Review on recent progress in on-line monitoring technology for atmospheric pollution source emissions in China.

Emissions from mobile sources and stationary sources contribute to atmospheric pollution in China, and its components, which include ultrafine particles (UFPs), volatile organic compounds (VOCs), and other reactive gases, such as NH3 and NOx, are the most harmful to human health. China has released various regulations and standards to address pollution from mobile and stationary sources. Thus, it is urgent to develop online monitoring technology for atmospheric pollution source emissions. This study provides an overview of the main progress in mobile and stationary source monitoring technology in China and describes the comprehensive application of some typical instruments in vital areas in recent years. These instruments have been applied to monitor emissions from motor vehicles, ships, airports, the chemical industry, and electric power generation. Not only has the level of atmospheric environment monitoring technology and equipment been improving, but relevant regulations and standards have also been constantly updated. Meanwhile, the developed instruments can provide scientific assistance for the successful implementation of regulations. According to the potential problem areas in atmospheric pollution in China, some research hotspots and future trends of atmospheric online monitoring technology are summarized. Furthermore, more advanced atmospheric online monitoring technology will contribute to a comprehensive understanding of atmospheric pollution and improve environmental monitoring capacity.

The Dehydrogenation of H-S Bond into Sulfur Species on Supported Pd Single Atoms Allows Highly Selective and Sensitive Hydrogen Sulfide Detection.

The supported metal catalysts on scaffolds usually reveal multiple active sites, resulting in the occurrence of side reaction and being detrimental to the achievement of highly consistent catalysis. Single atom catalysts (SACs), possessed with highly consistent single active sites, have great potentials for overcoming such issues. Herein, the authors used SACs to modulate kinetic process of gas sensitive reaction. The supported Pd SACs, established by a metal organic frameworks-templated approach, promoted greatly the detection capacity to hydrogen sulfide (H2 S) gas with a very high sensitivity and selectivity. Density functional theory calculations show that the supported Pd SACs not only increased the number of electrons transferring from H2 S molecules to Pd SACs, but strengthened surface affinity to H2 S. Moreover, the HS bonds of H2 S molecules absorbed on Pd atomic sites are more likely to be dehydrogenated directly into sulfur species. Significantly, quasi in situ XPS analysis confirmed the presence of sulfur species during H2 S detection process, which may be a major cause for such detection signal. Based on these results, a suitable sensing principle for H2 S gas driven by Pd SACs was put forward. This work will enrich catalytic electronics in chemiresistive gas sensing.

Improved SERS activity of non-stoichiometric copper sulfide nanostructures related to charge-transfer resonance.

The low enhancement factor of semiconductor SERS substrates is a major obstacle for their practical application. Therefore, there is a need to explore the facile synthesis of new SERS substrates and reveal the SERS enhancement mechanism. Here, we develop a simple, facile and low-cost two-step method to synthesize copper sulfide based nanostructures with different Cu7.2S4 contents. The as-synthesized sample is composed of nanosheets with the CuS phase structure. With the increase of the annealing temperature to 300 °C, the CuS content gradually decreases and disappears, and the content of Cu7.2S4 and CuSO4 appears and gradually increases. At the annealing temperature of 350 °C, only CuSO4 exists. Compared with pure CuS or pure CuSO4, the detection limit of R6G molecules is the lowest for the composite sample with a higher content of Cu7.2S4, indicating that the introduction of non-stoichiometric Cu7.2S4 can improve the SERS performance and the higher content of Cu7.2S4 leads to a higher SERS activity. Furthermore, to investigate the SERS mechanism, the energy band structures and energy-level diagrams of different probe molecules over CuS, Cu7.2S4 and CuxS are studied by DFT calculations. Theoretical calculations indicate that the excellent SERS behavior depends on charge transfer resonance. Our work provides a general approach for the construction of excellent metal compound semiconductor SERS active substrates.

Physical deposition improved SERS stability of morphology controlled periodic micro/nanostructured arrays based on colloidal templates.

