Development and comparative investigation of Ag-sensitive layer based SAW and QCM sensors for mercury sensing applications.

Piezoelectric acoustic wave devices integrated with noble metal surfaces provide exciting prospects for the direct measurement of toxic gas species such as mercury (Hg) in the atmosphere. Even though gold (Au) based acoustic wave sensors have been utilized extensively for detecting Hg, the potential of using other metal surfaces such as silver (Ag) is yet to be thoroughly studied. Here, we developed Ag sensitive layer-based surface acoustic wave (SAW) and quartz crystal microbalance (QCM) sensors and focused on their comparative analysis for Hg sensing applications with parameters such as the sensor sensitivity, selectivity, adsorption/desorption isotherm and Hg diffusion into the surface thoroughly studied. The SAW sensor was fabricated with nickel (Ni) interdigitated transducer (IDT) electrodes and a Ag thin film on the delay line of the device. In the case of the QCM sensor, the electrodes were constructed of Ag thin film and simultaneously employed as a sensitive layer. Mercury sensing experiments were conducted for a range of concentrations between 24-365 ppbv without/with the presence of some common industrial interfering gas species (i.e. ammonia, acetaldehyde, ethyl mercaptan, dimethyl disulphide, methyl ethyl ketone and humidity) at various operating temperatures in the range of 35-95 °C. The SAW sensor was found to possess up to 70 times higher response magnitudes than its QCM counterpart at 35 °C while up to 30 and 23 times higher response magnitudes were observed for the SAW sensor at elevated temperatures of 75 and 95 °C, respectively. Furthermore, the SAW sensor showed good selectivity (>89%) toward Hg(0) vapor in the presence of all the interferents tested at an operating temperature of 75 °C while the QCM sensor exhibited significant cross-sensitivity when ethyl mercaptan was introduced along with Hg(0) vapor. Overall, it is indicative that Ag-based acoustic wave sensors do have great potential for Hg sensing applications, given that right operating conditions are applied.

Microstructure and dynamics of vacancy-induced nanofilamentary switching network in donor doped SrTiO3-x memristors.

Donor doping of perovskite oxides has emerged as an attractive technique to create high performance and low energy non-volatile analog memories. Here, we examine the origins of improved switching performance and stable multi-state resistive switching in Nb-doped oxygen-deficient amorphous SrTiO3 (Nb:a-STO x ) metal-insulator-metal (MIM) devices. We probe the impact of substitutional dopants (i.e., Nb) in modulating the electronic structure and subsequent switching performance. Temperature stability and bias/time dependence of the switching behavior are used to ascertain the role of substitutional dopants and highlight their utility to modulate volatile and non-volatile behavior in a-STO x devices for adaptive and neuromorphic applications. We utilized a combination of transmission electron microscopy, photoluminescence emission properties, interfacial compositional evaluation, and activation energy measurements to investigate the microstructure of the nanofilamentary network responsible for switching. These results provide important insights into understanding mechanisms that govern the performance of donor-doped perovskite oxide-based memristive devices.

A Nanoengineered Conductometric Device for Accurate Analysis of Elemental Mercury Vapor.

We developed a novel conductometric device with nanostructured gold (Au) sensitive layer which showed high-performance for elemental mercury (Hg(0)) vapor detection under simulated conditions that resemble harsh industrial environments. That is, the Hg(0) vapor sensing performance of the developed sensor was investigated under different operating temperatures (30-130 °C) and working conditions (i.e., humid) as well as in the presence of various interfering gas species, including ammonia (NH3), hydrogen sulfide (H2S), nitric oxide (NO), carbon mono-oxide (CO), carbon dioxide (CO2), sulfur dioxide (SO2), hydrogen (H2), methane (CH4), and volatile organic compounds (VOCs) such as ethylmercaptan (EM), acetaldehyde (MeCHO) and methyl ethyl ketone (MEK) among others. The results indicate that the introduction of Au nanostructures (referred to as nanospikes) on the sensor's surface enhanced the sensitivity toward Hg(0) vapor by up-to 450%. The newly developed sensor exhibited a limit of detection (LoD) (∼35 µg/m(3)), repeatability (∼94%), desorption efficiency (100%) and selectivity (∼93%) when exposed to different concentrations of Hg(0) vapor (0.5 to 9.1 mg/m(3)) and interfering gas species at a chosen operating temperature of 105 °C. Furthermore, the sensor was also found to show 91% average selectivity when exposed toward harsher industrial gases such as NO, CO, CO2, and SO2 along with same concentrations of Hg(0) vapor in similar operating conditions. In fact, this is the first time a conductometric sensor is shown to have high selectivity toward Hg(0) vapor even in the presence of H2S. Overall results indicate that the developed sensor has immense potential to be used as accurate online Hg(0) vapor monitoring technology within industrial processes.

