Joule Heating a Palladium Nanowire Sensor for Accelerated Response and Recovery to Hydrogen Gas

The properties of a single heated palladium (Pd) nanowire for the detection of hydrogen gas (H₂) are explored. In these experiments, a Pd nanowire, 48–98 µm in length, performs three functions in parallel: 1) Joule self‐heating is used to elevate the nanowire temperature by up to 128 K, 2) the 4‐contact wire resistance in the absence of H₂ is used to measure its temperature, and 3) the nanowire resistance in the presence of H₂ is correlated with its concentration, allowing it to function as a H₂ sensor. Compared with the room‐temperature response of a Pd nanowire, the response of the heated nanowire to hydrogen is altered in two ways: First, the resistance change (ΔR/R₀) induced by H₂ exposure at any concentration is reduced by a factor of up to 30 and second, the rate of the resistance change – observed at the beginning (“response”) and at the end (“recovery”) of a pulse of H₂ – is increased by more than a factor of 50 at some H₂ concentrations. Heating nearly eliminates the retardation of response and recovery seen from 1–2% H₂, caused by the α → β phase transition of PdH_x, a pronounced effect for nanowires at room temperature. The activation energies associated with sensor response and recovery are measured and interpreted.     

Kinetics-Driven Dual Hydrogen Spillover Effects for Ultrasensitive Hydrogen Sensing

Palladium (Pd)-modified metal oxide semiconductors (MOSs) gas sensors often exhibit unexpected hydrogen (H₂) sensing activity through a spillover effect. However, sluggish kinetics over a limited Pd-MOS surface seriously restrict the sensing process. Here, a hollow Pd-NiO/SnO₂ buffered nanocavity is engineered to kinetically drive the H₂ spillover over dual yolk-shell surface for the ultrasensitive H₂ sensing. This unique nanocavity is found and can induce more H₂ absorption and markedly improve kinetical H₂ ab/desorption rates. Meanwhile, the limited buffer-room allows the H₂ molecules to adequately spillover in the inside-layer surface and thus realize dual H₂ spillover effect. Ex situ XPS, in situ Raman, and density functional theory (DFT) analysis further confirm that the Pd species can effectively combine H₂ to form Pd-H bonds and then dissociate the hydrogen species to NiO/SnO₂ surface. The final Pd-NiO/SnO₂ sensors exhibit an ultrasensitive response (0.1–1000 ppm H₂) and low actual detection limit (100 ppb) at the operating temperature of 230 °C, which surpass that of most reported H₂ sensors.     

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis

Among the large family of transition metal dichalcogenides, recently ReS₂ has stood out due to its nearly layer‐independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in‐plane anisotropy, and the presence of active sites at its surface makes ReS₂ interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time‐consuming and complex, therefore limiting its large‐scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS₂ at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution‐based synthesis with surface functionalization strategies, the feasibility of colloidal ReS₂ nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD‐grown ReS₂ and MoS₂. In addition, the integration of the ReS₂ nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H₂ production in both acid and alkaline conditions. Results from proof‐of‐principle devices show an electrocatalytic overpotential competitive with devices based on ReS₂ produced by CVD, and even with MoS₂, WS₂, and MoSe₂ electrocatalysts.     

Palladium‐Decorated Silicon Nanomesh Fabricated by Nanosphere Lithography for High Performance,Room Temperature Hydrogen Sensing

A hydrogen (H₂) gas sensor based on a silicon (Si) nanomesh structure decorated with palladium (Pd) nanoparticles is fabricated via polystyrene nanosphere lithography and top‐down fabrication processes. The gas sensor shows dramatically improved H₂ gas sensitivity compared with an Si thin film sensor without nanopatterns. Furthermore, a buffered oxide etchant treatment of the Si nanomesh structure results in an additional performance improvement. The final sensor device shows fast H₂ response and high selectivity to H₂ gas among other gases. The sensing performance is stable and shows repeatable responses in both dry and high humidity ambient environments. The sensor also shows high stability without noticeable performance degradation after one month. This approach allows the facile fabrication of high performance H₂ sensors via a cost‐effective, complementary metal–oxide–semiconductor (CMOS) compatible, and scalable nanopatterning method.     

Shape‐Dependent Interactions of Palladium Nanocrystals with Hydrogen

Elucidation of the nature of hydrogen interactions with palladium nanoparticles is expected to play an important role in the development of new catalysts and hydrogen‐storage nanomaterials. A facile scaled‐up synthesis of uniformly sized single‐crystalline palladium nanoparticles with various shapes, including regular nanocubes, nanocubes with protruded edges, rhombic dodecahedra, and branched nanoparticles, all stabilized with a mesoporous silica shell is developed. Interaction of hydrogen with these nanoparticles is studied by using temperature‐programmed desorption technique and by performing density functional theory modeling. It is found that due to favorable arrangement of Pd atoms on their surface, rhombic dodecahedral palladium nanoparticles enclosed by {110} planes release a larger volume of hydrogen and have a lower desorption energy than palladium nanocubes and branched nanoparticles. These results underline the important role of {110} surfaces in palladium nanoparticles in their interaction with hydrogen. This work provides insight into the mechanism of catalysis of hydrogenation/dehydrogenation reactions by palladium nanoparticles with different shapes.     

过渡金属氧化物表面修饰氢气传感器

以SnO2系为敏感材料制备气敏元件,在元件的表面涂敷一层Fe2O3,MnO2或CuO掺杂的活性氧化铝修饰膜,有效地隔离并消除乙醇、烟雾、有机蒸气等杂散气体对元件的干扰.     

