rGO-SnO2纳米复合物制备及室温下NH3气敏性能

采用沉淀-焙烧法制备了室温下对NH3具有高灵敏度和高选择性的rGO-SnO2纳米复合材料。利用X射线衍射（XRD），傅里叶红外光谱（FTIR），X射线光电子能谱（XPS），扫描电子显微镜（SEM），透射电子显微镜（TEM）和比表面积（BET）表征分析了纯SnO2与rGO(1.0%)-SnO2纳米复合物的属性。与纯SnO2相比，rGO(1.0%)-SnO2纳米复合物中SnO2晶体尺寸较小，约为6~20nm，比表面积更大，为33m2/g；rGO(1.0%)-SnO2纳米复合材料对0.01% NH3的灵敏度达到了49.6%，是相同NH3浓度下纯SnO2灵敏度的2.1倍，并且响应和恢复时间分别为21s和204s，比纯SnO2缩短了24s和10s，具有良好的重复性，选择性与稳定性；rGO(1.0%)-SnO2纳米复合材料优良的气敏性能是由rGO与SnO2产生的p-n异质结以及溶解的NH3电离出导电离子共同作用的结果。     

High selectivity and response H2 sensors based on ZnO@ZIF-71@Ag nanorod arrays

Hydrogen (H₂) is widely used in industrial and medical, however its flammable and explosive nature requires economical and effective monitoring to ensure safety. In this work, ZnO@ZIF-71@Ag nanorod arrays were synthesized to provide an effective adsorption response to H₂ through size effect and high catalytic activity by immobilizing Ag nanoparticles (NPs) into the pores of ZIF-71. The results of the gas sensitivity tests showed that the nanorod arrays were significantly more selective towards H₂. Moreover, the response of ZnO@ZIF-71@Ag to 50 ppm H₂ was 11 times higher than that of ZnO@ZIF-71 at a lower operating temperature (150°C). The size of the Ag NPs was demonstrated to be below 10 nm by TEM characterization, suggesting that Ag in the form of quantum dots (QDs) to bring an unignorable catalytic effect for breaking hydrogen molecule (H₂) into highly active atoms ([H]). In addition, the result of Density Function Theory (DFT) calculation revealed that the adsorption energy of Ag-catalyzed [H] (−8.255 eV) was much higher than that of H₂ (−4.222 eV) on ZnO (100), which results in elevated charge transfer to promote hydrogen sensing performance of ZnO@ZIF-71@Ag. In this study, a novel hydrogen sensor based on pore sieving and catalytic sensing mechanisms was obtained, which provides a new reference for the development of hydrogen sensors.     

Additive Manufacturing-Enabled Architected Nanocomposite Lattices Coated with Plasmonic Nanoparticles for Water Pollutants Detection

Novel low-cost materials to uptake and detect vestigial amounts of pesticides are highly desirable for water quality monitoring. Herein, are demonstrated, for the first time, surface-enhanced Raman scattering (SERS) sensors enabled via additively manufactured lattices coated with plasmonic nanoparticles (NPs) for detecting pesticides in real water samples. The architected lattices comprising polypropylene (PP) and multiwall carbon nanotubes (MWCNTs) are realized via fused filament fabrication (FFF). In the first stage, the SERS performance of the PP/MWCNT filaments coated with distinct metallic NPs (Ag NPs and Au NPs) is evaluated using methylene blue (MB) as molecular probe. Thereafter, distinctly architected hybrid SERS sensors with periodic porous and fully dense geometries are investigated as adsorbents to uptake MB from aqueous solutions and subsequent detection using SERS. The spatial distribution of MB and Ag NPs on the FFF-printed lattices is accomplished by SERS imaging. The best hybrid composite is used as SERS probing system to detect low amounts of pesticides (thiram and paraquat) and offers a detection limit of 100 nm for both pesticides. As a proof-of-concept, FFF-enabled test strips are used to detect in loco paraquat molecules spiked on real water samples (Estuary Aveiro water and tap water) using a portable Raman spectrometer.     