An effective and inexpensive method is developed to fabricate periodic arrays by sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. By a colloidal template induced precursor solution dipping strategy, different periodic arrays of semi-hollow sphere array, inverse opal with monolayer pore arrays and hole arrays are obtained under different conditions. After magnetron sputtering deposition, their morphologies are changed to novel micro/nanostructured arrays of honeycomb-shaped arrays, hollow cavity arrays, and regular network arrays due to multiple direction deposition of sputtering deposition and shadow effect. After coating a gold thin layer, these periodic micro/nanostructured arrays are used as SERS active substrates and demonstrate a very stable SERS performance compared with periodic arrays achieved by direct colloidal template-induced chemical deposition. Additionally, a honeycomb-shaped array displays better SERS enhancement than that of a hollow cavity array or a regular network array. After optimization of honeycomb-shaped arrays with different periodicities, an array with periodicity of 350 nm demonstrates much stronger SERS enhancement and possesses a low detection limit of 10(-11) M R6G. Such stable SERS performance is useful for practical application in portable Raman detecting devices to detect organic molecules.

Gold binary-structured arrays based on monolayer colloidal crystals and their optical properties.

A simple and flexible route is presented to fabricate a gold binary-structured ordered array by one step based on non-shadow deposition on a plasma etching-induced dualistic monolayer colloidal crystal. Such a Au binary-structure array is built of hexagonally arranged nanoshells and nanorings which stand between two adjacent nanoshells. Six gold nanorings surround each nanoshell. The obtained arrays exhibit both the controllable surface-plasmon-resonance (SPR) properties of Au nanoshells and the strong electromagnetic-field-enhancement effects of Au nanorings, with the high structural stability of ordered arrays, and show promising potential as the substrate of surface-enhanced Raman scattering (SERS)-based devices. The method could also be suitable for fabrication of other material binary-structured arrays. This study is important in designing and fabricating basal materials for the next generation of multifunctional nanostructured devices.

CuO-ZnO micro/nanoporous array-film-based chemosensors: new sensing properties to H2S.

CuO-ZnO micro/nanoporous array-films are synthesized by transferring a solution-dipped self-organized colloidal template onto a device substrate and sequent heat treatment. Their morphologies and structures are characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectrum analysis. Based on the sensing measurement, it is found that the CuO-ZnO films prepared with the composition of [Cu(2+)]/[Zn(2+)]=0.005, 0.01, and 0.05 all show a nice sensitivity to 10 ppm H2S. Interestingly, three different zones exist in the patterns of gas responses versus H2S concentrations: a platform zone, a rapidly increasing zone, and a slowly increasing zone. Further experiments show that the hybrid CuO-ZnO porous film sensor exhibits shorter recovery time and better selectivity to H2S gas against other interfering gases at a concentration of 10 ppm. These new sensing properties may be due to a depletion layer induced by p-n junction between p-type CuO and n-type ZnO and high chemical activity of CuO to H2S. This work will provide a new construction route of ZnO-based sensing materials, which can be used as H2S sensors with high performances.

Physical processes-aided periodic micro/nanostructured arrays by colloidal template technique: fabrication and applications.

It has been proven that the use of colloidal templates is a facile, flexible strategy to create the periodic micro/nanostructured arrays in comparison with photolithography, electron beam lithography etc. Utilizing colloidal monolayers as templates or masks, different periodic micro/nanostructured arrays including nanoparticle arrays, pore arrays, nanoring arrays and nanorod/nanotube arrays can be fabricated by chemical and physical processes. Chemical routes, including direct solution/sol dipping strategy, wet chemical etching, electrodeposition, electrophoretic deposition etc. have advantages of simple operation and low costs. However, they have some disadvantages of impurities on surface of arrays due to incomplete decomposition of precursors, residue of surfactants in self-assembling or electrochemical deposition. More importantly, it is quite difficult to achieve very uniform morphology of micro/nanostructure arrays on a large-area by the above routes. Whereas another method, a physical route (for instance: reactive ion etching, pulsed laser deposition, thermal evaporation deposition, atomic layer deposition, sputtering deposition), combining with colloidal monolayer template can well resolve these problems. In this review, we focus on introducing the recent progress in creating micro/nanostructured arrays based on colloidal templates with physical routes. The parameters of the microstructure or nanostructure can be tuned by colloidal templates with different periodicity and experimental conditions of the physical processes. The applications of micro/nanostructured arrays with controllable morphology and arrangement parameters in self-cleaning surfaces, enhanced catalytic properties, field emitters etc. are also presented in the following sections.

