Chemiresistive Sensor Array with Nanostructured Interfaces for Detection of Human Breaths with Simulated Lung Cancer Breath VOCs.

Timely screening of lung cancer represents a challenging task for early diagnosis and treatment, which calls for reliable, low-cost, and noninvasive detection tools. One type of promising tools for early-stage cancer detection is breath analyzers or sensors that detect breath volatile organic compounds (VOCs) as biomarkers in exhaled breaths. However, a major challenge is the lack of effective integration of the different sensor system components toward the desired portability, sensitivity, selectivity, and durability for many of the current breath sensors. In this report, we demonstrate herein a portable and wireless breath sensor testing system integrated with sensor electronics, breath sampling, data processing, and sensor arrays derived from nanoparticle-structured chemiresistive sensing interfaces for detection of VOCs relevant to lung cancer biomarkers in human breaths. In addition to showing the sensor viability for the targeted application by theoretical simulations of chemiresistive sensor array responses to the simulated VOCs in human breaths, the sensor system was tested experimentally with different combinations of VOCs and human breath samples spiked with lung cancer-specific VOCs. The sensor array exhibits high sensitivity to lung cancer VOC biomarkers and mixtures, with a limit of detection as low as 6 ppb. The results from testing the sensor array system in detecting breath samples with simulated lung cancer VOC constituents have demonstrated an excellent recognition rate in discriminating healthy human breath samples and those with lung cancer VOCs. The recognition statistics were analyzed, showing the potential viability and optimization toward achieving the desired sensitivity, selectivity, and accuracy in the breath screening of lung cancer.

Density functional theory based computational investigations on the stability of highly active trimetallic PtPdCu nanoalloys for electrochemical oxygen reduction.

Activity, cost, and durability are the trinity of catalysis research for the electrochemical oxygen reduction reaction (ORR). While studies towards increasing activity and reducing cost of ORR catalysts have been carried out extensively, much effort is needed in durability investigation of highly active ORR catalysts. In this work, we examined the stability of a trimetallic PtPdCu catalyst that has demonstrated high activity and incredible durability during ORR using density functional theory (DFT) based computations. Specifically, we studied the processes of dissolution/deposition and diffusion between the surface and inner layer of Cu species of Pt20Pd20Cu60 catalysts at electrode potentials up to 1.2 V to understand their role towards stabilizing Pt20Pd20Cu60 catalysts. The results show there is a dynamic Cu surface composition range that is dictated by the interplay of the four processes, dissolution, deposition, diffusion from the surface to inner layer, and diffusion from the inner layer to the surface of Cu species, in the stability and observed oscillation of lattice constants of Cu-rich PtPdCu nanoalloys.

Silver-Copper Alloy Nanoinks for Ambient Temperature Sintering.

There is an increasing need to reduce the silver content in silver-based inks or pastes and achieve low-temperature sintering for scalable and low-cost production of printed wearable electronics. This need depends on the ability to control the metal composition and the surface properties of the nanoinks. Alloying silver with copper provides a pathway for meeting the need in terms of cost reduction, but little is known about the composition controllability and the low-temperature sintering capability. We report herein a scalable wet chemical synthesis of bimetallic silver-copper alloy nanoinks with room temperature sintering properties. The bimetallic alloy nanoparticles with a controllable composition can be formulated as stable nanoinks. The nanoinks printed on paper substrates are shown to sinter under room temperature. In addition to composition dependence, the results reveal an intriguing dependence of sintering on humidity above the printed nanoink films. These findings are assessed based on theoretical simulation of the sintering processes via surface-mediated sintering and interparticle necking mechanisms in terms of nanoscale adsorption, adhesion and diffusion, and surface free energies. Implications of the findings for room temperature fabrication of wearable sensors are also discussed.

A Low-Current and Multi-Channel Chemiresistor Array Sensor Device.