Micro/nano-structured graphitic carbon nitride–Ag nanoparticle hybrids as surface-enhanced Raman scattering substrates with much improved long-term stability

Surface-enhanced Raman scattering (SERS) substrates with high SERS activity and stability are important for SERS sensors. A facile method was developed to fabricate efficient and stable SERS substrates by combining Ag nanoparticles (NPs) and micro-scale sheeted graphitic carbon nitride (g-C₃N₄). The g-C₃N₄/Ag NPs hybrid could provide a great number of hot spots and concentrated the analyte by the π–π stacking interaction between analyte molecules and g-C₃N₄, making a dramatic Raman enhancement. Moreover, the g-C₃N₄/Ag NPs hybrid uniformly immobilized Ag NPs on the surface and edges of g-C₃N₄ sheets by an interaction between Ag NPs and g-C₃N₄, leading to much improved long-term stability. This could be explained in terms of the electron–donor effect of g-C₃N₄, which was further confirmed by density functional theory calculations. The inherent Raman enhancing effect of g-C₃N₄ itself also contributed to the total SERS responses. Due to multiple enhancement contributions, the g-C₃N₄/Ag NPs hybrid exhibited a strong Raman enhancement effect for with an enhancement factor of 4.6 × 10⁸ (evaluated by using crystal violet as a probe), and possessed wide adaptability from dyes, pesticides to bio-molecules.     

The multiple synthesis of 2D layered Ti3C2Tx/Ag/MWCNTs/Ag composites with enhanced electrochemical properties

MXene, a novel two-dimensional material composed of alternating transition metal carbon/nitrogen, has the advantages of large specific surface area, many active sites, and short ion transport paths, and has shown great potential in the field of capacitors in the beginning. However, the unique two-dimensional structure is prone to collapse and accumulation, which inhibits the electron migration rate and ion penetration, resulting in poor energy storage capacity. In this paper, Ti₃C₂T_x/Ag/MWCNTs/Ag composites with good capacitive properties were successfully prepared by Ti₃C₂T_x which directly reduces silver nitrate solution and further introduces nanoscale MWCNTs. Ag NPs are introduced twice to grow and distribute uniformly on the surface and between the layers of Ti₃C₂T_x to play a supporting role. The introduction of MWCNTs in the intermediate process can enter the interlayer and act as spacers together with Ag NPs to prevent the collapse and stacking of Ti₃C₂T_x and improve its surface utilization. However, the preparation process unavoidably leads to partial oxidation of Ti₃C₂T_x, which deteriorates its electrochemical properties. Owing to the synergy between Ti₃C₂T_x, Ag NPs and MWCNTs, the Ti₃C₂T_x/Ag/MWCNTs/Ag composites show good electrical conductivity, low internal resistance (0.67 Ω) and extreme high capacitance contribution (97%) in electrochemical tests.     

Ultrafast hydrogen sensing through hybrids of semiconducting single-walled carbon nanotubes and tin oxide nanocrystals

We report an ultrafast and sensitive hydrogen (H(2)) sensing platform using semiconducting single-walled carbon nanotubes (SWCNTs) decorated with tin oxide (SnO(2)) nanocrystals (NCs). The hybrid SnO(2) NC-SWCNT platform shows a response time of 2-3 seconds to 1% H(2) under room temperature and can fully recover within a few minutes in air.     

Fabrication and properties of polysilsesquioxane-based trilayer core–shell structure latex coatings with fluorinated polyacrylate and silica nanocomposite as the shell layer

Polysilsesquioxanes (PSQ)-based core–shell fluorinated polyacrylate/silica hybrid latex coatings were synthesized with PSQ latex particles as the seeds, and methyl methacrylate, butyl acrylate, 3-(trimethoxysilyl) propyl methacrylate (MPS)-modified SiO₂ nanoparticles (NPs), 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) as the shell monomers by emulsifier-free miniemulsion polymerization. The results of Fourier transform IR spectroscopy, transmission electron microscopy, and dynamic light scattering suggested the obtained hybrid particles emerged with trilayer core–shell pattern. Contact angle analysis, x-ray photoelectron spectroscopy, and atom force microscopy results indicated that the hybrid film containing SiO₂ NPs showed higher hydrophobicity, lower surface free energy and water absorption, in comparison with the control system (without SiO₂ NPs). Compared with the control system, the hybrid latex film containing SiO₂ NPs in the fluorinated polyacrylate shell layer showed the higher content of fluorine atoms and a rougher morphology on the film surface. Additionally, thermogravimetric analysis demonstrated the enhanced thermostability of PSQ-based nanosilica composite fluorinated polyacrylate latex film.     

Functionalized multi‐wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor

Functionalized multi‐wall carbon nanotubes (MWCNTs) treated by mixed acids have been used to develop a capacitive humidity sensor based on MWCNTs/silicone rubber (SR) composite film. The MWCNTs/SR composites were prepared through conventional solution processed method. The micrographs of MWCNTs/SR composites were observed by transmission electron microscopy (TEM) and scanning electron microscope. The FT‐IR spectra demonstrated the successfully grafting of ? OH groups on the treated MWCNTs. The sensing properties of the composite at different relative humidity (RH) and frequency were characterized and linear sensing responses of the MWCNTs/SR composites to RH were observed. The treated MWCNTs/SR composite film (Tr‐film) had higher sensitivity than that of the untreated MWCNTs/SR composite film (Un‐film). Experimental data indicate that the Tr‐film exhibits an excellent long‐term stability, small hysteresis, and fine reproducibility. The response and recovery time of the Tr‐film were 30 and 27 s, respectively. Thereby, such Tr‐film had potential applications as humidity sensors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40342.     

