Humidity‐Tolerant Single‐Stranded DNA‐Functionalized Graphene Probe for Medical Applications of Exhaled Breath Analysis

Highly sensitive and selective chemiresistive sensors based on graphene functionalized by metals and metal oxides have attracted considerable attention in the fields of environmental monitoring and medical assessment because of their ultrasensitive gas detecting performance and cost‐effective fabrication. However, their operation, in terms of detection limit and reliability, is limited in traditional applications because of ambient humidity. Here, the enhanced sensitivity and selectivity of single‐stranded DNA‐functionalized graphene (ssDNA‐FG) sensors to NH₃ and H₂S vapors at high humidity are demonstrated and their sensing mechanism is suggested. It is found that depositing a layer of ssDNA molecules leads to effective modulation of carrier density in graphene, as a negative‐potential gating agent and the formation of an additional ion conduction path for proton hopping in the layer of hydronium ions (H₃O⁺) at high humidity (>80%). Considering that selectively responsive chemical vapors are biomarkers associated with human diseases, the obtained results strongly suggest that ssDNA‐FG sensors can be the key to developing a high‐performance exhaled breath analyzer for diagnosing halitosis and kidney disorder.     

Direct Freeform Laser Fabrication of 3D Conformable Electronics

3D conformable electronic devices on freeform surfaces show superior performance to the conventional, planar ones. They represent a trend of future electronics and have witnessed exponential growth in various applications. However, their potential is largely limited by a lack of sophisticated fabrication techniques. To tackle this challenge, a new direct freeform laser (DFL) fabrication method enabled by a 5-axis laser processing platform for directly fabricating 3D conformable electronics on targeted arbitrary surfaces is reported. Accordingly, representative laser-induced graphene (LIG), metals, and metal oxides are successfully fabricated as high-performance sensing and electrode materials from different material precursors on various types of substrates for applications in temperature/light/gas sensing, energy storage, and printed circuit board for circuit. Last but not the least, to demonstrate an application in smart homes, LIG-based conformable strain sensors are fabricated and distributed in designated locations of an artificial tree. The distributed sensors have the capability of monitoring the wind speed and direction with the assistance of well-trained machine-learning models. This novel process will pave a new and general route to fabricating 3D conformable electronic devices, thus creating new opportunities in robotics, biomedical sensing, structural health, environmental monitoring, and Internet of Things applications.     

Imparting Metal Oxides with High Sensitivity Toward Light-Activated NO2 Detection Via Tailored Interfacial Chemistry

Activation of metal oxides by light is a robust yet facile approach to manipulating their surface chemistry for favorable reactions with target molecules in heterogeneous catalysis and gas sensors. However, a limited understanding of interface chemistry and the involved mechanism impedes the development of a rational design of oxide interfaces for light-activated gas sensing. Herein, the TiO_x-assisted photosensitization of In₂O₃ toward NO₂ sensing is investigated as a case study to elucidate the detailed mechanism of light-activated surface chemistry at the metal/gas interface. The resultant heterogeneous oxides exhibit outstanding NO₂ sensing performance under light irradiation thanks to abundant photoexcited electrons and holes that serve as adsorption and desorption sites, respectively, to accelerate both surface reactions. Furthermore, the facile transfer of electrons and holes across the TiO_x-In₂O₃ interface contributes to improving the reversibility of sensing kinetics. Through this study, the mechanistic understanding is established of how the surface chemistry of metal oxide surfaces can be tuned by light activation providing an effective route to the design fabrication of high-performance gas sensors.     