Crack-free periodic porous thin films assisted by plasma irradiation at low temperature and their enhanced gas-sensing performance.

Homogenous thin films are preferable for high-performance gas sensors because of their remarkable reproducibility and long-term stability. In this work, a low-temperature fabrication route is presented to prepare crack-free and homogenous metal oxide periodic porous thin films by oxygen plasma irradiation instead of high temperature annealing by using a sacrificial colloidal template. Rutile SnO2 is taken as an example to demonstrate the validity of this route. The crack-free and homogenous porous thin films are successfully synthesized on the substrates in situ with electrodes. The SnO2 porous thin film obtained by plasma irradiation is rich in surface OH groups and hence superhydrophilic. It exhibits a more homogenous structure and lower resistance than porous films generated by annealing. More importantly, such thin films display higher sensitivity, a lower detection threshold (100 ppb to acetone) and better durability than those that have been directly annealed, resulting in enhanced gas-sensing performance. The presented method could be applied to synthesize other metal oxide homogenous thin films and to fabricate gas-sensing devices with high performances.

An invisible template method toward gold regular arrays of nanoflowers by electrodeposition.

A new approach, an invisible template method that is realized through controlling the interface electroconductivity of an electrode surface, is presented to synthesize gold regular arrays of nanoflowers with variable separations through further electrochemical deposition. Using polystyrene monolayer colloidal crystals as the first template, a hexagonally packed 1-hexadecanethiol pattern was self-assembled and used as an invisible template to control the interface electroconductivity. Further electrochemical deposition under appropriate conditions can easily lead to gold regular arrays of nanoflowers. This new approach demonstrates a simple route to the fabrication of novel gold micro/nanostructured arrays that may find applications as SERS active substrates, superhydrophobic materials, and so forth.

Wafer-Level Manufacturing of MEMS H2 Sensing Chips Based on Pd Nanoparticles Modified SnO2 Film Patterns.

In this manuscript, a simple method combining atomic layer deposition and magnetron sputtering is developed to fabricate high-performance Pd/SnO2 film patterns applied for micro-electro-mechanical systems (MEMS) H2 sensing chips. SnO2 film is first accurately deposited in the central areas of MEMS micro hotplate arrays by a mask-assistant method, leading the patterns with wafer-level high consistency in thickness. The grain size and density of Pd nanoparticles modified on the surface of the SnO2 film are further regulated to obtain an optimized sensing performance. The resulting MEMS H2 sensing chips show a wide detection range from 0.5 to 500 ppm, high resolution, and good repeatability. Based on the experiments and density functional theory calculations, a sensing enhancement mechanism is also proposed: a certain amount of Pd nanoparticles modified on the SnO2 surface could bring stronger H2 adsorption followed by dissociation, diffusion, and reaction with surface adsorbed oxygen species. Obviously, the method provided here is quite simple and effective for the manufacturing of MEMS H2 sensing chips with high consistency and optimized performance, which may also find broad applications in other MEMS chip technologies.

High-performance field-effect transistor glucose biosensors based on bimetallic Ni/Cu metal-organic frameworks.

Accurate detection of glucose is essential for the diagnosis of diabetes, wherein effective and sensitive biosensors for glucose detection are needed. Here, we fabricated a glucose sensor based on field-effect transistor (FET) with bimetallic nickel-copper metal-organic frameworks (Ni/Cu-MOFs) as its channel layers which were grown in-situ through a simple one-step hydrothermal method and modified with glucose oxidase (GOD) by using glutaraldehyde (GA) as linkers. Due to the synergistic effect of Ni ions and Cu ions in MOFs, the sensor (GOD-GA-Ni/Cu-MOFs-FET) showed good field effect performance and great responses to glucose through enzymatic reactions. It displayed a piecewise linear relationship in the wide range (1 µM-20 mM), and provided high sensitivity (26.05 µAcm-2mM-1) in the low concentration (1-100 µM) and a low detection limit (0.51 µM). The sensor also had these advantages of high specificity, excellent reproducibility, good short-term stability and fast response time. Especially, it is indicated that the Ni/Cu-MOFs-FETs with high performance have the potential to be available sensors, paving the way for the application of bimetallic MOFs in biosensing.