This paper describes the design of a low-current, multichannel, handheld electronic device integrated with nanostructured chemiresistor sensor arrays. A key design feature of the electronic circuit board is its low excitation current for achieving optimal performance with the arrays. The electronics can rapidly acquire the resistances for different sensors, not only spanning several orders of magnitude, but also as high as several hundreds of megaohms. The device tested is designed using a chemiresistor array with nanostructured sensing films prepared by molecularly-mediated assemblies of gold nanoparticles for detection. The low-current, wide-range, and auto-locking capabilities, along with the effective coupling with the nanostructured chemiresistor arrays, meet the desired performances of a low excitation current and low power consumption, and also address the potential instability of the sensors in a complex sensing environment. The results are promising for potential applications of the device as a portable sensor for the point-of-need monitoring of air quality and as a biosensor for point-of-care human breath screening for disease biomarkers.

Nano-Filamented Textile Sensor Platform with High Structure Sensitivity.

A key challenge to the creation of chemically responsive electro-functionality of nonconductive, hydrophobic, and free-contacted textile or fibrous network materials is how to impart the 3D structure with functional filaments to enable responsive structure sensitivity, which is critical in establishing the fibrous platform technology for sensor applications. We demonstrate this capability using an electrospun polymeric fibrous substrate embedded with nano-filaments defined by size-tunable gold nanoparticles and structurally sensitive dendrons as crosslinkers. The resulting interparticle properties strongly depend on the assembly of the nano-filaments, enabling an interface with high structure sensitivity to molecular interactions. This is demonstrated with chemiresistive responses to vaporous alcohol molecules with different chain lengths and isomers, which is critical in breath and sweat sensing involving a high-moisture or -humidity background. The sensitivity scales with the chain length and varies with their isomers. This approach harnesses the multifunctional tunability of the nano-filaments in a sensor array format, showing high structure sensitivity to the alcohol molecules with different chain lengths and isomers. The high structure sensitivity and its implications for a paradigm shift in the design of textile sensor arrays for multiplexing human performance monitoring via breath or sweat sensing and environmental monitoring of air quality are also discussed.

Lattice Strain and Surface Activity of Ternary Nanoalloys under the Propane Oxidation Condition.

The ability to harness the catalytic oxidation of hydrocarbons is critical for both clean energy production and air pollutant elimination, which requires a detailed understanding of the dynamic role of the nanophase structure and surface reactivity under the reaction conditions. We report here findings of an in situ/operando study of such details of a ternary nanoalloy under the propane oxidation condition using high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalysts are derived by alloying Pt with different combinations of second (Pd) and third (Ni) transition metals, showing a strong dependence of the catalytic activity on the Ni content. The evolution of the phase structure of the nanoalloy is characterized by HE-XRD/PDF probing of the lattice strain, whereas the surface activity is monitored by DRIFTS detection of the surface intermediate formation during the oxidation of propane by oxygen. The results reveal the dominance of the surface intermediate species featuring a lower degree of oxygenation upon the first C-C bond cleavage on the lower-Ni-content nanoalloy and a higher degree of oxygenation upon the second C-C bond cleavage on the higher-Ni-content nanoalloy. The face-centered-cubic-type phase structures of the nanoalloys under the oxidation condition are shown to exhibit Ni-content-dependent changes of lattice strains, featuring the strongest strain with little variation for the higher-Ni-content nanoalloy, in contrast to the weaker strains with oscillatory variation for the lower-Ni-content nanoalloys. This process is also accompanied by oxygenation of the metal components in the nanoalloy, showing a higher degree of oxygenation for the higher-Ni-content nanoalloy. These subtle differences in phase structure and surface activity changes correlate with the Ni-composition-dependent catalytic activity of the nanoalloys, which sheds a fresh light on the correlation between the dynamic change of atomic strains and the surface reactivity and has significant implications for the design of oxidation catalysts with enhanced activities.

Assessing Plasmonic Nanoprobes in Electromagnetic Field Enhancement for SERS Detection of Biomarkers.