Novel Christmas Branched Like NiO/NiWO4/WO3 (p–p–n) Nanowire Heterostructures for Chemical Sensing

Establishing a platform comprising different nanostructured oxides is an emerging idea to develop highly sensitive and selective sensing devices. Herein, novel 3D-heterostructures (p–p–n) consisting of 1D nanowires of NiO and WO₃ along with their intermediate reactive product, i.e., NiWO₄ seed, are produced by a two-steps vapor phase growth method. In-depth morphological and structural investigations describing the growth mechanism of these heterostructures are presented. Finally, the p–p–n heterostructures are integrated into conductometric sensing devices and their performances are investigated toward different gases. It is observed that by modulating the charge-carrier transport with temperature, the heterostructure sensors exhibit selective behavior toward different gas analytes. Indeed, at 300 °C, the heterostructure sensors show relatively selective behavior toward NO₂, while at 400 °C, high selectivity toward VOCs is observed. The improvement in sensing performances is mainly based on charge carrier transport through the two interfaces (one at WO₃/NiWO₄ (n–p) and the other at NiWO₄/NiO (p–p)) and the modulation of charge carriers in the electron depletion layer of WO₃ and hole accumulation layer of NiO and NiWO₄. The remarkable performance of these complex heterostructures with low ppb-level detection limits makes them excellent candidates for chemical/ gas sensing applications in e-noses.     

Two‐Dimensional Nanostructured Materials for Gas Sensing

Two‐dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface‐to‐volume ratio and good compatibility with device design. In recent years 2D nanostructures of various materials including metal oxides, graphene, metal dichalcogenides, phosphorene, BN and MXenes, have demonstrated significant potential for gas sensors. This review aims to provide the most recent advancements in utilization of various 2D nanomaterials for gas sensing. The common methods for the preparation of 2D nanostructures are briefly summarized first. The focus is then placed on the sensing performances provided by devices integrating 2D nanostructures. Strategies for optimizing the sensing features are also discussed. By combining both the experimental results and the theoretical studies available, structure‐properties correlations are discussed. The conclusion gives some perspectives on the open challenges and future prospects for engineering advanced 2D nanostructures for high‐performance gas sensors devices.     

SnO_2-ZnO的乙醇气敏特性研究

为了解决乙醇传感器灵敏度不够高和选择性较差的问题,使用稀土金属氧化物代替贵金属及其化合物作为催化剂和添加剂制成了以SnO2-ZnO为主体的气敏材料,并对其气敏性能进行了研究。结果表明,此方法可有效提高SnO2-ZnO气敏材料对乙醇气体的灵敏度及选择性;利用制成的SnO2-ZnO气敏材料,可以生产出高灵敏度、高选择性的乙醇传感器。     

High Performance Three‐Dimensional Chemical Sensor Platform Using Reduced Graphene Oxide Formed on High Aspect‐Ratio Micro‐Pillars

The sensing performance of chemical sensors can be achieved not only by modification or hybridization of sensing materials but also through new design in device geometry. The performance of a chemical sensing device can be enhenced from a simple three‐dimensional (3D) chemiresistor‐based gas sensor platform with an increased surface area by forming networked, self‐assembled reduced graphene oxide (R‐GO) nanosheets on 3D SU8 micro‐pillar arrays. The 3D R‐GO sensor is highly responsive to low concentration of ammonia (NH₃) and nitrogen dioxide (NO₂) diluted in dry air at room temperature. Compared to the two‐dimensional planar R‐GO sensor structure, as the result of the increase in sensing area and interaction cross‐section of R‐GO on the same device area, the 3D R‐GO gas sensors show improved sensing performance with faster response (about 2%/s exposure), higher sensitivity, and even a possibly lower limit of detection towards NH₃ at room temperature.     

Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

Recent Advances in Sensing Applications of Graphene Assemblies and Their Composites

Development of next‐generation sensor devices is gaining tremendous attention in both academia and industry because of their broad applications in manufacturing processes, food and environment control, medicine, disease diagnostics, security and defense, aerospace, and so forth. Current challenges include the development of low‐cost, ultrahigh, and user‐friendly sensors, which have high selectivity, fast response and recovery times, and small dimensions. The critical demands of these new sensors are typically associated with advanced nanoscale sensing materials. Among them, graphene and its derivatives have demonstrated the ideal properties to overcome these challenges and have merged as one of the most popular sensing platforms for diverse applications. A broad range of graphene assemblies with different architectures, morphologies, and scales (from nano‐, micro‐, to macrosize) have been explored in recent years for designing new high‐performing sensing devices. Herein, this study presents and discusses recent advances in synthesis strategies of assembled graphene‐based superstructures of 1D, 2D, and 3D macroscopic shapes in the forms of fibers, thin films, and foams/aerogels. The fabricated state‐of‐the‐art applications of these materials in gas and vapor, biomedical, piezoresistive strain and pressure, heavy metal ion, and temperature sensors are also systematically reviewed and discussed, and their sensing performance is compared.     