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy‐storage and conversion‐related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation‐resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano‐MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg₂NiH₄ single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas–solid reactions. This well‐defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas‐selective permeability to prevent further oxidation of Mg₂NiH₄ meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol^–1) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents.     

Two-dimensional Aluminum Oxide Nanosheets Decorated with Palladium Oxide Nanodots for Highly Stable and Selective Hydrogen Sensing

Hydrogen (H₂) sensing materials such as semiconductor metal oxides may suffer from poor long-term stability against humidity and unsatisfactory selectivity against other interfering gases. To address the above issues, highly stable and selective H₂ sensing built with palladium oxide nanodots decorating aluminum oxide nanosheets (PdO NDs//Al₂O₃ NSs) has been achieved via combined template synthesis, photochemical deposition, and oxidation. Typically, the PdO NDs//Al₂O₃ NSs are observed with thin NSs (≈17 nm thick) decorated with nanodots (≈3.3 nm in diameter). Beneficially, the sensor prototypes built with PdO NDs//Al₂O₃ NSs show excellent long-term stability for 278 days, high selectivity against interfering gases, and outstanding stability against humidity at 300 °C. Remarkably, the sensor prototypes enable detection of a wide-range of 20 ppm – 6 V/V% H₂, and the response and recovery times are ≈5 and 16 s to 1 V/V% H₂, respectively. Theoretically, the heterojunctions of PdO NDs-Al₂O₃ NSs with a large specific surface ratio and Al₂O₃ NSs as the support exhibit excellent stability and selective H₂ sensing. Practically, a sensing device integrated with the PdO NDs//Al₂O₃ NSs sensor prototype is simulated for detecting H₂ with reliable sensing response.     

硫化氢气体检测仪检定注意事项及常见故障处理

硫化氢气体检测仪作为检测环境中硫化氢气体含量的计量仪器,要保证其检测结果的准确可靠,以便能够及时发现硫化氢气体泄漏,有效预防人身伤害以及爆炸事故的发生,依法合规地开展硫化氢气体检测仪的检定和正确地使用维护非常重要。本文在总结大量日常检定工作经验的基础上介绍了硫化氢气体检测仪在检定过程中需要注意的细节问题,并且针对一些常见的故障及其产生的原因进行了分析,提出了具体的解决方法。     

Flexible and Transparent Gas Molecule Sensor Integrated with Sensing and Heating Graphene Layers

Graphene leading to high surface‐to‐volume ratio and outstanding conductivity is applied for gas molecule sensing with fully utilizing its unique transparent and flexible functionalities which cannot be expected from solid‐state gas sensors. In order to attain a fast response and rapid recovering time, the flexible sensors also require integrated flexible and transparent heaters. Here, large‐scale flexible and transparent gas molecule sensor devices, integrated with a graphene sensing channel and a graphene transparent heater for fast recovering operation, are demonstrated. This combined all‐graphene device structure enables an overall device optical transmittance that exceeds 90% and reliable sensing performance with a bending strain of less than 1.4%. In particular, it is possible to classify the fast (≈14 s) and slow (≈95 s) response due to sp²‐carbon bonding and disorders on graphene and the self‐integrated graphene heater leads to the rapid recovery (≈11 s) of a 2 cm × 2 cm sized sensor with reproducible sensing cycles, including full recovery steps without significant signal degradation under exposure to NO₂ gas.     

MOF-Derived In2O3/CuO p-n Heterojunction Photoanode Incorporating Graphene Nanoribbons for Solar Hydrogen Generation

Solar-driven photoelectrochemical (PEC) water splitting is a promising approach toward sustainable hydrogen (H₂) generation. However, the design and synthesis of efficient semiconductor photocatalysts via a facile method remains a significant challenge, especially p-n heterojunctions based on composite metal oxides. Herein, a MOF-on-MOF (metal-organic framework) template is employed as the precursor to synthesize In₂O₃/CuO p-n heterojunction composite. After incorporation of small amounts of graphene nanoribbons (GNRs), the optimized PEC devices exhibited a maximum current density of 1.51 mA cm⁻² (at 1.6 V vs RHE) under one sun illumination (AM 1.5G, 100 mW cm⁻²), which is approximately four times higher than that of the reference device based on only In₂O₃ photoanodes. The improvement in the performance of these hybrid anodes is attributed to the presence of a p-n heterojunction that enhances the separation efficiency of photogenerated electron-hole pairs and suppresses charge recombination, as well as the presence of GNRs that can increase the conductivity by offering better path for electron transport, thus reducing the charge transfer resistance. The proposed MOF-derived In₂O₃/CuO p-n heterojunction composite is used to demonstrate a high-performance PEC device for hydrogen generation.     

Sensor Selective Gas Analyzer for Small Concentrations of Hydrogen Sulfide

A sensor (based on a MDS-capacitor) gas analyzer for hydrogen sulfide concentration in the range 5–200 ppb at the level of the limiting permissible concentration for a health zone is suggested. The gas analyzer is selective with respect to hydrogen sulfide.     

低浓度氟化氢标准气体的FTIR分析方法研究

提出一种基于FTIR的氟化氢标准气体分析方法,使用其特征吸收区域(波数4100～4300cm-1)进行定量分析。通过稀释方法形成120、 100、 80.0、 60.0、 40.0、 20.0μmol/mol共6个浓度点的氟化氢标准气体,并对其重复性、标准曲线线性、检出限进行考察。结果显示：在20.0～120μmol/mol范围内仪器响应值与标气浓度呈线性,R2为0.9979; 各浓度点的重复性介于0.34%～1.1%之间; 检出限约为2.04μmol/mol。