Real-Time Monitoring of Gas-Phase and Dissolved CO2 Using a Mixed-Matrix Composite Integrated Fiber Optic Sensor for Carbon Storage Application.

Novel chemical sensors that improve detection and quantification of CO2 are critical to ensuring safe and cost-effective monitoring of carbon storage sites. Fiber optic (FO)-based chemical sensor systems are promising field-deployable systems for real-time monitoring of CO2 in geological formations for long-range distributed sensing. In this work, a mixed-matrix composite integrated FO sensor system was developed with a purely optical readout that reliably operates as a detector for gas-phase and dissolved CO2. A mixed-matrix composite sensor coating consisting of plasmonic nanocrystals and hydrophobic zeolite embedded in a polymer matrix was integrated on the FO sensor. The mixed-matrix composite FO sensor showed excellent reversibility/stability in a high humidity environment and sensitivity to gas-phase CO2 over a large concentration range. This remarkable sensing performance was enabled by using plasmonic nanocrystals to significantly enhance the sensitivity and a hydrophobic zeolite to effectively mitigate interference from water vapor. The sensor exhibited the ability to sense CO2 in the presence of other geologically relevant gases, which is of importance for applications in geological formations. A prototype FO sensor configuration, which possesses a robust sensing capability for monitoring dissolved CO2 in natural water, was demonstrated. Reproducibility was confirmed over many cycles, both in a laboratory setting and in the field. More importantly, we demonstrated on-line monitoring capabilities with a wireless telemetry system, which transferred the data from the field to a website. The combination of outstanding CO2 sensing properties and facile coating processability makes this mixed-matrix composite FO sensor a good candidate for practical carbon storage applications.

Breath Acetone Sensing Based on Single-Walled Carbon Nanotube-Titanium Dioxide Hybrids Enabled by a Custom-Built Dehumidifier.

Acetone is a metabolic byproduct found in the exhaled breath and can be measured to monitor the metabolic degree of ketosis. In this state, the body uses free fatty acids as its main source of fuel because there is limited access to glucose. Monitoring ketosis is important for type I diabetes patients to prevent ketoacidosis, a potentially fatal condition, and individuals adjusting to a low-carbohydrate diet. Here, we demonstrate that a chemiresistor fabricated from oxidized single-walled carbon nanotubes functionalized with titanium dioxide (SWCNT@TiO2) can be used to detect acetone in dried breath samples. Initially, due to the high cross sensitivity of the acetone sensor to water vapor, the acetone sensor was unable to detect acetone in humid gas samples. To resolve this cross-sensitivity issue, a dehumidifier was designed and fabricated to dehydrate the breath samples. Sensor response to the acetone in dried breath samples from three volunteers was shown to be linearly correlated with the two other ketone bodies, acetoacetic acid in urine and ß-hydroxybutyric acid in the blood. The breath sampling and analysis methodology had a calculated acetone detection limit of 1.6 ppm and capable of detecting up to at least 100 ppm of acetone, which is the dynamic range of breath acetone for someone with ketosis. Finally, the application of the sensor as a breath acetone detector was studied by incorporating the sensor into a handheld prototype breathalyzer.

Influence of the Anionic Zinc-Adeninate Metal-Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams.

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal-organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

Centimeter-Scale Pillared-Layer Metal-Organic Framework Thin Films Mediated by Hydroxy Double Salt Intermediates for CO2 Sensor Applications.

Fabrication of metal-organic framework (MOF) thin films over macroscopic surface areas is a subject of great interest for gas sensor application platforms such as optics and microelectronics. However, a direct synthesis of MOF films at ambient conditions, in particular pillared-layer MOF films due to their anisotropic structures, remains a significant challenge. Herein, we demonstrate for the first time a facile construction of dense and continuous pillared-layer MOF thin films on a centimeter scale via an aluminum-doped zinc oxide template and hydroxy double salt (HDS) intermediates at room temperature. A series of Cu(II)-based pillared MOFs with different 1,4-benzenedicarboxylic acid (bdc) ligands were explored for optimizing MOF film formation for CO2 sensor applications. Nonpolar ligands with lower water solubility preferentially formed crystalline pillared MOF structures from HDS intermediates. A Cu2(ndc)2(dabco) (ndc = 1,4-naphthalene-bdc; dabco = 1,4-diazabicyclo[2.2.2]octane) MOF demonstrated the most dense and uniform film growth with micrometer thickness over one square centimeter area. This synthetic approach for growing Cu2(ndc)2(dabco) MOF thin films was successfully translated toward two sensing platforms: a quartz crystal microbalance and an optical fiber sensor. These Cu2(ndc)2(dabco) MOF-coated sensors displayed sensitivity toward CO2 and response/recovery time on the scale of seconds, even at moderate humidity levels. This work provides a road map for producing continuous and anisotropic crystalline MOF thin films over a centimeter scale area on various substrates, which will greatly facilitate their utilization in MOF-based sensor devices, among other applications.