Microwave Combustion for Modification of Transition Metal Oxides

The introduction of oxygen vacancy for transition metal oxide is an effective method to tune their conductivity. Here, microwave combustion method is used to quickly synthesize reduced metal oxides and graphene hybrid composite in several minutes. Among these as‐synthesized composites, the reduced orthorhombic Nb₂O₅ and graphene oxide (rNb₂O₅/rGO) composite demonstrates great electrochemical performance with a reversible specific capacity of 726.2 C g^?1 at 2 mV s^?1 in organic electrolyte as well as a good capacity retention of 87% after 3000 cycles at 10 A g^?1. It is believed that this strategy can be a common route to quickly produce oxygen vacancy in oxides and satisfy much more application requirements even for the possibility of industrialization.     

Single‐Crystal‐to‐Single‐Crystal Transformation of a Europium(III) Metal–Organic Framework Producing a Multi‐responsive Luminescent Sensor

A sensor with a red‐emission signal is successfully obtained by the solvothermal reaction of Eu³⁺ and heterofunctional ligand bpydbH₂ (4,4′‐(4,4′‐bipyridine‐2,6‐diyl) dibenzoic acid), followed by terminal‐ligand exchange in a single‐crystal‐to‐single‐crystal transformation. As a result of treatments both before and after the metal–organic framework formation, accessible Lewis‐base sites and coordinated water molecules are successfully anchored onto the host material, and they act as signal transmission media for the recognition of analytes at the molecular level. This is the first reported sensor based on a metal–organic framework (MOF) with multi‐responsive optical sensing properties. It is capable of sensing small organic molecules and inorganic ions, and unprecedentedly it can discriminate among the homologues and isomers of aliphatic alcohols as well as detect highly explosive 2,4,6‐trinitrophenol (TNP) in water or in the vapor phase. This work highlights the practical application of luminescent MOFs as sensors, and it paves the way toward other multi‐responsive sensors by demonstrating the incorporation of various functional groups into a single framework.     

Sandwich‐Like Nanocomposite of CoNiOx/Reduced Graphene Oxide for Enhanced Electrocatalytic Water Oxidation

The development of cost‐effective and high‐performance electrocatalysts for oxygen evolution reaction (OER) is essential for sustainable energy storage and conversion processes. This study reports a novel and facile approach to the hierarchical‐structured sheet‐on‐sheet sandwich‐like nanocomposite of CoNiO _x /reduced graphene oxide as highly active electrocatalysts for water oxidation. Notably, the as‐prepared composite can operate smoothly both in 0.1 and 1.0 m KOH alkaline media, displaying extremely low overpotentials, fast kinetics, and strong durability over long‐term continuous electrolysis. Impressively, it is found that its catalytic activity can be further promoted by anodic conditioning owing to the in situ generation of electrocatalytic active species (i.e., metal hydroxide/(oxy)hydroxides) and the enriched oxygen deficiencies at the surface. The achieved ultrahigh performance is unmatched by most of the transition‐metal/nonmetal‐based catalysts reported so far, and even better than the state‐of‐the‐art noble‐metal catalysts, which can be attributed to its special well‐defined physicochemical textural features including hierarchical architecture, large surface area, porous thin nanosheets constructed from CoNiO _x nanoparticles (≈5 nm in size), and the incorporation of charge‐conducting graphene. This work provides a promising strategy to develop earth‐abundant advanced OER electrocatalysts to replace noble metals for a multitude of renewable energy technologies.     

