Light-assisted room temperature gas sensing performance and mechanism of direct Z-scheme MoS2/SnO2 crystal faceted heterojunctions.

Light assistance and construction of heterojunctions are both promising means to improve the room temperature gas sensing performance of MoS2 recently. However, enhancing the separation efficiency of photo-generated carriers at interface and adsorption ability of surface have become the bottleneck problem to further improve the room temperature gas sensing performance of MoS2-based heterojunctions under light assistance. In the present study, a novel direct Z-scheme MoS2/SnO2 heterojunction was designed through crystal facets engineering and its room temperature gas sensing properties under light assistance was studied. It was found that the heterojunction showed outstanding room temperature NO2 sensing performance with a high response of 208.66 toward 10 ppm NO2, together with excellent recovery characteristics and selectivity. The gas sensing mechanism study suggested that high-energy {221} crystal facets of SnO2 and MoS2 directly formed Z-scheme heterojunction, which could greatly improve the separation efficiency of photo-generated carriers with high redox capacity. Moreover, {221} facets greatly enhanced adsorption ability towards NO2. This work not only opens up the application of Z-scheme heterojunctions in gas sensing, which will greatly promotes the development of room temperature light-assisted gas sensors, but also provides a new idea for the construction of direct Z-scheme heterojunctions through crystal facets engineering.

Highly Mesoporous Cobalt-Hybridized 2D Cu3P Nanosheet Arrays as Boosting Janus Electrocatalysts for Water Splitting.

Recently, developing economical electrocatalysts with high performance in water decomposition has become a research hotspot. Herein, two kinds of cobalt-hybridized Cu3P nanostructure array electrocatalysts (including highly mesoporous 2D nanosheets and sugar gourd-like 1D nanowires) were controllably grown on a nickel foam substrate through a simple hydrothermal method combined with a subsequent phosphating treatment method. An electrocatalytic test indicated that the as-prepared 2D nanosheet array exhibited excellent activity and stability toward hydrogen evolution reaction under alkaline conditions, which offered a low overpotential of 99 mV at 10 mA/cm2 and a small Tafel slope of 70.4 mV/dec, whereas a competitive overpotential of 272 mV was required for oxygen evolution reaction. In addition, the 2D nanosheet array delivered a low cell voltage of 1.66 V at 10 mA/cm2 in a symmetric two-electrode system, implying its huge potential in overall water decomposition. The electrocatalytic performance is superior to the as-prepared 1D nanowire array and most of the Cu3P-related electrocatalysts previously reported. Experimental measurements and first-principles calculations show that the excellent performance of the 2D nanosheet array can be attributed to its unique 2D mesoporous structure and hybridization of cobalt, which not only provide a large electrochemically active surface and fast electrocatalytic reaction kinetics but also weaken the binding strength of electrocatalytic reaction intermediates. The present study provides a simple and controllable approach to synthesize Cu3P-based bimetallic phosphide nanostructures, which can be used as boosting Janus electrocatalysts for water decomposition.

Tunable resistance of MOFs films via an anion exchange strategy for advanced gas sensing.

Because of their ultra-high surface area, large porosity and excellent structural tailorability, metal-organic frameworks (MOFs) are considered as outstanding candidates among sensing materials for hazardous gas detection. However, most of MOFs-based sensing films show weak film adhesion and low conductivity due to the poor formation ability of MOFs films by traditional sensor fabrication methods as well as the intrinsic insulating character of these MOFs. In this work, we propose a novel strategy to directly grow robust gas-sensing films based on pristine MOFs arrays (ZIF-67 nanosheets) in-situ on the surface of ceramic substrates. To improve the conductivity of MOFs arrays, anion-exchange method is applied to couple Prussian blue analogue (PBA) on the surface of ZIF-67 arrays. Structural characterization revealed that this permutation reaction can significantly improve the conductivity of the MOF films while their sheet-like structures can be mainly remained. Benefiting from the robust structure and improved conductivity, the as-designed ZIF-67/PBA films exhibited superior sensing performances such as good reproducibility, high response value (Rg/Ra=11.7), and fast response/recovery speed (5/182 s) towards triethylamine. This work provides a new strategy to fabricate MOFs gas sensors and paves a new way to modulate the conductivity of MOF films.

Crystal facets engineering and rGO hybridizing for synergistic enhancement of photocatalytic activity of nickel disulfide.