The exploration of the plasmonic field enhancement of nanoprobes consisting of gold and magnetic core@gold shell nanoparticles has found increasing application for the development of surface-enhanced Raman spectroscopy (SERS)-based biosensors. The understanding of factors controlling the electromagnetic field enhancement, as a result of the plasmonic field enhancement of the nanoprobes in SERS biosensing applications, is critical for the design and preparation of the optimal nanoprobes. This report describes findings from theoretical calculations of the electromagnetic field intensity of dimer models of gold and magnetic core@gold shell nanoparticles in immunoassay SERS detection of biomarkers. The electromagnetic field intensities for a series of dimeric nanoprobes with antibody-antigen-antibody binding defined interparticle distances were examined in terms of nanoparticle sizes, core-shell sizes, and interparticle spacing. The results reveal that the electromagnetic field enhancement not only depended on the nanoparticle size and the relative core size and shell thicknesses of the magnetic core@shell nanoparticles but also strongly on the interparticle spacing. Some of the dependencies are also compared with experimental data from SERS detection of selected cancer biomarkers, showing good agreement. The findings have implications for the design and optimization of functional nanoprobes for SERS-based biosensors.

Engineering Active Sites of Gold-Cuprous Oxide Catalysts for Electrocatalytic Oxygen Reduction Reaction.

Understanding how the catalyst morphology influences surface sites is crucial for designing active and stable catalysts and electrocatalysts. We here report a new approach to this understanding by decorating gold (Au) nanoparticles on the surface of cuprous oxides (Cu2O) with three different shape morphologies (spheres, cubes, and petals). The Au-Cu2O particles are dispersed onto carbon nanotube (CNT) matrix with high surface area, stability, and conductivity for oxygen reduction reaction. A clear morphology-dependent enhancement of the electrocatalytic activity is revealed. Oxygenated gold species (AuO-) are found to coexist with Au0 on the cube and petal catalysts, whereas only Au0 species are present on the sphere catalyst. The AuO- species function effectively as active sites, resulting in the improved catalytic performance by changing the reaction mechanism. The enhanced catalytic performance of the petal-shaped catalyst in terms of onset potential, half-wave potential, diffusion-limited current density, and stability is closely associated with the presence of the most abundant AuO- species on its surface. Highly active AuO- species are identified on the surface of the catalysts as a result of the unique structural characteristics, which is attributed to the structural origin of high activity and stability. This insight constitutes the basis for assessing the detailed correlation between the morphology and the electrocatalytic properties of the nanocomposite catalysts, which has implications for the design of surface-active sites on metal/metal oxide electrocatalysts.

Magneto-Plasmonic Nanoparticle Grid Biosensor with Enhanced Raman Scattering and Electrochemical Transduction for the Development of Nanocarriers for Targeted Delivery of Protected Anticancer Drugs.

Safe administration of highly cytotoxic chemotherapeutic drugs is a challenging problem in cancer treatment due to the adverse side effects and collateral damage to non-tumorigenic cells. To mitigate these problems, promising new approaches, based on the paradigm of controlled targeted drug delivery (TDD), and utilizing drug nanocarriers with biorecognition ability to selectively target neoplastic cells, are being considered in cancer therapy. Herein, we report on the design and testing of a nanoparticle-grid based biosensing platform to aid in the development of new targeted drug nanocarriers. The proposed sensor grid consists of superparamagnetic gold-coated core-shell Fe2Ni@Au nanoparticles, further functionalized with folic acid targeting ligand, model thiolated chemotherapeutic drug doxorubicin (DOX), and a biocompatibility agent, 3,6-dioxa-octanethiol (DOOT). The employed dual transduction method based on electrochemical and enhanced Raman scattering detection has enabled efficient monitoring of the drug loading onto the nanocarriers, attaching to the sensor surface, as well as the drug release under simulated intracellular conditions. The grid's nanoparticles serve here as the model nanocarriers for new TDD systems under design and optimization. The superparamagnetic properties of the Fe2Ni@Au NPs aid in nanoparticles' handling and constructing a dense sensor grid with high plasmonic enhancement of the Raman signals due to the minimal interparticle distance.

Strain sensors fabricated by surface assembly of nanoparticles.