Graphene‐Based Mesoporous SnO2 with Enhanced Electrochemical Performance for Lithium‐Ion Batteries

Graphene‐based metal oxides generally show outstanding electrochemical performance due to the superior properties of graphene. However, the aggregation of active metal oxide nanoparticles on the graphene surface may result in a capacity fading and poor cycle performance. Here, a mesostructured graphene‐based SnO₂ composite is prepared through in situ growth of SnO₂ particles on the graphene surface using cetyltrimethylammonium bromide as the structure‐directing agent. This novel mesoporous composite inherits the advantages of graphene nanosheets and mesoporous materials and exhibits higher reversible capacity, better cycle performance, and better rate capability compared to pure mesoporous SnO₂ and graphene‐based nonporous SnO₂. It is concluded that the synergetic effect between graphene and mesostructure benefits the improvement of the electrochemical properties of the hybrid composites. This facile method may offer an attractive alternative approach for preparation of the graphene‐based mesoporous composites as high‐ performance electrodes for lithium‐ion batteries.     

High selective gas sensors based on surface modified polymer transistor

Gas sensors based on organic field effect transistors have attracted great attentions and achieved much progress because of their inherent merits such as low-cost, room operating temperature, good portability and flexibility. However, high sensitivity and good selectivity are still challenging issues blocking their further development. Herein, we demonstrate a promising strategy for fabricating high selective organic gas sensors through introducing surface modification. Modified substrate with different self-assembling monolayers (SAMs), the sensing properties of polymer OFET gas sensors are varied with terminal group attached on the SAM. The bare device shows significant sensitive to NH₃, while it becomes much more sensitive to NO₂ if a fluorine substituent SAM adopted. The NH₂-terminal SAM and CH₃-terminal SAM bring moderate sensitivity to gases like NH₃ and NO₂. Those various sensitivity and device parameter evolution are promising to generate a patterning recognition for different gases, which may provide a potential promising approach for improving selectivity of organic gas sensors.     

Critical Aspects and Recent Advances in Structural Engineering of Photocatalysts for Sunlight‐Driven Photocatalytic Reduction of CO2 into Fuels

The catalytic conversion of CO₂ into valuable fuels is a compelling solution for tackling the global warming and fuel crisis. Light absorption and charge separation, as well as adsorption/activation of CO₂ on the photocatalyst surface, are essential steps for this process. This article reviews the CO₂ photoreduction mechanisms and critical aspects that greatly affect the photoreduction efficiency. Additionally, different materials for CO₂ photoreduction are provided, including d⁰ and d¹⁰ metal oxides/mixed oxides, sulfides, polymeric materials, and metal phosphides with visible response, metal‐organic frameworks, and layer double hydroxides. Furthermore, various structural engineering strategies and corresponding state‐of‐the‐art photocatalytic systems are reviewed and discussed, such as bandgap engineering, geometrical nanostructure engineering, and heterostructure engineering. Each strategy has advantages and disadvantages, requiring further adjustment to further improve the photocatalytic performance of the photocatalyst. Based on this review, it is greatly expected that efficiently artificial systems and the breakthrough technologies for CO₂ reduction will be successfully developed in the future to solve the energy shortage as well as the environmental problem.     

石墨烯基超级电容器电极材料研究进展

从表面改性剂、过渡金属氧化物粒子以及导电聚合物三个方面,综述了利用物理及化学方法对石墨烯进行表面改性的研究进展,展望了改性的石墨烯基复合材料在超级电容器电极材料上的良好应用前景,以及今后的研究方向.     

A Plant-inspired Light Transducer for High-performance Near-infrared Light Mediated Gas Sensing

Constructing near-infrared light (NIR) light-enhanced room temperature gas sensors is becoming more promising for practical application. In this study, learning from the structure and photosynthetic process of chlorophyll thylakoid membranes in plants, the first “Thylakoid membrane” structural formaldehyde (HCHO) sensor is constructed by matching the upconversion emission of the lanthanide-doped upconversion nanoparticles (UCNPs) and the UV–vis adsorption of the as-prepared nanocomposites. The NIR-mediated sensor exhibits excellent performances, including ultra-high response (R_a / R_g = 2.22, 1 ppm), low practical limit of detection (50 ppb), reliable repeatability, high selectivity, and broadband spectral response. The practicality of the NIR-mediated gas sensor is confirmed through the remote and external stimulation test. A study of sensing mechanism demonstrates that it is the UCNPs-based light transducer produces more light-induced oxygen species for gas response in the process of non-radiative/radiative energy transfer, playing a key role in significantly improving the sensing properties of the sensor. The universality of NIR-mediated gas sensors based on UCNPs is verified using ZnO, In₂O_3, and SnO₂ systems. This work paves a way for fabricating high-performance NIR-mediated gas sensors and will expand the application fields of NIR light.     