Gas sensing properties of conducting polymer/Au-loaded ZnO nanoparticle composite materials at room temperature

In this work, a new poly (3-hexylthiophene):1.00 mol% Au-loaded zinc oxide nanoparticles (P3HT:Au/ZnO NPs) hybrid sensor is developed and systematically studied for ammonia sensing applications. The 1.00 mol% Au/ZnO NPs were synthesized by a one-step flame spray pyrolysis (FSP) process and mixed with P3HT at different mixing ratios (1:1, 2:1, 3:1, 4:1, and 1:2) before drop casting on an Al₂O₃ substrate with interdigitated gold electrodes to form thick film sensors. Particle characterizations by X-ray diffraction (XRD), nitrogen adsorption analysis, and high-resolution transmission electron microscopy (HR-TEM) showed highly crystalline ZnO nanoparticles (5 to 15 nm) loaded with ultrafine Au nanoparticles (1 to 2 nm). Film characterizations by XRD, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, and atomic force microscopy (AFM) revealed the presence of P3HT/ZnO mixed phases and porous nanoparticle structures in the composite thick film. The gas sensing properties of P3HT:1.00 mol% Au/ZnO NPs composite sensors were studied for reducing and oxidizing gases (NH₃, C₂H₅OH, CO, H₂S, NO₂, and H₂O) at room temperature. It was found that the composite film with 4:1 of P3HT:1.00 mol% Au/ZnO NPs exhibited the best NH₃ sensing performances with high response (approximately 32 to 1,000 ppm of NH₃), fast response time (4.2 s), and high selectivity at room temperature. Plausible mechanisms explaining the enhanced NH₃ response by composite films were discussed.     

Spin localization for NO adsorption on surface O atoms of metal oxides

The adsorption of NO on the oxygen site of several metal oxide surfaces is discussed. It is shown that the strength of the interaction and the variation of the bond lengths are not always correlated to the electron transfer from NO to the surface atoms. In cases of irreducible metal oxides, NO₂²⁻ may be strongly adsorbed. The formation of NO₂⁻ on reducible metal oxide is difficult unless terminal oxygen is present on the surface. Then, the reduction of the surface by transferring the unpaired electron from the NO to the surface appears in DFT calculations (VASP code).     

Raman, FTIR and Theoretical Evidence for Dynamic Structural Rearrangements of Vanadia/Titania DeNOx Catalysts

Insight into the selective catalytic reduction (SCR) of NO by NH₃ over vanadia/titania catalysts is obtained from a combination of Raman and FTIR spectroscopic investigations and density functional theory (DFT) calculations. Studies of the V–OH and V=O functional groups under different conditions coupled with calculations of the stability and mobility of H atoms provide evidence that dynamic structural rearrangements may occur during the SCR reaction. Hydrogen atoms are bonded more strongly to oxygen atoms that are coordinated to a single vanadium atom (V=O species), compared to bonding at oxygen atoms that are coordinated to multiple vanadium atoms (e.g., V–O–V species); and, activation energy barriers for hydrogen transfer from a V=O species to another V=O species and to a V–O–V species are estimated from DFT calculations to be 60 and 130 kJ/mol, respectively. This dynamic nature of hydrogen transfer between oxygen atoms having different coordination environments also appears to explain some of the spectroscopic changes observed for vanadia/titania catalysts having different vanadia loadings.     

High-Responsivity Heterojunction Photodetector Based on Bi2O3-Decorated MWCNTs Nanostructure Grown on Silicon via Laser Ablation in Liquid

We prepared a high-responsivity bismuth oxide Bi₂O₃ nanoparticles-decorated multiwalled carbon nanotubes MWCNTs/Si heterojunction photodetector by two-step laser ablation in liquid. The structural properties of the hybrid Bi₂O₃NPs-decorated MWCNTs were investigated by X-ray diffraction, which revealed the formation of α-Bi₂O₃ NPs with a monoclinic phase and graphite at the C(002) plane. Scanning electron microscopy results show the formation of spherical Bi₂O₃NPs attached to well-dispersed MWCNTs. The nanotubes' diameters ranged from 30 to 50 nm, their lengths from 1 to 3 m, and the average particle size of Bi₂O₃ NPs is 25 nm. The I–V characteristics for the Bi₂O₃NPs-decorated MWCNTs/Si photodetector were investigated in the dark and under illumination. The Bi₂O₃NPs-decorated MWCNTs/n-Si photodetectors show a responsivity of 1.37 A/W at a wavelength of 560 nm, with a corresponding external quantum efficiency of 3?×?10²%. At equilibrium, band alignment for Bi₂O₃-MWCNTs /Si heterojunction was realized.

