Critical Sensing Modalities for Hydrogen: Technical Needs and Status of the Field to Support a Changing Energy Landscape.

Decarbonization of the energy system is a key aspect of the energy transition. Energy storage in the form of chemical bonds has long been viewed as an optimal scheme for energy conversion. With advances in systems engineering, hydrogen has the potential to become a low cost, low emission, energy carrier. However, hydrogen is difficult to contain, it exhibits a low flammability limit (>40000 ppm or 4%), low ignition energy (0.02 mJ), and it is a short-lived climate forcer. Beyond commercially available sensors to ensure safety through spot checks in enclosed environments, new sensors are necessary to support the development of low emission infrastructure for production, transmission, storage, and end use. Efficient scalable broad area hydrogen monitoring motivates lowering the detection limit below that (10 ppm) of best in class commercial technologies. In this perspective, we evaluate recent advances in hydrogen gas sensing to highlight technologies that may find broad utility in the hydrogen sector. It is clear in the near term that a sensor technology suite is required to meet the variable constraints (e.g., power, size/weight, connectivity, cost) that characterize the breadth of the application space, ranging from industrial complexes to remote pipelines. This perspective is not intended to be another standard hydrogen sensor review, but rather provide a critical evaluation of technologies with detection limits preferably below 1 ppm and low power requirements. Given projections for rapid market growth, promising techniques will also be amenable to rapid development in technical readiness for commercial deployment. As such, methods that do not meet these requirements will not be considered in depth.

Flexible Phenanthracene Nanotubes for Explosive Detection.

Phenanthracene nanotubes with arylene-ethynylene-butadiynylene rims and phenanthracene walls are synthesized in a modular bottom-up approach. One of the rims carries hexadecyloxy side chains, mediating the affinity to highly oriented pyrolytic graphite. Molecular dynamics simulations show that the nanotubes are much more flexible than their structural formulas suggest: In 12, the phenanthracene units act as hinges that flip the two macrocycles relative to each other to one of two possible sites, as quantum mechanical models suggest and scanning tunneling microscopy investigations prove. Unexpectedly, both theory and experiment show for 13 that the three phenanthracene hinges are deflected from the upright position, accompanied by a deformation of both macrocycles from their idealized sturdy macroporous geometry. This flexibility together with their affinity to carbon-rich substrates allows for an efficient host-guest chemistry at the solid/gas interface opening the potential for applications in single-walled carbon nanotube-based sensing, and the applicability to build new sensors for the detection of 2,4,6-trinitrotoluene via nitroaromatic markers is shown.

Wireless Detection of Trace Ammonia: A Chronic Kidney Disease Biomarker.

Elevated levels of ammonia in breath can be linked to medical complications, such as chronic kidney disease (CKD), that disturb the urea balance in the body. However, early stage CKD is usually asymptomatic, and mass screening is hindered by high instrumentation and operation requirements and accessible and reliable detection methods for CKD biomarkers, such as trace ammonia in breath. Enabling methods would have significance in population screening for early stage CKD patients. We herein report a method to effectively immobilize transition metal selectors in close proximity to a single-walled carbon nanotube (SWCNT) surface using pentiptycene polymers containing metal-chelating backbone structures. The robust and modular nature of the pentiptycene metallopolymer/SWCNT complexes creates a platform that accelerates sensor discovery and optimization. Using these methods, we have identified sensitive, selective, and robust copper-based chemiresistive ammonia sensors that display low parts per billion detection limits. We have added these hybrid materials to the resonant radio frequency circuits of commercial near-field communication (NFC) tags to achieve robust wireless detection of ammonia at physiologically relevant levels. The integrated devices offer a noninvasive and cost-effective approach for early detection and monitoring of CKD.

Continuous flow synthesis of pyridinium salts accelerated by multi-objective Bayesian optimization with active learning.

We report a human-in-the-loop implementation of the multi-objective experimental design via a Bayesian optimization platform (EDBO+) towards the optimization of butylpyridinium bromide synthesis under continuous flow conditions. The algorithm simultaneously optimized reaction yield and production rate (or space-time yield) and generated a well defined Pareto front. The versatility of EDBO+ was demonstrated by expanding the reaction space mid-campaign by increasing the upper temperature limit. Incorporation of continuous flow techniques enabled improved control over reaction parameters compared to common batch chemistry processes, while providing a route towards future automated syntheses and improved scalability. To that end, we applied the open-source Python module, nmrglue, for semi-automated nuclear magnetic resonance (NMR) spectroscopy analysis, and compared the acquired outputs against those obtained through manual processing methods from spectra collected on both low-field (60 MHz) and high-field (400 MHz) NMR spectrometers. The EDBO+ based model was retrained with these four different datasets and the resulting Pareto front predictions provided insight into the effect of data analysis on model predictions. Finally, quaternization of poly(4-vinylpyridine) with bromobutane illustrated the extension of continuous flow chemistry to synthesize functional materials.

