRC is explored using functionalized titania nanotubular arrays (TNAs)-based sensor. These signature biomarkers are shown to be detected using nickel-functionalized TNA as an electrochemical sensor. The sensing mechanism is based on the electrochemical interaction of nickel-functionalized nanotubes with signature biomarkers. A detailed mechanism of the sensor response is also presented.

Augmented Z scheme blueprint for efficient solar water splitting system using quaternary chalcogenide absorber material.

Photoelectrochemical hydrogen (H2) production from water is a key method of addressing energy needs using an environmentally friendly approach. In the last two decades we have witnessed the evolution of many different expensive catalysts, photoelectrodes and related technologies, especially those involving precious metals and use of acidic or basic electrolytes for hydrogen production. Cu2ZnSnS4 (CZTS) is a relatively new candidate in the category of efficient photocathodes, due to its high absorption coefficient and near optimal energy band gap. In this paper, we demonstrate photoelectrochemical viability of CZTS in combination with other photoanodes such as TiO2, BiVO4, and WO3 for H2 production with the use of an electrolyte of near neutral pH, a single redox mediator, and insignificant potential biasing. A systematic study was performed to understand CZTS performance with each photoanode, band energetics of CZTS with other photoanodes, impedance behavior of each photoelectrode, and utility of a CZTS photocell in place of a CZTS photocathode. Our assessment indicates that a protected CZTS photocell performs well when used in a Z-scheme containing TiO2 nanotubular array-CZTS or nanocrystalline WO3-CZTS. Preliminary experiments indicated that apart from band energetics, porosity and effective surface area of the photoanodes play a crucial role in determining the photoelectrochemical performance of the system.

Development of a field enhanced photocatalytic device for biocide of coliform bacteria.

A field enhanced flow reactor using bias assisted photocatalysis was developed for bacterial disinfection in lab-synthesized and natural waters. The reactor provided complete inactivation of contaminated waters with flow rates of 50mL/min. The device consisted of titanium dioxide nanotube arrays, with an externally applied bias of up to 6V. Light intensity, applied voltage, background electrolytes and bacteria concentration were all found to impact the device performance. Complete inactivation of Escherichia coli W3110 (~8×10(3)CFU/mL) occurred in 15sec in the reactor irradiated at 25mW/cm(2) with an applied voltage of 4V in a 100ppm NaCl solution. Real world testing was conducted using source water from Emigration Creek in Salt Lake City, Utah. Disinfection of natural creek water proved more challenging, providing complete bacterial inactivation after 25sec at 6V. A reduction in bactericidal efficacy was attributed to the presence of inorganic and organic species, as well as the increase in robustness of natural bacteria.

Electrochemical capacitance of iron oxide nanotube (Fe-NT): effect of annealing atmospheres.

The effect of annealing atmosphere on the supercapacitance behavior of iron oxide nanotube (Fe-NT) electrodes has been explored and reported here. Iron oxide nanotubes were synthesized on a pure iron substrate through an electrochemical anodization process in an ethylene glycol solution containing 3% H2O and 0.5 wt.% NH4F. Subsequently, the annealing of the nanotubes was carried out at 500 °C for 2 h in various gas atmospheres such as air, oxygen (O2), nitrogen (N2), and argon (Ar). The morphology and crystal phases evolved after the annealing processes were examined via field emission scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical capacitance properties of the annealed Fe-NT electrodes were evaluated by conducting cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy tests in the Li2SO4 electrolyte. Based on these experiments, it was found that the capacitance of the Fe-NT electrodes annealed in air and O2 atmospheres shows mixed behavior comprising both the electric double layer and pseudocapacitance. However, annealing in N2 and Ar environments resulted in well-defined redox peaks in the CV profiles of the Fe-NT electrodes, which are therefore attributed to the relatively higher pseudonature of the capacitance in these electrodes. Based on the galvanostatic charge-discharge studies, the specific capacitance achieved in the Fe-NT electrode after annealing in Ar was about 300 mF cm(-2), which was about twice the value obtained for N2-annealed Fe-NTs and three times higher than those annealed in air and O2. The experiments also demonstrated excellent cycle stability for the Fe-NT electrodes with 83%-85% capacitance retention, even after many charge-discharge cycles, irrespective of the gas atmospheres used during annealing. The increase in the specific capacitance was discussed in terms of increased oxygen vacancies as a result of the enhanced transformation of the hematite (α-Fe2O3) phase to the magnetite (Fe3O4) phase for the electrodes annealed in the N2 and Ar atmospheres.