     

A straightforward preparation and characterization of novel poly(vinyl alcohol)/organoclay/silver tricomponent nanocomposite films

In the present investigation, novel poly(vinyl alcohol)/organoclay/silver (PVA/OMMT/Ag) tricomponent nanocomposite (NC) films with different compositions were prepared by solution intercalation method under ultrasonic irradiation process. The NC films were obtained by mixing a colloidal solution consisting of Ag nanoparticles (NPs) (3, 5, 7 and 9 wt%) with a water solution of PVA and OMMT (10 wt%) via solution casting method. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis (TGA) were utilized to characterize the morphology and properties of the PVA/OMMT/Ag NC films. TGA confirmed that the heat stability of the nanocomposite was improved. The enhancement in the thermal properties of the hybrid materials was due to strong hydrogen bonding between OH groups of PVA, free acid functionalized groups of OMMT, and the Ag NPs. SEM and TEM results also showed that the OMMT and Ag NPs were dispersed homogeneously in the PVA matrix on nanoscale.     

聚噻吩/WO_3纳米复合材料的制备及气敏性能研究

采用化学氧化聚合法制备出了不同聚噻吩(PTh)掺杂量的PTh/WO3纳米复合材料进行制备,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)对PTh/WO3纳米复合材料的晶体结构和形貌进行了表征;并研究了PTh/WO3纳米复合材料制备的气敏元件对H2S气体气敏性能。结果表明:PTh/WO3纳米复合材料对H2S气体具有较高的灵敏度,用PTh质量分数为50%的复合材料制成的气敏元件在工作温度为60℃时,对500×10-6的H2S灵敏度达到98,且具有较快的响应与恢复时间。     

Polyethylene glycol-directed SnO2 nanowires for enhanced gas-sensing properties

SnO(2) nanowires with lengths in the tens of micrometres range have been synthesized on a large scale via a facile polyethylene glycol-directed method at ambient temperature followed by a suitable thermal treatment of the precursor nanowires. The morphology of the precursor of the SnO(2) nanowires is tunable by changing the concentration of either SnCl(2) or polyethylene glycol. After calcination, the resulting SnO(2) nanowires retain a similar shape to the precursor, but with hierarchical architecture, which can be considered as one-dimensional nanowires assembled by interconnected SnO(2) nanoparticles with a high surface-to-volume ratio. The SnO(2) nanowires are investigated with XRD, SEM, TEM, and gas sensing tests for detecting CO and H(2). It is found that the present SnO(2) nanowires exhibit a remarkable sensitivity and low detection limit (10 ppm for H(2)), as well as good reproducibility and short response/recovery times, which benefit from the unique hierarchical structure with a high surface-to-volume ratio and the 3D network formed by the nanowires.     

基于导电涂层微结构TPU柔性传感器的制备和性能

将具有表面微结构和平整的热塑性聚氨酯（TPU）传感基片封装成压阻型柔性压力传感器，其中前者（尺寸为10 mm×10 mm）的表面喷涂不同质量（0.02、0.05、0.1 g）的多壁碳纳米管（MWCNTs），并对微结构柔性传感基片表面形貌及传感器性能进行了表征和分析。结果表明，微结构传感基片表面上微柱顶面形成一定厚度的MWCNTs层，层内MWCNTs形成网络；喷涂较高MWCNTs质量时，传感器具有较高的灵敏度和较低的检测限，这归因于压力所致MWCNTs的网络搭接程度和传感基片间接触面积的增加量较大；喷涂0.1 g MWCNTs时，传感器的灵敏度为0.143 kPa^-1（0~3 kPa），检测限低至100 Pa，在较宽压力范围内（3~200 kPa）仍有一定的压阻响应，能在4 000次的循环压缩/释放测试（峰值压力约200 kPa）中保持稳定的压阻响应，且可准确检测典型人体运动所产生的压阻响应，具有应用于智能穿戴领域的潜能。     

Fabrication of bimetallic nanoparticles/multi-walled carbon nanotubes composites for microelectronic circuits