Controlling core/shell formation of Nanocubic p-Cu2O/n-ZnO toward enhanced photocatalytic performance.

p-Type Cu2O/n-type ZnO core/shell photocatalysts has been demonstrated to be an efficient photocatalyst as a result of their interfacial structure tendency to reduce the recombination rate of photogenerated electron-hole pairs. Monodispersed Cu2O nanocubes were synthesized and functioned as the core, on which ZnO nanoparticles were coated as the shells having varying morphologies. The evenly distributed ZnO decoration as well as assembled nanospheres of ZnO were carried out by changing the molar concentration ratio of Zn/Cu. The results indicate that the photocatalytic performance is initially increased, owing to formation of small ZnO nanoparticles and production of efficient p-n junction heterostructures. However, with increasing Zn concentration, the decorated ZnO nanoparticles tend to form large spherical assemblies resulting in decreased photocatalytic activity due to the interparticle recombination between the agglomerated ZnO nanoparticles. Therefore, photocatalytic activity of Cu2O/ZnO heterostructures can be optimized by controlling the assembly and morphology of the ZnO shell.

Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

Preparation of Au nanoparticles on a magnetically responsive support via pyrolysis of a Prussian blue composite.

A strategy is described for the direct preparation of Au nanoparticles (AuNPs) on a Fe-based support, coated with porous carbon (PC), via pyrolysis of an AuCN functionalised Prussian Blue (PB) metal organic framework (MOF). The composite starting material was prepared with an even distribution of AuCN on the surface via galvanic exchange of PB with a gold salt in solution. The resulting structures after pyrolysis were shown to be active Au-based nanomaterials for model applications including catalysis (4-nitrophenol reduction) and electroanalysis (arsenic (III) detection), suggesting broad application where Au nanoparticles are required at a liquid-solid interface. The Fe based support was seen to consist of Fe, Fe3C and Fe4C phases, and the carbon coating increased the stability and improved the conductivity of the materials. The temperature of pyrolysis was seen to affect the activity of the supported nanoparticles, with an increased Au surface area obtained at the higher pyrolysis temperature (650 °C) tested. A general strategy is thus confirmed for preparation of noble metal nanoparticles evenly distributed on a magnetic support, allowing easy separation of catalysts from products in heterogeneous applications.

SERS and fluorescence-based ultrasensitive detection of mercury in water.

The development of reliable and ultrasensitive detection marker for mercury ions (Hg2+) in drinking water is of great interest for toxicology assessment, environmental protection and human health. Although many Hg2+ detection methods have been developed, only few offer sensitivities below 1pM. Herein, we describe a simple histidine (H) conjugated perylene diimide (PDI) bolaamphiphile (HPH) as a dual-responsive optical marker to develop highly selective and sensitive probe as visible (sol-to-gel transformation), fluorescence and SERS-based Hg2+sensor platform in the water. Remarkably, HPH as a SERS marker supported on Au deposited monodispersed nanospheres monolayers (Au-MNM) of polystyrene offers an unprecedented selectivity and the best ever reported detection limit (LOD) of 60 attomolar (aM, 0.01 parts-per-quadrillion (ppq)) for Hg2+ in water. This is ten orders of magnitude lower than the United States Environmental Protection Agency (USEPA) tolerance limit of Hg2+ in drinking water (10nM, 2 ppb). This simple and effective design principle of host-guest interactions driven fluorescence and SERS-based detection may inspire the future molecular engineering strategies for the development of ultrasensitive toxic analyte sensor platforms.

Fluorescence brightness and photostability of individual copper (I) oxide nanocubes.