Site-specific and patterned growth of TiO2 nanotube arrays from e-beam evaporated thin titanium film on Si wafer.

Growth of TiO(2) nanotubes on thin Ti film deposited on Si wafers with site-specific and patterned growth using a photolithography technique is demonstrated for the first time. Ti films were deposited via e-beam evaporation to a thickness of 350-1000 nm. The use of a fluorinated organic electrolyte at room temperature produced the growth of nanotubes with varying applied voltages of 10-60 V (DC) which remained stable after annealing at 500 °C. It was found that variation of the thickness of the deposited Ti film could be used to control the length of the nanotubes regardless of longer anodization time/voltage. Growth of the nanotubes on a SiO(2) barrier layer over a Si wafer, along with site-specific and patterned growth, enables potential application of TiO(2) nanotubes in NEMS/MEMS-type devices.

Bifacial dye-sensitized solar cells based on vertically oriented TiO2 nanotube arrays.

In this work we describe a novel bifacial design concept for dye-sensitized solar cells (DSCs). Bifacial DSCs are fabricated with ruthenium complex chemisorbed double-sided TiO(2) nanotube arrays on a Ti metal substrate, in combination with two electron-collecting counter electrodes. Our investigation shows that the present bifacial DSCs have similar conversion efficiencies when illuminated from either their front or rear side, and a summated output power when illuminated on both sides. Furthermore, this type of bifacial DSC is also able to summate the output power of each side when working at an 'unsymmetrical' mode, in which much different output powers are generated by the front and rear sides. Therefore, this bifacial design concept exhibits a promising potential to reduce the cost of solar electricity when DSCs are operated at a location where a high albedo radiation is available.

Formation of chelating agent driven anodized TiO(2) nanotubular membrane and its photovoltaic application.

Titania (TiO(2)) nanotubular arrays provide an exciting material for dye sensitizing solar cells (DSSC) because of their large surface area, lower recombination losses, and fast charge transport properties along the nanotubes. In this paper, design of a next generation DSSC using a TiO(2) nanotubular membrane is discussed. A single step, green process is developed to produce stable large area, free-standing TiO(2) nanotubular films (in a short time, 30-60 min) by anodizing Ti using an organic electrolyte, containing disodium salt of ethylene diaminetetraacetic acid (Na(2)[H(2)EDTA]) as complexing agent, and subsequent drying. Transparent, crack-free TiO(2) films, 20-41 microm thick containing ordered hexagonal TiO(2) nanotubes are achieved by this process. Films having a geometrical area up to 16.5 cm(2) with pore openings of 182 nm have been obtained. These films have been etched to form membranes which provide an exciting prospect for front side illuminated DSSC with good mass and photon transport properties as well as wettability. A photovoltaic efficiency of 2.7% is achieved using a front side illuminated DSSC compared to 1.77% using back side illumination.

The detection of improvised nonmilitary peroxide based explosives using a titania nanotube array sensor.

There is a critical need to develop an efficient, reliable and highly selective sensor for the detection of improvised nonmilitary explosives. This paper describes the utilization of functionalized titania nanotube arrays for sensing improvised organic peroxide explosives such as triacetone triperoxide (TATP). TATP forms complexes with titania nanotube arrays (prepared by anodization and sensitized with zinc ions) and thus affects the electron state of the nanosensing device, which is signaled as a change in current of the overall nanotube material. The response is rapid and a signal of five to eight orders of magnitude is observed. These nanotube array sensors can be used as hand-held miniaturized devices as well as large scale portable units for military and homeland security applications.

Enhancement of the photoelectrochemical conversion efficiency of nanotubular TiO2 photoanodes using nitrogen plasma assisted surface modification.