A method for the fabrication of electrically-conducting polymer composites has been developed by mixing modified multi-walled carbon nanotubes (MWCNTs) functionalized by bimetallic nanoparticles (Ag/Ni/MWCNTs) into a UV curable resin. MWCNTs were treated by a concentrated H₂SO₄/HNO₃ mixture followed by ultrasonication with AgNO₃ and NiSO₄ in an ethylene glycol solution, producing MWCNTs decorated with Ag and Ni nanoparticles. The microstructure and surface morphology of the Ag/Ni/MWCNTs were investigated by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectrometry. It was found that the addition sequences of NiSO₄ and AgNO₃ influence the morphology of the Ag/Ni/MWCNTs. The electrically-conducting polymer composites were obtained by dispersing the prefabricated Ag/Ni/MWCNTs in UV curable resin, the curing process of which was tracked by Fourier transform infrared spectroscopy, and the electrical resistance was measured using the four-probe method. The fabrication of microelectronic patterns made by screen printing on different substrates was described.     

Cu掺杂SnO_2纳米粉体的制备及气敏特性

控制不同n(Cu2+)/n(Sn4+),用均匀共沉淀法制备了平均粒径约80 nm的金红石型结构Cu掺杂SnO2纳米粉体;并以白云母为基片制备出Cu掺杂SnO2气敏元件。用TG-DSC、XRD、SEM对样品的相变、结构、形貌进行了分析,并测试了气敏元件的阻温特性和75℃氢气敏感性能。结果表明,Cu掺杂抑制了SnO2晶核的生长,使SnO2结晶度由约75%减小到50%,晶粒尺寸由约18 nm减小到6 nm;Cu掺杂使n型半导体SnO2的空气电阻值由1~8 kΩ提高到9×105~3×107MΩ,并使元件在75℃对体积分数为2 000×10-6氢气的灵敏度提高约20倍;n(Cu2+)/n(Sn4+)≈0.01时,元件对体积分数为4 000×10-6氢气的灵敏度高达约42。     

多壁碳纳米管的改性及其复合材料的制备

用H2SO4/HNO3（体积比3∶1）对碳纳米管进行改性,结果研究表明：与原始碳纳米管相比,改性后的多壁碳纳米管的自身的分散性非常好,表面带有了更多的-OH和-COOH等官能团,碳纳米管在空气中的热稳定性明显下降,而且在碳酸氢铵与氨水和少量SDBS的混合溶液中分散稳定性更好。然后采用原位聚合的方法制备了多壁碳纳米管/碳酸铝铵复合材料,复合粉体的TEM和XRD表明改性后的多壁碳纳米管可以在碳酸铝铵粉体中进行良好的分散。     

Revealing charge-transfer effects in gas-phase water chemistry

An understanding of the interactions involving water and other small hydrogenated molecules such as H(2)S and NH(3) at the molecular level is an important and elusive scientific goal with potential implications for fields ranging from biochemistry to astrochemistry. One longstanding question about water's intermolecular interactions, and notably hydrogen bonding, is the extent and importance of charge transfer (CT) , which can have important implications for the development of reliable model potentials for water chemistry, among other applications. The weakly bound adducts, commonly regarded as pure van der Waals systems, formed by H(2)O, H(2)S, and NH(3) with noble gases or simple molecules such as H(2), provide an interesting case study for these interactions. Their binding energies are approximately 1 or 2 kJ/mol at most, and CT effects in these systems are thought to be negligible. Our laboratory has performed high-resolution molecular-beam scattering experiments that probe the (absolute scale) intermolecular potential of various types of these gas-phase binary complexes with extreme sensitivity. These experiments have yielded surprising and intriguing quantitative results. The key experimental measurable is the "glory" quantum interference shift that shows a systematic, anomalous energy stabilization for the water complexes and clearly points to a significant role for CT effects. To investigate these findings, we have performed very accurate theoretical calculations and devised a simple approach to study the electron displacement that accompanies gas-phase binary intermolecular interactions in extreme detail. These calculations are based on a partial progressive integration of the electron density changes. The results unambiguously show that water's intermolecular interactions are not typical van der Waals complexes. Instead, these interactions possess a definite, strongly stereospecific CT component, even when very weak, where a water molecule may act as electron donor or acceptor depending on its orientation. CT is mediated by an asymmetric role played by the two hydrogen atoms, which causes strong orientation effects. The careful comparison of these calculations with the experimental results shows that the stabilization energy associated to CT is approximately 2-3 eV per electron transferred and may make up for a large portion of the total interaction energy. A simple electron delocalization model helps to validate and explain these findings.