General synthesis of 2D ordered hollow sphere arrays based on nonshadow deposition dominated colloidal lithography.

A general strategy, nonshadow deposition dominated colloidal lithography (NSCL), was proposed for the synthesis of two-dimensional (2D) ordered hollow sphere arrays of conductive materials. Gold, polypyrrole, CdS, and ZnO were taken as model materials to demonstrate the NSCL strategy, and built as 2D hollow sphere arrays successfully. In this strategy, a thin gold coating is first introduced on a polystyrene sphere (PS) colloidal monolayer via ion-sputtering deposition, and a hollow sphere array can thus be obtained by further electrochemical deposition on such a monolayer and by subsequent removal of PSs. The proposed strategy is flexible and facile to control the microstructure and size of the hollow sphere array, and the features are as follows: (i) controllable shell of the hollow sphere from single-layer to multilayer with single or multiple compositions, (ii) tunable morphology from simple structure to hierarchical micro/nanostructure, and (iii) changeable arrangement of hollow spheres from close-packing to non-close-packing. Besides these, the hollow sphere size and the shell thickness can also be controlled by changing the colloidal sphere and deposition time, respectively. Further investigation indicates that the success of NSCL should be owed to a key step, that is, an ion-sputtering induced nonshadow deposition surrounding the whole surfaces of colloidal spheres. This allows an equipotential face and thus homogeneous deposition surrounding the surfaces of PSs in an electrochemical deposition process, and final formation of hollow sphere structure. The 2D ordered hollow sphere arrays with controllable microstructure and size could exhibit importance both in fundamental research and in practical applications.

Au-Decorated ZnFe2O4 Yolk-Shell Spheres for Trace Sensing of Chlorobenzene.

Noble metals supported on metal oxides are promising materials for widely applying on gas sensors because of their enviable physical and chemical properties in enhancing the sensitivity and selectivity. Herein, pristine ZFO yolk-shell spheres composed of ultrathin nanosheets and ultrasmall nanoparticles decorated with nanosized Au particles with a diameter of 1-2 nm are fabricated using the method of solution-phase deposition-precipitation. As a result, the Au@ZFO yolk-shell sphere based sensor exhibits significantly sensing performances for chlorobenzene (CB). In comparison with pristine ZFO, the response (Rair/Rgas= 90.9) of a Au@ZFO based sensor with a low detection limit of 100 ppb increases 4-fold when exposed to 10 ppm chlorobezene at 150 °C. Excitingly, the sensing response for chlorobenzene is the highest among metal oxides semiconductor based sensors. Moreover, the sensors can be further applied in the field of chlorobenzene monitoring, owing to its outstanding selectivity. The results elaborated that the enhanced sensing mechanism is mainly attributed to the effects of electronic sensitization and chemical sensitization, which are induced by the Au nanoparticles on the surface of ZFO yolk-shell spheres. Density functional theory (DFT) calculations further illustrated that the existence of Au nanoparticles exhibits higher adsorption energy and net charge transfer for CB. In addition, the relationship between the sensing performances of pristine ZFO and Au@ZFO yolk-shell spheres for chlorobenzene and the factors of Au loading amount, operating temperature, and humidity was also fully investigated in this work.

Morphology dependent magnetic properties of two-dimensional alpha-Fe2O3 ordered nanostructured arrays.