Harnessing interparticle spatial properties of surface assembly of nanoparticles (SAN) on flexible substrates is a rapidly emerging front of research in the design and fabrication of highly-sensitive strain sensors. It has recently shown promising potentials for applications in wearable sensors and skin electronics. SANs feature 3D structural tunability of the interparticle spatial properties at both molecular and nanoscale levels, which is transformative for the design of intriguing strain sensors. This review will present a comprehensive overview of the recent research development in exploring SAN-structured strain sensors for wearable applications. It starts from the basic principle governing the strain sensing characteristics of SANs on flexible substrates in terms of thermally-activated interparticle electron tunneling and conductive percolation. This discussion is followed by descriptions of the fabrication of the sensors and the proof-of-concept demonstrations of the strain sensing characteristics. The nanoparticles in the SANs are controllable in terms of size, shape, and composition, whereas the interparticle molecules enable the tunability of the electrical properties in terms of interparticle spatial properties. The design of SAN-derived strain sensors is further highlighted by describing several recent examples in the explorations of their applications in wearable biosensor and bioelectronics. Fundamental understanding of the role of interparticle spatial properties within SANs at both molecular and device levels is the focal point. The future direction of the SAN-derived wearable sensors will also be discussed, shining lights on a potential paradigm shift in materials design in exploring the emerging opportunities in wearable sensors and skin electronics.

Molecularly-tunable nanoelectrode arrays created by harnessing intermolecular interactions.

Intermolecular interactions play a critical role in the binding strength of molecular assemblies on surfaces. The ability to harness them enables molecularly-tunable interfacial structures and properties. Herein we report the tuning of the intermolecular interactions in monolayer assemblies derived from organothiols of different structures for the creation of nanoelectrode arrays or ensembles with effective mass transport by a molecular-level perforation strategy. The homo- and hetero-intermolecular interactions can be fully controlled, which is demonstrated not only by thermodynamic analysis of the fractional coverage but also by surface infrared reflection absorption and X-ray photoelectron spectroscopic characterizations. This understanding enables controllable electrochemical perforation for the creation of ensembles or arrays of channels across the monolayer thickness with molecular and nanoscale dimensions. Redox reactions on the nanoelectrode array display molecular tunability with a radial diffusion characteristic in good agreement with theoretical simulation results. These findings have implications for designing membrane-type ion-gating, electrochemical sensing, and electrochemical energy storage devices with molecular level tunability.

Recent Advances in Electrocatalysts for Proton Exchange Membrane Fuel Cells and Alkaline Membrane Fuel Cells.

The rapid progress of proton exchange membrane fuel cells (PEMFCs) and alkaline exchange membrane fuel cells (AMFCs) has boosted the hydrogen economy concept via diverse energy applications in the past decades. For a holistic understanding of the development status of PEMFCs and AMFCs, recent advancements in electrocatalyst design and catalyst layer optimization, along with cell performance in terms of activity and durability in PEMFCs and AMFCs, are summarized here. The activity, stability, and fuel cell performance of different types of electrocatalysts for both oxygen reduction reaction and hydrogen oxidation reaction are discussed and compared. Research directions on the further development of active, stable, and low-cost electrocatalysts to meet the ultimate commercialization of PEMFCs and AMFCs are also discussed.

Hydrogen production from water electrolysis: role of catalysts.

As a promising substitute for fossil fuels, hydrogen has emerged as a clean and renewable energy. A key challenge is the efficient production of hydrogen to meet the commercial-scale demand of hydrogen. Water splitting electrolysis is a promising pathway to achieve the efficient hydrogen production in terms of energy conversion and storage in which catalysis or electrocatalysis plays a critical role. The development of active, stable, and low-cost catalysts or electrocatalysts is an essential prerequisite for achieving the desired electrocatalytic hydrogen production from water splitting for practical use, which constitutes the central focus of this review. It will start with an introduction of the water splitting performance evaluation of various electrocatalysts in terms of activity, stability, and efficiency. This will be followed by outlining current knowledge on the two half-cell reactions, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), in terms of reaction mechanisms in alkaline and acidic media. Recent advances in the design and preparation of nanostructured noble-metal and non-noble metal-based electrocatalysts will be discussed. New strategies and insights in exploring the synergistic structure, morphology, composition, and active sites of the nanostructured electrocatalysts for increasing the electrocatalytic activity and stability in HER and OER will be highlighted. Finally, future challenges and perspectives in the design of active and robust electrocatalysts for HER and OER towards efficient production of hydrogen from water splitting electrolysis will also be outlined.