Conventional organic fluorophores lose their ability to fluoresce after repeated exposure to excitation light due to photobleaching. Therefore, research into emerging bright and photostable nanomaterials has become of great interest for a range of applications such as bio-imaging and tracking. Among these emerging fluorophores, metal oxide-based nanomaterials have attracted significant attention as a potential multifunctional material with photocatalytic and angeogenisis abilities in addition to fluorescnce applications. However, most of these applications are highly dependent on size, morphology, and chemo-physical properties of individual particles. In this manuscript, we present a method to study the intrinsic optical characteristics of individual copper (I) oxide (Cu2O) nanocubes. When excited at 520 nm using only 11 µW excitation power (1.7 W/cm2), individual nanocubes were observed to emit light with peak wavelengths ~760 nm which is conveniently within the near-infrared 1 (NIR1) biological window where tissue autofluorescence is minimal. Bright and photostable fluorescence was observed with intensities up to 487 K counts/s under constant illumination for at least 2 minutes with a brightness approximately four times higher than the autofluorescence from a fixed cumulus-oocyte complex. With near-IR emission, high fluorescence brightness, and outstanding photostability, Cu2O nanocubes are attractive candidates for long-term fluorescent bioimaging applications.

Nickel-gold bimetallic monolayer colloidal crystals fabricated via galvanic replacement as a highly sensitive electrochemical sensor.

Bimetallic Ni-Au monolayer colloidal crystals (MCCs) were fabricated by galvanic replacement of Ni monolayers with Au salt. The influence of Au concentration used in the galvanic replacement solutions on the morphology and structure of the resulting Ni-Au surface is studied. It was found that the use of monolayer colloidal crystals, which display cohesive structure formations across the monolayer, results in the galvanic replacement reaction occurring more evenly over the surface when compared to the thin film counterpart. The fabricated devices were analyzed under alkaline conditions using chronoamperometric techniques to detect glucose concentrations ranging between 20 µM and 10 mM. The optimum Ni-Au MCC substrate was produced using 0.1 mM Au salt solution and showed a very low experimental detection limit of 14.9 µM and a calculated sensitivity of 506 µA mM-1 cm-2, which was ∼3 times larger than that of the plain Ni MCC substrate. The Ni-Au MCC substrate also showed minimal current response changes in the presence of common physiological contaminants, thus being a highly selective electrochemical glucose sensor.

Ordered Monolayer Gold Nano-urchin Structures and Their Size Induced Control for High Gas Sensing Performance.

The synthesis of ordered monolayers of gold nano-urchin (Au-NU) nanostructures with controlled size, directly on thin films using a simple electrochemical method is reported in this study. In order to demonstrate one of the vast potential applications, the developed Au-NUs were formed on the electrodes of transducers (QCM) to selectively detect low concentrations of elemental mercury (Hg(0)) vapor. It was found that the sensitivity and selectivity of the sensor device is enhanced by increasing the size of the nanospikes on the Au-NUs. The Au-NU-12 min QCM (Au-NUs with nanospikes grown on it for a period of 12 min) had the best performance in terms of transducer based Hg(0) vapor detection. The sensor had 98% accuracy, 92% recovery, 96% precision (repeatability) and significantly, showed the highest sensitivity reported to date, resulting in a limit of detection (LoD) of only 32 µg/m3 at 75 °C. When compared to the control counterpart, the accuracy and sensitivity of the Au-NU-12 min was enhanced by ~2 and ~5 times, respectively. The results demonstrate the excellent activity of the developed materials which can be applied to a range of applications due to their long range order, tunable size and ability to form directly on thin-films.

Fe-doped CeO2 nanorods for enhanced peroxidase-like activity and their application towards glucose detection.