A synergistic combination of nanostructure synthesis and plasma surface modification was used to enhance the photoelectrochemical activity of titania (TiO(2)) anodes. Titania nanotubular photoanodes were synthesized by electrochemical anodization of Ti thin foils. Nitrogen plasma was used to dope N at the surface of the photoanodes while removing chemisorbed species. X-ray photoelectron spectroscopy analysis showed an increase in the surface concentration of nitrogen. The photocurrent density of plasma treated samples was approximately 80% higher than that of the control. The open circuit potential of the plasma treated samples was more negative compared to that of the control, implying a favorable energetics for water splitting. This increase in photoactivity could be ascribed to: (1) increased absorption of visible light due to bandgap reduction, (2) minimization of charge carrier traps, (3) optimal oxygen vacancies, and (4) increased surface area for enhanced optical absorption and improved charge carrier generation.

Theoretical and experimental study of sensing triacetone triperoxide (TATP) explosive through nanostructured TiO2 substrate.

The present study focuses on understanding of the principle of interaction of explosive molecule triacetonetriperoxide (TATP) with metal sensitized TiO2 nanotube composite material through theoretical modeling. This effort has also been extended in developing a laboratory scale sensor set up to detect TATP based on comprehensive computational modeling outcome and subsequent experimentation. Sensing mechanism depends on the nature of metal, where the TATP interaction with metal functionalized TiO2 prompts a change in conductivity of the sensor platform. Therefore, a metal with higher affinity towards TATP would enhance the conductance, thereby promoting the efficiency of the sensor platform. DFT methodology has been used to identify metal with high affinity to TATP. It was found that Co(2+) metal ion shows significantly higher affinity towards TATP, selected from an array of metal ions with different valency, from monovalent to tetravalent. The preliminary experimental data also suggests that Co(2+) ion detects TATP by inducing a change in conductivity of the sensor substrate.

Self-Ordered Titanium Dioxide Nanotube Arrays: Anodic Synthesis and Their Photo/Electro-Catalytic Applications.

Metal oxide nanotubes have become a widely investigated material, more specifically, self-organized titania nanotube arrays synthesized by electrochemical anodization. As a highly investigated material with a wide gamut of applications, the majority of published literature focuses on the solar-based applications of this material. The scope of this review summarizes some of the recent advances made using metal oxide nanotube arrays formed via anodization in solar-based applications. A general methodology for theoretical modeling of titania surfaces in solar applications is also presented.

Redox-induced enhancement in interfacial capacitance of the titania nanotube/bismuth oxide composite electrode.

Bismuth oxide (Bi2O3) decorated titania nanotube array (T-NT) composite materials were synthesized by a simple, yet versatile electrodeposition method. The effects of deposition current density and time on morphology evolution of the bismuth oxide phase were analyzed. It was found that an optimum deposition condition in terms of current density and time could be reached to achieve uniform and equiaxed crystal morphology of the deposited oxide phase. The morphology, shape, size distribution, and crystal structure of the bismuth oxide phase were evaluated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopic techniques. The electrochemical capacitance of the T-NT/Bi2O3 composites was studied by conducting cyclic voltammetry and galvanostatic charge-discharge experiments. These studies indicated that the capacitance behavior of the composite material was dependent on the morphology and distribution of the bismuth oxide phase. The capacitance was greatly enhanced for the composite having equiaxed and uniformly distributed bismuth oxide particles. The maximum interfacial capacitance achieved in this study was approximately 430 mF cm(-2). Galvanostatic charge-discharge experiments conducted on the composite materials suggested stable capacitance behavior together with excellent capacitance retention even after 500 cycles of continuous charge-discharge operation.

Light-assisted anodized TiO2 nanotube arrays.

Self-assembled arrays of titania nanotubes are synthesized via electrochemical anodization of Ti foils under the presence of UV-vis irradiation. Compared to control samples (anodized without light), the light-assisted anodized samples exhibit larger diameters as well as thicker nanotube walls, whereas the length of the nanotubes remains the same under otherwise similar synthesis conditions. Enhanced photoelectrochemical performance with light-assisted anodized samples under simulated AM 1.5 irradiation is observed by an increase in photocurrent density of 45-73% at 1.23 V (RHE). The enhanced photoelectrochemical performance is correlated to improved charge separation analyzed by Mott-Schottky. A mechanism on the photoeffect during anodization is presented. The morphology and improved properties obtained from the synthesis methodology may also find application in other fields such as sensing and catalysis.

Growth and characterization of TiO2 nanotubes from sputtered Ti film on Si substrate.