Alloying-realloying enabled high durability for Pt-Pd-3d-transition metal nanoparticle fuel cell catalysts.

Alloying noble metals with non-noble metals enables high activity while reducing the cost of electrocatalysts in fuel cells. However, under fuel cell operating conditions, state-of-the-art oxygen reduction reaction alloy catalysts either feature high atomic percentages of noble metals (>70%) with limited durability or show poor durability when lower percentages of noble metals (<50%) are used. Here, we demonstrate a highly-durable alloy catalyst derived by alloying PtPd (<50%) with 3d-transition metals (Cu, Ni or Co) in ternary compositions. The origin of the high durability is probed by in-situ/operando high-energy synchrotron X-ray diffraction coupled with pair distribution function analysis of atomic phase structures and strains, revealing an important role of realloying in the compressively-strained single-phase alloy state despite the occurrence of dealloying. The implication of the finding, a striking departure from previous perceptions of phase-segregated noble metal skin or complete dealloying of non-noble metals, is the fulfilling of the promise of alloy catalysts for mass commercialization of fuel cells.

A multifunctional anode with P-doped Si nanoparticles in a stress-buffering network of poly-γ-glutamate and graphene.

Here, a new strategy is reported for the preparation of a new class of nanocomposite anode materials consisting of ppm-level phosphorus-doped Si nanoparticles (P-Si) wrapped in a network of poly-γ-glutamate and graphene. The network produces not only a conductivity-enhanced conduit but also a mechanical stress buffer. The incorporation of poly-γ-glutamate in the nanocomposite enables self-healing capability and maintains the electrode structural integrity. This multifunctionality has significant implications for advancing the design of stable Si-based nanomaterials as high-performance anodes in Li-ion batteries.

Dynamic Core-Shell and Alloy Structures of Multimetallic Nanomaterials and Their Catalytic Synergies.

ConspectusMultimetallic nanomaterials containing noble metals (NM) and non-noble 3d-transition metals (3d-TMs) exhibit unique catalytic properties as a result of the synergistic combination of NMs and 3d-TMs in the nanostructure. The exploration of such a synergy depends heavily on the understanding of the atomic-scale structural details of NMs and 3d-TMs in the nanomaterials. This has attracted a great deal of recent interest in the field of catalysis science, especially concerning the core-shell and alloy nanostructures. A rarely asked question of fundamental significance is how the core-shell and alloy structural arrangements of atoms in the multimetallic nanomaterials dynamically change under reaction conditions, including reaction temperature, surface adsorbate, chemical environment, applied electrochemical potential, etc. The dynamic evolution of the core-shell/alloy structures under the reaction conditions plays a crucial role in the catalytic performance of the multimetallic nanocatalysts.This Account focuses on the dynamic structure characteristics for several different types of composition-tunable alloy and core-shell nanomaterials, including phase-segregated, elemental-enriched, dynamically evolved, and structurally different core-shell structures. In addition to outlining core-shell/alloy structure formation via processes such as seed-mediated growth, thermochemical calcination, adsorbate-induced evolution, chemical dealloying, underpotential deposition/galvanic displacement, etc., this Account will highlight the progress in understanding the dynamic core-shell/alloy structures under chemical or catalytic reaction conditions, which has become an important focal point of the research fronts in catalysis and electrocatalysis. The employment of advanced techniques, especially in situ/operando synchrotron high-energy X-ray diffraction and pair distribution function analyses, has provided significant insights into the dynamic evolution processes of NM/3d-TM nanocatalysts under electrocatalytic or fuel cell operating conditions. Examples will highlight Pt- or Pd-based nanoparticles and nanowires alloyed with various 3d-TMs with a focus on their structural evolution under reaction conditions. While the dynamic process is complex, the ability to gain an insight into the evolution of core-shell and alloy structures under the catalytic reaction condition is essential for advancing the design of multimetallic nanocatalysts. This Account serves as a springboard from fundamental understanding of the core-shell and alloy structural dynamics to the various applications of nanostructured catalysts/electrocatalysts, especially in the fronts of energy and environmental sustainability.