Interaction of N-nitrosamines with binuclear copper complexes for luminescent detection.

Cu(I) from tetrakis(acetonitrile)copper(I) hexafluorophosphate ([Cu(MeCN)4]PF6) was complexed with five structurally related phosphines containing N-heterocycles. The interactions between the resulting complexes and some N-nitrosamines were studied using X-ray crystallography as well as emission spectroscopy. Upon complexation, three phosphine ligands bridge two Cu(I) centers to give paddlewheel type structures that displayed a range of emission wavelengths spanning the visible region. N-Nitrosodimethylamine (NDMA) was shown to coordinate to one of the two copper centers in some of the paddlewheel complexes in the solid state and this interaction also quenches their emissions in solution. The influence of the weakly coordinating anion on crystal and spectroscopic properties of one of the paddlewheel complexes was also examined using tetrakis(acetonitrile)copper(I) perchlorate ([Cu(MeCN)4]ClO4) as an alternative Cu(I) source. Similarly, copper(II) perchlorate hexahydrate (Cu(ClO4)2·6H2O) was used for complexation to observe the impact of metal oxidation state on the two aforementioned properties. Lastly, the spectroscopic properties of the complex between Ph2P(1-Isoquinoline) and Cu(I) was shown to exhibit solvent dependence when the counterion is ClO4-. These Cu(I) complexes are bench stable solids and may be useful materials for developing a fluorescence based detection method for N-nitrosamines.

Ion sensors with crown ether-functionalized nanodiamonds.

Alkali metal ions such as sodium and potassium cations play fundamental roles in biology. Developing highly sensitive and selective methods to both detect and quantify these ions is of considerable importance for medical diagnostics and bioimaging. Fluorescent nanoparticles have emerged as powerful tools for nanoscale imaging, but their optical properties need to be supplemented with specificity to particular chemical and biological signals in order to provide further information about biological processes. Nitrogen-vacancy (NV) centers in diamond are particularly attractive as fluorescence markers, thanks to their optical stability, biocompatibility and further ability to serve as highly sensitive quantum sensors of temperature, magnetic and electric fields in ambient conditions. In this work, by covalently grafting crown ether structures on the surface of nanodiamonds (NDs), we build sensors that are capable of detecting specific alkali ions such as sodium cations. We will show that the presence of these metal ions modifies the charge state of NV centers inside the ND, which can then be read out by measuring their photoluminescence spectrum. Our work paves the way for designing selective biosensors based on NV centers in diamond.

Chemiresistive Hydrogen Sensing with Size-Limited Palladium Nanoparticles in Iptycene-Containing Poly(arylene ether)s.

Metal nanoparticles have been widely employed in chemical sensing due to their high reactivity toward various gases. The size of the metal nanoparticles often dictates their reactivity and hence their performance as chemiresistive sensors. Herein, we report that iptycene-containing poly(arylene ether)s (PAEs) have been shown to limit the growth of palladium nanoparticles (Pd NPs) and stabilize the Pd NPs dispersion. These porous PAEs also facilitate the efficient transport of analytes. Single-walled carbon nanotube (SWCNT)-based chemiresistors and graphene field-effect transistors (GFETs) using these PAE-supported small Pd NPs are sensitive, selective, and robust sensory materials for hydrogen gas under ambient conditions. Generalizable strategies including presorting SWCNTs with pentiptycene-containing poly(p-phenylene ethynylene)s (PPEs) and thermal annealing demonstrated significant improvements in the chemiresistive performance. The polymer:NP colloids produced in this study are readily synthesized and solution processable, and these methods are of general utility.

Cyclodextrin-Functionalized Polypyrrole Particles for the Extraction of Aromatics from Water.

We describe the preparation of oil-in-water (o/w) colloidal particles with a polypyrrole (pPy) shell in which cyclodextrin has been incorporated at the oil-water interface via either physical adsorption or reaction with the pPy shell. The utility of these particles was assessed by the extraction of organic dyes from water. In all cases, we found that cyclodextrin incorporation significantly improved dye uptake, giving up to 78 ± 11% dye extraction in the case of a 100 ppm solution of 4-nitroaniline with a covalently incorporated cyclodextrin. We demonstrated the ability of our colloidal particles to extract nicotine-derived nitrosamine ketone (NNK), a potent carcinogen, from aqueous solution. By treating the solution containing 100 ppm NNK with our particles over 24 and 48 h, we found that NNK removal reached 65 ± 2 and 83 ± 1%, respectively. The uptake could be improved by re-treating a solution with additional freshly prepared particles, to achieve 95 ± 1% NNK extraction with a covalently incorporated cyclodextrin.

Wireless Lateral Flow Device for Biosensing.