Crystal facets engineering and graphene hybridizing have been proved to be effective means to improve the photocatalytic activities of semiconductor photocatalysts in recent years. However, most of these efforts are concentrated in metal oxides. In the present study, crystal facets effect on the photocatalytic activity of metal sulfide NiS2 was studied for the first time. It was found that the {111}-faceted NiS2 nanocrystals showed improved photocatalytic activity in the degradation of various typical pollutants in water compared with {100}-faceted NiS2 nanocrystals. Moreover, through hybridizing with rGO nanosheets, the photocatalytic activity of the {111}-faceted NiS2 nanocrystals can be further improved, resulting in the complete degradation of heavy metal hexavalent chromium and organic dyes. The photocatalytic mechanism was studied in detail through theory calculation and experimental characterization. It was found that both the surface energies of Ni-terminated and S-terminated {111} facets were much higher than that of {100} facets, indicating that {111} facets were more active. Besides, rGO hybridizing can realize the effective separation of photogenerated electrons and holes. The results provide important guidance for the further development of efficient metal sulfide photocatalysts.

High selectivity of sulfur-doped SnO2 in NO2 detection at lower operating temperatures.

Resistive gas sensors based on metal oxides have aroused great interest in the sensing of NO2 gas due to their low cost, good stability, and easy fabrication. However, drawbacks such as low sensitivity and a lack of selectivity, which originate from the limited kinds of intrinsic active centers on the surface of the metal oxides that could be involved in the gas-sensing reaction, remain great challenges to overcome. To solve these problems, surface modification of SnO2 by S-doping was carried out by the sintering of flower-like SnS2. Gas-sensing tests revealed that the S-doped SnO2 showed ultra-high sensitivity to NO2 (Rg/Ra = 600 toward 5 ppm) with low optimal operating temperature (50 °C). The detection limit of the sensor was as low as 50 ppb (Rg/Ra = 11). Notably, the S-doped SnO2 showed negligible cross-responses to alcohol, acetone, HCHO, SO2, H2S, and xylene. The ultra-high sensitivity and selectivity toward NO2 were closely related to the content of the S-dopant. This phenomenon is attributed to the active role of S-dopant during the surface reactions with NO2, which was substantiated by in situ Raman characterization and DFT-based calculations. This study offers an important guide for surface modification by doping to improve the sensitivity and selectivity of metal oxides and sheds new light on material design to develop resistive gas sensors for NO2 detection.

One-Dimensional Zinc Oxide Decorated Cobalt Oxide Nanospheres for Enhanced Gas-Sensing Properties.

In this study, one-dimensional (1D) zinc oxide was loaded on the surface of cobalt oxide microspheres, which were assembled by single-crystalline porous nanosheets, via a simple heteroepitaxial growth process. This elaborate structure possessed an excellent transducer function from the single-crystalline feature of Co3O4 nanosheets and the receptor function from the zinc oxide nanorods. The structure of the as-prepared hybrid was confirmed via a Scanning Electron Microscope (SEM), X-ray diffraction (XRD), and a Transmission Electron Microscope (TEM). Gas-sensing tests showed that the gas-sensing properties of the as-designed hybrid were largely improved. The response was about 161 (Ra/Rg) to 100 ppm ethanol, which is 110 and 10 times higher than that of Co3O4 (Rg/Ra = 1.47) and ZnO (Ra/Rg = 15), respectively. And the as-designed ZnO/Co3O4 hybrid also showed a high selectivity to ethanol. The superior gas-sensing properties were mainly attributed to the as-designed nanostructures that contained a super transducer function and a super receptor function. The design strategy for gas-sensing materials in this work shed a new light on the exploration of high-performance gas sensors.

Improved ethanol gas sensing performances of a ZnO/Co3O4 composite induced by its flytrap-like structure.