Surface oxygenation of multicomponent nanoparticles toward active and stable oxidation catalysts.

The need for active and stable oxidation catalysts is driven by the demands in production of valuable chemicals, remediation of hydrocarbon pollutants and energy sustainability. Traditional approaches focus on oxygen-activating oxides as support which provides the oxygen activation at the catalyst-support peripheral interface. Here we report a new approach to oxidation catalysts for total oxidation of hydrocarbons (e.g., propane) by surface oxygenation of platinum (Pt)-alloyed multicomponent nanoparticles (e.g., platinum-nickel cobalt (Pt-NiCo)). The in-situ/operando time-resolved studies, including high-energy synchrotron X-ray diffraction and diffuse reflectance infrared Fourier transform spectroscopy, demonstrate the formation of oxygenated Pt-NiOCoO surface layer and disordered ternary alloy core. The results reveal largely-irregular oscillatory kinetics associated with the dynamic lattice expansion/shrinking, ordering/disordering, and formation of surface-oxygenated sites and intermediates. The catalytic synergy is responsible for reduction of the oxidation temperature by ~100 °C and the high stability under 800 °C hydrothermal aging in comparison with Pt, and may represent a paradigm shift in the design of self-supported catalysts.

Surface-Mediated Interconnections of Nanoparticles in Cellulosic Fibrous Materials toward 3D Sensors.

Fibrous materials serve as an intriguing class of 3D materials to meet the growing demands for flexible, foldable, biocompatible, biodegradable, disposable, inexpensive, and wearable sensors and the rising desires for higher sensitivity, greater miniaturization, lower cost, and better wearability. The use of such materials for the creation of a fibrous sensor substrate that interfaces with a sensing film in 3D with the transducing electronics is however difficult by conventional photolithographic methods. Here, a highly effective pathway featuring surface-mediated interconnection (SMI) of metal nanoclusters (NCs) and nanoparticles (NPs) in fibrous materials at ambient conditions is demonstrated for fabricating fibrous sensor substrates or platforms. Bimodally distributed gold-copper alloy NCs and NPs are used as a model system to demonstrate the semiconductive-to-metallic conductivity transition, quantized capacitive charging, and anisotropic conductivity characteristics. Upon coupling SMI of NCs/NPs as electrically conductive microelectrodes and surface-mediated assembly (SMA) of the NCs/NPs as chemically sensitive interfaces, the resulting fibrous chemiresistors function as sensitive and selective sensors for gaseous and vaporous analytes. This new SMI-SMA strategy has significant implications for manufacturing high-performance fibrous platforms to meet the growing demands of the advanced multifunctional sensors and biosensors.

Strain-Modulated Platinum-Palladium Nanowires for Oxygen Reduction Reaction.

Electrocatalytic activity of alloy nanocatalytsts can be manipulated effectively by tuning their physical properties (ensemble, geometric, and ligand effects) to afford optimal surface structure and compositions for proton exchange membrane fuel cell (PEMFC) application. Herein, highly catalytic platinum-palladium nanowires (PtnPd100-n NWs) with a subtle lattice strain and Boerdijk-Coxeter helix type morphology are synthesized through a surfactant-free, thermal single phase solvent method. X-ray diffraction results show that PtnPd100-n NWs are exposed through the (111) facets and their shrinking or expanding lattice parameters can be modulated by the alloy compositions. Electrochemical results reveal that their high catalytic activity correlates with the lattice shrinking, facets, and bimetallic compositions, showing higher activity when the ratio of Pt and Pd is ∼78:22, which is further supported by DFT results. Compared to the nanoparticle type platinum-palladium alloyed catalysts with similar metal compositions (PtnPd100-n NPs), the PtnPd100-n NWs exhibit significantly improved electrocatalytic activity and stability for the oxygen reduction reaction. These findings open new strategies to design the highly active and stable alloy nanocatalysts with controllable compositions.