In this paper, we present the synthesis of self-organized TiO2 nanotube arrays formed by anodization of thin Ti film deposited on Si wafers by direct current (D.C.) sputtering. Organic electrolyte was used to demonstrate the growth of stable nanotubes at room temperature with voltages varying from 10 to 60 V (D.C.). The tubes were about 1.4 times longer than the thickness of the sputtered Ti film, showing little undesired dissolution of the metal in the electrolyte during anodization. By varying the thickness of the deposited Ti film, the length of the nanotubes could be controlled precisely irrespective of longer anodization time and/or anodization voltage. Scanning electron microscopy, atomic force microscopy, diffuse-reflectance UV-vis spectroscopy, and X-ray diffraction were used to characterize the thin film nanotubes. The tubes exhibited good adhesion to the wafer and did not peel off after annealing in air at 350 °C to form anatase TiO2. With TiO2 nanotubes on planar/stable Si substrates, one can envision their integration with the current micro-fabrication technique large-scale fabrication of TiO2 nanotube-based devices.

Dye-sensitized photovoltaic wires using highly ordered TiO2 nanotube arrays.

Dye-sensitized photovoltaic wires (DSPVWs) are developed using anodized Ti wires that contain ordered arrays of TiO2 nanotubes. The prototype DSPVW consists of N719 dye-adsorbed TiO2 nanotube arrays around a Ti wire as a working electrode, a platinum wire as a counter electrode, and an organic electrolyte encased in a capillary glass tube. The effect of length of nanotube arrays on the photovoltaic performance of DSPVWs is studied systematically. A solar-to-electric conversion efficiency of 2.78% is achieved with 55 microm long nanotubes under 98.3 mW/cm(2) AM 1.5 simulated full light. The prototype device is capable of achieving a long distance transport of photocurrent and harvesting all light from any direction in surroundings to generate electricity.

Double-wall anodic titania nanotube arrays for water photooxidation.

Vertically oriented double-wall titania nanotube (external diameters of 82 and 206 nm) arrays are synthesized by a sonoelectrochemical anodization technique in combination with a unique room-temperature ionic liquid and organic electrolyte. Compared to similar single-wall nanotubes (0.638 mA/cm(2)) and commercial nanoparticles (0.365 mA/cm(2)), these double-wall nanotube arrays show 2-4 times more photoactivity to split water under solar light illumination to generate hydrogen and oxygen. Partial doping of B and C into the TiO(2) matrix gives rise to these double-wall nanotubes which absorb visible solar light more efficiently than the intrinsic TiO(2). The structural properties of these novel structures have been studied extensively using various spectroscopic, analytical, and electrochemical techniques.

Synthesis of TaON nanotube arrays by sonoelectrochemical anodization followed by nitridation: a novel catalyst for photoelectrochemical hydrogen generation from water.

This communication reports the synthesis of TaON nanotube arrays as efficient visible light driven photocatalysts for photoelectrochemical generation of hydrogen from water.

A green process for producing biodiesel from feather meal.

This paper describes a new and environmentally friendly process for developing biodiesel from commercial feather meal, a waste product of the poultry industry. Currently, feather meal is used as an animal feed, given its high protein content, and also as a fertilizer because of its high nitrogen content. In this work, we have extracted fat from the feather meal in boiling water (70 degrees C) and then transesterified the fat into biodiesel using KOH and methanol; 7-11% biodiesel (on a dry basis) is produced in this process. ASTM analysis of the prepared feather meal biodiesel confirmed that the biodiesel is of good quality and comparable to other biodiesels made from other common feedstocks. Given the amount of feather meal produced by the poultry industry, it is estimated that this process can create 150-200 million gallons of biodiesel in the United States and 593.2 million gallons worldwide.

Spent coffee grounds as a versatile source of green energy.

The production of energy from renewable and waste materials is an attractive alternative to the conventional agricultural feed stocks such as corn and soybean. This paper describes an approach to extract oil from spent coffee grounds and to further transesterify the processed oil to convert it into biodiesel. This process yields 10-15% oil depending on the coffee species (Arabica or Robusta). The biodiesel derived from the coffee grounds (100% conversion of oil to biodiesel) was found to be stable for more than 1 month under ambient conditions. It is projected that 340 million gallons of biodiesel can be produced from the waste coffee grounds around the world. The coffee grounds after oil extraction are ideal materials for garden fertilizer, feedstock for ethanol, and as fuel pellets.