Development of Film Sensors Based on Conjugated Polymers for Copper (II) Ion Detection

A fluorescent film sensor was prepared by chemical modification of a polyfluorene derivative on a glass‐plate surface. X‐ray photoelectron spectroscopy and ellipsometry measurements demonstrate the covalent attachment of the polyfluorene derivative to the glass‐plate surface. The sensor was used to detect Cu²⁺ ions in aqueous solution by a mechanism exploiting fluorescence quenching of conjugated polymers. Among the tested metal ions, the film sensor presents good selectivity towards Cu²⁺ ions. Further experiments show that the sensing process is reversible. Moreover, sensory microarrays based on conjugated polymers targeting Cu²⁺ ions are constructed, which display similar sensing performance to that of the film sensor. The structural motif in which conjugated polymers are covalently confined to a solid substrate surface offers several attractive advantages for sensing applications. First, in comparison with film sensors in which small fluorescent molecules are employed as sensing elements, the sensitivity of our new film sensor is enhanced due to the signal‐amplifying effect of the conjugated polymers. Second, the film sensors or microarrays can be used in aqueous environments, which is crucial for their potential use in a wide range of real‐world systems. Since the sensing process is reversible, the sensing materials can be reused. Third, unlike physically coated polymer chains, the covalent attachment of the grafted chains onto a material surface precludes desorption and imparts long‐term stability of the polymer chains.     

Degenerately Hydrogen Doped Molybdenum Oxide Nanodisks for Ultrasensitive Plasmonic Biosensing

Plasmonic biosensors based on noble metals generally suffer from low sensitivities if the perturbation of refractive‐index in the ambient is not significant. By contrast, the features of degenerately doped semiconductors offer new dimensions for plasmonic biosensing, by allowing charge‐based detection. Here, this concept is demonstrated in plasmonic hydrogen doped molybdenum oxides (H_xMoO₃), with the morphology of 2D nanodisks, using a representative enzymatic glucose sensing model. Based on the ultrahigh capacity of the molybdenum oxide nanodisks for accommodating H⁺, the plasmon resonance wavelengths of H_xMoO₃ are shifted into visible‐near‐infrared wavelengths. These plasmonic features alter significantly as a function of the intercalated H⁺ concentration. The facile H⁺ deintercalation out of H_xMoO₃ provides an exceptional sensitivity and fast kinetics to charge perturbations during enzymatic oxidation. The optimum sensing response is found at H_1.55MoO₃, achieving a detection limit of 2 × 10^?9m at 410 nm, even when the biosensing platform is adapted into a light‐emitting diode‐photodetector setup. The performance is superior in comparison to all previously reported plasmonic enzymatic glucose sensors, providing a great opportunity in developing high performance biosensors.     

Stretchable,Skin‐Mountable,and Wearable Strain Sensors and Their Potential Applications: A Review

There is a growing demand for flexible and soft electronic devices. In particular, stretchable, skin‐mountable, and wearable strain sensors are needed for several potential applications including personalized health‐monitoring, human motion detection, human‐machine interfaces, soft robotics, and so forth. This Feature Article presents recent advancements in the development of flexible and stretchable strain sensors. The article shows that highly stretchable strain sensors are successfully being developed by new mechanisms such as disconnection between overlapped nanomaterials, crack propagation in thin films, and tunneling effect, different from traditional strain sensing mechanisms. Strain sensing performances of recently reported strain sensors are comprehensively studied and discussed, showing that appropriate choice of composite structures as well as suitable interaction between functional nanomaterials and polymers are essential for the high performance strain sensing. Next, simulation results of piezoresistivity of stretchable strain sensors by computational models are reported. Finally, potential applications of flexible strain sensors are described. This survey reveals that flexible, skin‐mountable, and wearable strain sensors have potential in diverse applications while several grand challenges have to be still overcome.