Many biosensing methods rely on signals produced by enzyme-catalyzed reactions and efficient methods to detect and record this activity. Herein, we report a wireless lateral flow device and demonstrate the conversion of oxidase reactions to changes in the resonance of radio frequency identification (RFID) circuits. The detection is triggered by polyoxometalate-catalyzed oxidative doping of polypyrrole (pPy) when exposed to oxidase-generated H2O2. We have integrated this transduction and RFID capability into a lateral flow device to create a low-cost, rapid, and portable method for quantitative biological signal detection. We further report a new method for creating functional coatings from pPy core-shell colloidal particles bioconjugated for streptavidin-biotin recognition with glucose oxidase or pyruvate oxidase. The biofunctionalized pPy particles coalesce on the nitrocellulose membrane to produce a chemiresistive band. Glucose or pyruvate solutions result in formation of H2O2 at the pPy bands, functionalized with the respective oxidase, to produce conductivity enhancements exceeding 7·105%. Placing the pPy band in the RFID circuit converts the resistivity response to a change of RF resonance. The enzymatic response of glucose oxidase is recorded within 30 min with as low as 0.6 mM of glucose using this lateral flow device. Pyruvate is also shown to produce large responses. The oxidase enzymes/pPy transduction establishes a resistivity-based platform for the construction of a new family of lateral flow devices capable of detecting and quantifying biological targets.

Integrated biosensor platform based on graphene transistor arrays for real-time high-accuracy ion sensing.

Two-dimensional materials such as graphene have shown great promise as biosensors, but suffer from large device-to-device variation due to non-uniform material synthesis and device fabrication technologies. Here, we develop a robust bioelectronic sensing platform  composed of  more than 200 integrated sensing units, custom-built high-speed readout electronics, and machine learning inference that overcomes these challenges to achieve rapid, portable, and reliable measurements. The platform demonstrates reconfigurable multi-ion electrolyte sensing capability and provides highly sensitive, reversible, and real-time response for potassium, sodium, and calcium ions in complex solutions despite variations in device performance. A calibration method leveraging the sensor redundancy and device-to-device variation is also proposed, while a machine learning model trained with multi-dimensional information collected through the multiplexed sensor array is used to enhance the sensing system's functionality and accuracy in ion classification.

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts.

In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents.

Bottom-Up Synthesized All-Thermal-Catalyst Aerogels for Heat-Regenerative Air Filtration.

Airborne particular matter (PM) pollution is an increasing global issue and alternative sources of filter fibers are now an area of significant focus. Compared with relatively mature hazardous gas treatments, state of the art high-efficiency PM filters still lack thermal decomposition ability for organic PM pollutants, such as soot from coal-fired power plants and waste-combustion incinerators, resulting in frequent replacement, high cost, and second-hand pollution. In this manuscript, we propose a bottom-up synthesis method to make the first all-thermal-catalyst air filter (ATCAF). Self-assembled from ∼50 nm diameter TiO2 fibers, ATCAF could not only capture the combustion-generated PM pollutants with >99.999% efficiency but also catalyze the complete decomposition of the as-captured hydrocarbon pollutants at high temperature. It has the potential of in situ eliminating the PM pollutants from burning of hydrocarbon materials leveraging the burning heat.

Trace Hydrogen Sulfide Sensing Inspired by Polyoxometalate-Mediated Aerobic Oxidation.

A high-performance chemiresistive gas sensor is described for the detection of hydrogen sulfide (H2S), an acutely toxic and corrosive gas. The chemiresistor operates at room temperature with low power requirements potentially suitable for wearable sensors or for rapid in-field detection of H2S in settings such as pipelines and wastewater treatment plants. Specifically, we report chemiresistors based on single-walled carbon nanotubes (SWCNTs) containing highly oxidizing platinum-polyoxometalate (Pt-POM) selectors. We show that by tuning the vanadium content and thereby the oxidation reactivity of the constituent POMs, an efficient chemiresistive sensor is obtained that is proposed to operate by modulating CNT doping during aerobic H2S oxidation. The sensor shows exceptional sensitivity to trace H2S in air with a ppb-level detection limit, multimonth stability under ambient conditions, and high selectivity for H2S over a wide range of interferants, including thiols, thioethers, and thiophene. Finally, we demonstrate that the robust sensing material can be used to fabricate flexible devices by covalently immobilizing the SWCNT-P4VP network onto a polyimide substrate, further extending the potentially broad utility of the chemiresistors. The strategy presented herein highlights the applicability of concepts in molecular aerobic oxidation catalysis to the development of low-cost analyte detection technologies.

Electrocatalytic Isoxazoline-Nanocarbon Metal Complexes.