Magnetic properties of two-dimensional alpha-Fe2O3 ordered bowl-like pore and ring arrays, fabricated by solution-dipping on a colloidal monolayer, were studied. All the alpha-Fe2O3 nanostructured arrays exhibit weak ferromagnetic properties at room temperature, while the hysteresis loops strongly depend on the morphology of the arrays. Some novel magnetic properties, such as plateau regions and jumps in hysteresis loops, have been observed for the ring and bowl-like pore arrays at room temperature, respectively. The morphology-dependent magnetic properties will exhibit the potential applications in nanodevices, such as giant magnetoresistance spin-valve devices and magnetic data storage.

Self-Assembly of Cu2O Monolayer Colloidal Particle Film Allows the Fabrication of CuO Sensor with Superselectivity for Hydrogen Sulfide.

CuO monolayer colloidal particle films with controllable thickness and homogeneous microstructure were prepared by self-assembly and subsequent calcination based on Cu2O colloidal particles. Large-scale CuO monolayer colloidal particle films have the particle size of 300-500 nm, and CuO colloidal particles are hollow. It was found that such a structure exhibits excellent room-temperature H2S-gas-sensing properties. It not only has high sensing response and excellent selectivity, but also has a low limit of detection of 100 ppb. The sensors exhibit different sensitive characteristics at low and high concentrations of H2S. At low concentration (100-500 ppb), the sensor can be recovered with the increase of gas response, although it takes a longer recovery time at room temperature. At medium concentration (1-100 ppm), although the gas response still increases, the sensor is irreversible at room temperature. When the concentration continues to increase (>100 ppm), the sensor is irreversible at room temperature, and the gas response first increases and then decreases. Two reaction mechanisms are proposed to explain the above-mentioned sensing behavior. More importantly, quasi in situ X-ray photoelectron spectra confirm the existence of CuS. The CuO sensor with room-temperature response and superselectivity will find potential applications in industry, environment, or intelligent electronics.

Facile Synthesis of the Composites of Polyaniline and TiO2 Nanoparticles Using Self-Assembly Method and Their Application in Gas Sensing.

The composites of polyaniline and TiO2 nanoparticles with different contents were prepared in the aqueous solution of phosphoric acid, in which the phosphoric acid was selected as the protonic acid to improve the conductivity of polyaniline. In the composites, the TiO2 nanoparticles with the size of about 20 nm were coated by a layer of polyaniline film with a thickness of about 5 nm. Then, the gas sensors were constructed by a liquid⁻gas interfacial self-assembly method. The gas-sensing properties of the composites-based gas sensors obviously improved after doping with TiO2 nanoparticles, and the sensor response of the composites increased several times to NH3 from 10 ppm to 50 ppm than that of pure polyaniline. Especially when the mass ratio of TiO2 to aniline monomer was 2, it exhibited the best gas response (about 11.2⁻50 ppm NH3), repeatability and good selectivity to NH3 at room temperature. The p⁻n junction structure consisting of the polyaniline and TiO2 nanoparticles played an important role in improving gas-sensing properties. This paper will provide a method to improve the gas-sensing properties of polyaniline and optimum doping proportion of TiO2 nanoparticles.

Field-Effect Transistor Based on an in Situ Grown Metal-Organic Framework Film as a Liquid-Gated Sensing Device.

Ni3(HITP)2, a novel and promising two-dimensional metal-organic framework (MOF) material, has been utilized in the areas of catalysis, sensing, and supercapacitors. It is very suitable for preparing field-effect transistor (FET) devices due to its good conductivity, porous structure, as well as easy film formation. Nevertheless, there is a challenge to transfer membrane materials undamaged to the substrates. Here, we reported a simple approach to fabricate the Ni-MOF-based FET with an in situ grown Ni3(HITP)2 membrane as the channel material of the FET. With this method, we obtained a large-area, dense, and uniform film composed of thin sheets, and the thickness and density of the MOF film were tunable through changing the reaction time. The as-prepared Ni-MOF-FET had a good mobility of 45.4 cm2 V-1 s-1 and on/off current ratio of 2.29 × 103. Moreover, this FET served as a liquid-gated device for the first time with bipolar behavior and good response to the gluconic acid at the range from 10-6 to 10-3 g/mL, verifying the potential of the Ni-MOF-FET as biosensors.