Modification of Carbon Nitride/Reduced Graphene Oxide van der Waals Heterostructure with Copper Nanoparticles To Improve CO2 Sensitivity.

Carbon nitride/reduced graphene oxide (rGO) van der Waals heterostructures (vdWH) have previously shown exceptional oxygen sensitivity via a photoredox mechanism, making it a potential material candidate for various applications such as oxygen reduction reaction catalysis and oxygen sensing. In this work, the electronic structure of a carbon nitride/rGO composite is modified through the introduction of copper nanoparticles (NPs). When incorporated into a chemiresistor device, this vdWH displayed a newfound CO2 sensitivity. The effects of humidity and light were investigated and found to be crucial components for the CO2 sensitivity. Density functional theory calculations performed on a carbon nitride/copper NP@rGO model system found an enhanced stabilization of CO2 caused by H-bonds between the carbon nitride layer and chemisorbed CO2 on copper, pointing to the important role played by humidity. The synergetic effect between the carbon nitride layer interfaced with CuNP@rGO, in combination with humidity and light (395 nm) irradiation, is found to be responsible for the newfound sensitivity toward CO2.

Growth of ZIF-8 on molecularly ordered 2-methylimidazole/single-walled carbon nanotubes to form highly porous, electrically conductive composites.

The combination of porosity and electrical conductivity in a single nanomaterial is important for a variety of applications. In this work, we demonstrate the growth of ZIF-8 on the surface of single-walled carbon nanotubes (SWCNTs). The growth mechanism was investigated and a molecularly ordered imidazole solvation layer was found to disperse SWCNTs and promote crystal growth on the sidewalls. The resultant ZIF-8/SWCNT composite demonstrates high microporosity and electrical conductivity. The ZIF-8/SWCNT composite displayed semiconducting electrical behavior and an increase in sensor sensitivity toward ethanol vapors versus pristine SWCNTs.

Uncondensed Graphitic Carbon Nitride on Reduced Graphene Oxide for Oxygen Sensing via a Photoredox Mechanism.

Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure, has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Because of the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ = 365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis for sensing oxygen gas in the concentration range 300-100 000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. This work provides an example of a metal-free system for solid-gas interface sensing via a photoredox mechanism.

In Situ Grown TiO2 Nanospindles Facilitate the Formation of Holey Reduced Graphene Oxide by Photodegradation.

Titanium dioxide (TiO2) nanostructures and TiO2/graphene nanocomposites are intensively studied materials for energy conversion, energy storage, and organic contaminant photodegradation. However, for TiO2/graphene composites, impermeability across the graphitic basal plane for electrolytes, metal ions, and gas molecules hinders their practical applications. Herein we report a simple, environmentally friendly synthetic route for mesoporous anatase TiO2 nanospindles, and successfully apply this method to obtain in situ grown TiO2 nanospindles/graphene oxide composite. After a thermal reduction at 400 °C, holes are created in the reduced graphene oxide (RGO) sheets through a photocatalytic oxidation mechanism. The formation of holes in RGO is promoted by photogenerated hydroxyl radicals that oxidize and subsequently decarboxylate the graphitic surface of RGO. The proposed mechanism was supported by photocatalytic electrochemical properties of the nanomaterials. The resulting TiO2/holey RGO composites may overcome the original impermeability of graphene sheets and find applications in catalysis, energy conversion/storage devices, and sensors.

Carbon Nanotube Based Gas Sensors toward Breath Analysis.