The construction of highly efficient inorganic mimetic enzymes (nanozymes) is much needed to replace natural enzymes due to their instability and high cost. Recently, nanoscale CeO2 has been attracting significant interest due to its unique properties such as facile redox behaviour (Ce4+↔ Ce3+) and surface defects. In the present work, various amounts of Fe3+-doped CeO2 nanorods (NRs) (with 3, 6, 9, and 12% Fe doping) were synthesized using a facile hydrothermal method and investigated for peroxidase-like activity and glucose detection. The peroxidase-like activity results revealed that 6 at% doping is the optimal Fe doping level to demonstrate superior catalytic performance over un-doped and Fe3+-doped CeO2 NRs. Steady state kinetic analysis also confirms that the 6% Fe3+-doped CeO2 (6Fe/CeO2) NRs exhibited excellent catalytic performance towards 3,3',5,5'tetramethylbenzidine (TMB) oxidation with a Km and Vm of 0.176 mM and 8.6 × 10-8 M s-1, respectively, as compared to horseradish peroxidase (HRP) enzymes (0.434 mM and 10.0 × 10-8 M s-1). Typical colour reactions arising from the catalytic oxidation of the TMB substrate over 6Fe/CeO2 NRs with H2O2 have been utilized to establish a simple sensitive and selective colorimetric assay for the determination of glucose concentration in buffer, diluted fruit juices and foetal bovine serum samples. The superior catalytic performance of 6Fe/CeO2 NRs could be attributed to abundant surface defects, high surface area and pore volume, and preferential exposure of the highly reactive (110) planes.

Nanosphere monolayer on a transducer for enhanced detection of gaseous heavy metal.

This study reports for the first time that polystyrene monodispersed nanosphere monolayer (PS-MNM) based Au (Au-MNM) and Ag (Ag-MNM) nanostructures deposited on quartz crystal microbalance (QCM) transducers can be used for nonoptical based chemical sensing with extremely high sensitivity and selectivity. This was demonstrated by exposing the Au-MNM and Ag-MNM based QCMs to low concentrations of Hg(0) vapor in the presence interferent gas species (i.e., H2O, NH3, volatile organics, etc.) at operating temperatures of 30 and 75 °C. At 30 °C, the Au-MNM and Ag-MNM based QCMs showed ∼16 and ∼20 times higher response magnitude toward Hg(0) vapor concentration of 3.26 mg/m(3) (364 parts per billion by volume (ppbv)) relative to their unmodified control counterparts, respectively. The results indicated that the extremely high sensitivity was not due to the increased surface area (only 4.62 times increase) but due to their long-range interspatial order and high number of surface defect formation which are selectively active toward Hg(0) vapor sorption. The Au-MNM and Ag-MNM also had more than an order of magnitude lower detection limits (<3 ppbv) toward Hg(0) vapor compared to their unmodified control counterparts (>30 ppbv). When the operating temperature was increased from 30 to 75 °C, it was found that the sensors exhibited lower drift, better accuracy, and better selectivity toward Hg(0) vapor but at the compromise of higher detection limits. The high repeatability (84%), accuracy (97%), and stability of Au-MNM in particular make it practical to potentially be used as nonspectroscopic based Hg(0) vapor sensor in many industries either as mercury emission monitoring or as part of a mercury control feedback system.

Zinc oxide/silver nanoarrays as reusable SERS substrates with controllable 'hot-spots' for highly reproducible molecular sensing.

HYPOTHESIS: The reproducible surface enhanced Raman scattering (SERS)-based sensing of an analyte relies on high quality SERS substrates that offer uniformity over large areas. Uniform ZnO nanoarrays are expected to offer an appropriate platform for SERS sensing. Moreover, since ZnO has good photocatalytic properties, controllable decoration of silver nanoparticles on ZnO nanoarrays may offer an additional opportunity to clean up SERS substrates after each sensing event. EXPERIMENTS: This study employs a facile soft chemical synthesis strategy to fabricate Raman-active and recyclable ZnO/Ag nanorod arrays as reproducible SERS substrates. Arrays of ZnO nanorods were synthesized using hydrothermal method, which was followed by controllable decoration of ZnO with silver nanoparticles (AgNPs) using an electroless plating technique. FINDINGS: The uniform density of SERS-active 'hot-spots' on ZnO nanoarrays could be controlled on a large 1×1 cm(2) substrate. These ZnO/Ag nanoarrays showed high reproducibility (0.132 RSD) towards acquiring SERS spectra of rhodamine B (RB) at 30 random locations on a single substrate. The photocatalytic nature of ZnO/Ag semiconductor/metal hybrid endowed these substrates with reusability characteristics. By controlling metal loading on a semiconductor surface, photocatalytic activity and high SERS performance can be integrated within a single package to obtain high quality, reproducible, stable and recyclable SERS substrates.