Pd-Catalyzed Reaction-Producing Intermediate S on a Pd/In2O3 Surface: A Key To Achieve the Enhanced CS2-Sensing Performances.

Although chemiresistive gas sensors, based on metal-oxide semiconductors, have exhibited particular promise for the monitoring of air pollution, they are often limited because of poor selectivity. In that case, to overcome this issue, according to the essence of the gas-sensing process, the method of reforming the surface reaction path on the surface of the sensing materials was used. Here, we report that Pd nanoparticles supported over the In2O3 composites, featured with a yolk-shell structure, enable the trace detection of carbon disulfide (CS2) gas molecules, which are immensely dangerous to humans and animals. Moreover, the prominent enhancement of the gas response and the ultraselective CS2-sensing characteristic were acquired in comparison with pristine In2O3 sensors. Significantly, density functional theory calculations revealed that the Pd supported on In2O3 greatly facilitates the adsorption capacity to CS2, and the intermediate S, produced by Pd-catalyzed desulfurization reaction, on the Pd/In2O3 surface during the sensing process is a key to achieving a high CS2 gas response as well as ultraselectivity, which is well in agreement with the X-ray photoelectron spectroscopy analysis results. On the basis of these results, a new sensing mechanism model for the CS2-sensing process was put forward.

The Fabrication of Au@C Core/Shell Nanoparticles by Laser Ablation in Solutions and Their Enhancements to a Gas Sensor.

A convenient and flexible route is presented to fabricate gold noble metal nanoparticles wrapped with a controllable ultrathin carbon layer (Au@C) in one step based on laser ablation of the noble metal targets in toluene-ethanol mixed solutions. The obtained metal nanoparticles were <20 nm in size after ablation, and the thickness of the wrapped ultrathin carbon layer was 2 nm in a typical reaction. The size of the inner noble metal nanoparticles could be controlled by adjusting the power of laser ablation, and the thickness of the ultrathin carbon layer can be controlled from 0.6 to 2 nm by laser ablation in different components of organic solution. Then the resultant Au@C core/shell nanoparticles were modified on the surface of In2O3 films through a sol-gel technique, and the hydrogen sulfide (H2S) gas-sensing characteristics of the products were examined. Compared to pure and Au-modified In2O3, the Au@C-modified In2O3 materials exhibited a revertible and reproducible performance with good sensitivity and very low response times (few seconds) for H2S gas with a concentrations of 1 to 5 ppm at room temperature. Evidence proved that the ultrathin carbon layer played an important role in the improved H2S sensor performance. Other noble metals wrapped by the homogeneous carbon shell, such as Ag@C, could also be prepared with this method.

Ultrafine Pt NPs-Decorated SnO2/α-Fe2O3 Hollow Nanospheres with Highly Enhanced Sensing Performances for Styrene.

Styrene, a chronic toxic gas, is of great harm to human health. It is urgently required to develop a portable, efficient, and inexpensive method to detect this toxic gas. Chemiresistive gas sensor based on semiconductor metal-oxides is considered as one of the best candidate suited to above features, while its sensitivity and selectivity are not enough high for the applications. Herein, the ultrafine Pt NPs embellished SnO2/α-Fe2O3 hollow nanoheterojunctions were achieved by in-situ reduction and subsequent calcination treatment. Particularly, such yielding products exhibited excellent styrene sensing performances with a detection limit of 50 ppb and extremely fast response/recovery time (3/15 s, respectively). More importantly, this SnO2/α-Fe2O3/Pt sensing platform revealed improved styrene selectivity against other malodorous gases. Additionally, the significant enhancement for styrene sensing response was also obtained compared to other two sensors (pristine SnO2 and SnO2/α-Fe2O3, respectively). Further studies demonstrated that such enhanced performances possibly be owing to the "catalytic sensitization" effect driven by Pt NPs and "electronic sensitization" effect triggered through the formation of Schottky junction as well as n-n nanoheterojunction. Based on these sensing features, it is probably great promising in the detection of styrene gas in the future.