Nanocomposite materials with excellent receptor and transducer functions are promising in ameliorating their gas sensing properties. However, due to the abrupt changes of receptor and transducer functions when different components are combined together, structural engineering that considers both the receptor and transducer functions to design such desirable sensing materials still remains a great challenge. Here, a nanocomposite material composed of 1D ZnO nanorods and 3D Co3O4 microspheres assembled by single-crystalline porous nanosheets has been designed, which was inspired by the high-efficiency receptor-transducer-response structure of venus flytraps. The as-designed ZnO/Co3O4 composite exhibited high response (Ra/Rg = 125 to 100 ppm ethanol) which was 84 times and 8 times higher than those of Co3O4 (Rg/Ra = 1.43) and ZnO (Ra/Rg = 15). The excellent sensing properties are ascribed to the as-designed flytrap-like structure which possesses a super receptor function from 1D ZnO with a large surface area, p-n heterojunctions with an amplified response signal, as well as excellent transducer functions from single-crystalline porous Co3O4 with fast charge transport channels. This strategy provides us with new guidance on the exploration of high-performance gas sensors which could further extend to other bio-structures that are abundant in nature.

Facile synthesis of diverse graphene nanomeshes based on simultaneous regulation of pore size and surface structure.

Recently, graphene nanomesh (GNM) has attracted great attentions due to its unique porous structure, abundant active sites, finite band gap and possesses potential applications in the fields of electronics, gas sensor/storage, catalysis, etc. Therefore, diverse GNMs with different physical and chemical properties are required urgently to meet different applications. Herein we demonstrate a facile synthetic method based on the famous Fenton reaction to prepare GNM, by using economically fabricated graphene oxide (GO) as a starting material. By precisely controlling the reaction time, simultaneous regulation of pore size from 2.9 to 11.1 nm and surface structure can be realized. Ultimately, diverse GNMs with tunable band gap and work function can be obtained. Specially, the band gap decreases from 4.5-2.3 eV for GO, which is an insulator, to 3.9-1.24 eV for GNM-5 h, which approaches to a semiconductor. The dual nature of electrophilic addition and oxidizability of HO(•) is responsible for this controllable synthesis. This efficient, low-cost, inherently scalable synthetic method is suitable for provide diverse and optional GNMs, and may be generalized to a universal technique.

Interface Bonds Determined Gas-Sensing of SnO2-SnS2 Hybrids to Ammonia at Room Temperature.

Unique gas-sensing properties of semiconducting hybrids that are mainly related to the heterogeneous interfaces have been considerably reported. However, the effect of heterogeneous interfaces on the gas-sensing properties is still unclear, which hinders the development of semiconducting hybrids in gas-sensing applications. In this work, SnO2-SnS2 hybrids were synthesized by the oxidation of SnS2 at 300 °C with different times and exhibited high response to NH3 at room temperature. With the increasing oxidation time, the relative concentration of interfacial Sn bonds, O-Sn-S, among the total Sn species of the SnO2-SnS2 hybrids increased first and then decreased. Interestingly, it can be found that the response of SnO2-SnS2 hybrids to NH3 at room temperature exhibited a strong dependence on the interfacial bonds. With more chemical bonds at the interface, the lower interface state density and the higher charge density of SnO2 led to more chemisorbed oxygen, resulting in a high response to NH3. Our results revealed the real roles of the heterogeneous interface in gas-sensing properties of hybrids and the importance of the interfacial bonds, which offers guidance for the material design to develop hybrid-based sensors.

Room temperature NO2 sensing: what advantage does the rGO-NiO nanocomposite have over pristine NiO?

In recent years, there has been increasing interest in synthesis of reduced graphene oxide (rGO)-metal oxide semiconductor (MOS) nanocomposites for room temperature gas sensing applications. Generally, the sensitivity of a MOS can be obviously enhanced by the incorporation of rGO. However, a lack of knowledge regarding how rGO can enhance gas-sensing performances of MOSs impedes its sensing applications. Herein, in order to get an insight into the sensing mechanism of rGO-MOS nanocomposites and further improve the sensing performances of NiO-based sensors at room temperature, an rGO-NiO nanocomposite was synthesized. Through a comparison study on room temperature NO2 sensing of rGO-NiO and pristine NiO, an inverse gas-sensing behavior in different NO2 concentration ranges was observed and the sensitivity of rGO-NiO was enhanced obviously in the high concentration range (7-60 ppm). Significantly, the stimulating effect of rGO on the recovery rate was confirmed by the sensing characteristics of rGO-NiO that was advantageous for the development of NO2 sensors at room temperature. By comprehending the electronic interactions between the rGO-MOS nanocomposite and the target gas, this work may open up new possibilities for further improvement of graphene-based hybrid materials with even higher sensing performances.