Breath analysis is a promising method for rapid, inexpensive, noninvasive disease diagnosis and health monitoring owing to the correlative relationship between breath biomarker concentrations and abnormal health conditions. However, current methods to identify and quantify breath components rely on large, bench-top analytical instruments. Carbon nanotube (CNT)-based gas sensors are desirable candidates to replace benchtop instruments because of their sensitive chemical-to-electrical transducer capability, high degree of chemical functionality options, and potential for miniaturization. This review seeks to give an overview of the synthetic methods used to functionalize CNT-based gas sensors, specifically those sensors that target biologically relevant breath markers. Specific examples are provided to highlight the sensing mechanisms behind different classes of CNT hybrid composites. Finally, the current challenges and prospective solutions of applying CNT-based sensors to breath analysis are discussed.

Indium Oxide-Single-Walled Carbon Nanotube Composite for Ethanol Sensing at Room Temperature.

Utilizing a sol-gel synthesis, indium oxide is grown on the surface of oxidized single-walled carbon nanotubes (SWCNT) to form a hybrid material with high conductivity and sensitivity toward certain organic vapors. The room-temperature sensing of dilute ethanol and acetone vapors on the surface of indium oxide/SWCNT hybrid material is studied using electrical conductance experiments in a nonoxidizing environment. Through testing of variously calcinated materials, it was observed that the degree of annealing greatly affects the material's response to acetone and ethanol, such that the intermediate calcination condition yields the best sensitivity. DFT simulations are used to study the interface between defective SWCNT and indium oxide, as well as the interaction between ethanol and acetone molecules with the indium oxide/SWCNT hybrid material.

Regional analysis of climate, primary production, and livestock density in inner Mongolia.

Overstocking is believed to be one of the principal causes for grassland degradation in northern China. For this reason, quantification of overstocking and spatiotemporal analysis are needed for this area. In this study, the relationship between annual rainfall and grassland aboveground net primary production (ANPP) was analyzed using data from 1982 to 1991 in the Inner Mongolia Autonomous Region (IMAR), China. Subsequently, rainfall-based livestock carrying capacity was estimated and combined with livestock density calculated from county-level livestock data from 1982 to 1991 to determine spatial and temporal patterns of a stocking rate index and its relationship with climatic factors. The results indicate the following. First, there was a significant linear relationship between annual rainfall and ANPP in IMAR and the slope of ANPP versus rainfall was greater than those found in South America and Africa, indicating higher rain-use efficiency. Second, temporally averaged livestock density showed overstocking in most of the rural counties except for those in the cold north, where human populations are low and transportation systems are poor. Third, the stocking rate index increased with temperature, from less than 1.0 in the north, to greater than 2.0 in most of the southern IMAR. Within the central IMAR, the index increased from west to east, along the gradient of increasing rainfall. Fourth, long-term dynamics of livestock density depicted continuous overstocking, more than 20%, from 1982 to 1991 along the western part of the NorthEast China Transect (NECT) within IMAR. Spatial planning of livestock densities according to carrying capacities and improved pastoral management are needed in this area.

An ecosystem approach to population management of ungulates.

Harvest objectives for wild ungulates have traditionally been based on population models that do not consider ecosystem effects of ungulate herbivory, nor interactions between native and domestic ungulate species. There is a need for ecosystem models to allow wildlife managers to evaluate potential ecosystem effects of management scenarios. The utility of the SAVANNA simulation model for estimating elk population objectives within an ecosystem context was demonstrated for North Park, Colorado, USA. Effects of different elk population levels were evaluated for range condition, elk and cattle forage, elk and cattle condition, forage and condition of mule deer and moose, plant production, and plant community composition. Analyses were based on 30-year simulation runs using variable, historical weather. Another set of analyses utilized stochastic weather patterns. For management scenarios using the historical climate pattern, increasing elk populations caused biomass reductions of palatable plant species, particularly on areas of high winter density, where mean leaf biomass of palatable shrubs declined from 26.97 g/m2 at 0 elk to 20.82 g/m2 at 4000 elk (3.73 elk/km2), a 23% decline. At population levels of 5000 elk (4.68 elk/km2) or greater, elk body condition declined sharply following a severe winter. The availability of palatable browse on critical winter range was likely the limiting factor. However, when random climate patterns were simulated for the same scenarios, the threshold level for density-dependent effects varied with climate, ranging from 2000 to 10,000 elk. We suggest that elk population levels from 4000 to 5000 animals represent a conservative population objective for the North Park elk herd. Also, increasing elk population levels appears to intensify intraspecific competition among elk, far more than interspecific competition with cattle. Resolution of elk-cattle conflicts is likely to be facilitated by managing elk distribution, rather than overall elk population levels.