We report the synthesis of new carbon-nanomaterial-based metal chelates that enable effective electronic coupling to electrocatalytic transition metals. In particular, multiwalled carbon nanotubes (MWCNTs) and few-layered graphene (FLG) were covalently functionalized by a microwave-assisted cycloaddition with nitrile oxides to form metal-binding isoxazoline functional groups with high densities. The covalent attachment was evidenced by Raman spectroscopy, and the chemical identity of the surface functional groups was confirmed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The functional carbon nanomaterials effectively chelate precious metals Ir(III), Pt(II), and Ru(III), as well as earth-abundant metals such as Ni(II), to afford materials with metal contents as high as 3.0 atom %. The molecularly dispersed nature of the catalysts was confirmed by X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping. The interplay between the chelate structure on the graphene surface and its metal binding ability has also been investigated by a combination of experimental and computational studies. The defined ligands on the graphene surfaces enable the formation of structurally precise heterogeneous molecular catalysts. The direct attachment of the isoxazoline functional group on the graphene surfaces provides strong electronic coupling between the chelated metal species and the conductive carbon nanomaterial support. We demonstrate that the metal-chelated carbon nanomaterials are effective heterogeneous catalysts in the oxygen evolution reaction with low overpotentials and tunable catalytic activity.

Reconfigurable Pickering Emulsions with Functionalized Carbon Nanotubes.

Pickering emulsions (PEs) achieve interfacial stabilization by colloidal particle surfactants and are commonly used in food, cosmetics, and pharmaceuticals. Carbon nanotubes (CNTs) have recently been used as stabilizing materials to create dynamic single emulsions. In this study, we used the formation of Meisenheimer complexes on functionalized CNTs to fabricate complex biphasic emulsions containing hydrocarbons (HCs) and fluorocarbons (FCs). The reversible nature of Meisenheimer complex formation allows for further functionalization at the droplet-water interface. The strong affinity of fluorofluorescent perylene bisimide (F-PBI) to the CNTs was used to enhance the assembly of CNTs on the FC-water interface. The combination of different concentrations of the functionalized CNTs and the pelene additive enables predictable complex emulsion morphologies. Reversible morphology reconfiguration was explored with the addition of molecular surfactants. Our results show that the interfacial properties of functionalized CNTs have considerable utility in the fabrication of complex dynamic emulsions.

A chemiresistive methane sensor.

A chemiresistive sensor is described for the detection of methane (CH4), a potent greenhouse gas that also poses an explosion hazard in air. The chemiresistor allows for the low-power, low-cost, and distributed sensing of CH4 at room temperature in air with environmental implications for gas leak detection in homes, production facilities, and pipelines. Specifically, the chemiresistors are based on single-walled carbon nanotubes (SWCNTs) noncovalently functionalized with poly(4-vinylpyridine) (P4VP) that enables the incorporation of a platinum-polyoxometalate (Pt-POM) CH4 oxidation precatalyst into the sensor by P4VP coordination. The resulting SWCNT-P4VP-Pt-POM composite showed ppm-level sensitivity to CH4 and good stability to air as well as time, wherein the generation of a high-valent platinum intermediate during CH4 oxidation is proposed as the origin of the observed chemiresistive response. The chemiresistor was found to exhibit selectivity for CH4 over heavier hydrocarbons such as n-hexane, benzene, toluene, and o-xylene, as well as gases, including carbon dioxide and hydrogen. The utility of the sensor in detecting CH4 using a simple handheld multimeter was also demonstrated.

Pentiptycene Polymer/Single-Walled Carbon Nanotube Complexes: Applications in Benzene, Toluene, and o-Xylene Detection.

We report the dispersion of single-walled carbon nanotubes (SWCNTs) using pentiptycene polymers and their use in chemiresistance-based and QCM-D sensors. Poly(p-phenylene ethynylene)s (PPEs) incorporating pentiptycene moieties present a concave surface that promotes π-π interactions and van der Waals interactions with SWCNTs. In contrast to more common polymer-dispersing mechanisms that involve the wrapping of polymers around the SWCNTs, we conclude that the H-shape of pentiptycene groups and the linear rigid-rod structure creates a slot for nanotube binding. UV-vis-NIR, Raman, and fluorescence spectra and TEM images of polymer/SWCNTs support this dispersion model, which shows size selectivity to SWCNTs with diameters of 0.8-0.9 nm. Steric bulk on the channels is problematic, and tert-butylated pentiptycenes do not form stable dispersions with SWCNTs. This result, along with the diameter preference, supports the model in which the SWCNTs are bound to the concave clefts of the pentiptycenes. The binding model suggests that the polymer/SWCNTs complex creates galleries, and we have demonstrated the binding of benzene, toluene, and o-xylene (BTX) vapors as the basis for a robust, sensitive, and selective sensing platform for BTX detection. The utility of our sensors is demonstrated by the detection of benzene at the OSHA short-term exposure limit of 5 ppm in air.