A 2D-0D-2D Sandwich Heterostructure toward High-Performance Room-Temperature Gas Sensing.

The construction of two-dimensional (2D) van der Waals (vdW) heterostructures over black phosphorus (BP) has been attracting significant attention to better utilize its inherent properties. The sandwich of zero-dimensional (0D) noble metals within BP-based vdW heterostructures can provide efficient catalytic channels, modulating their surface redox potentials and therefore inducing versatile functionalities. Herein, we realize a 2D WS2-Au-BP heterostructure, in which Au nanoparticles are connected between BP and WS2 via ionic bonds. The ultralow conduction band minimum position, the reduced adsorption energies of O2, and the increased dissociation barrier energy of O2- into 2O contribute greatly to improving the long-term stability of BP in the air. The formation of heterostructures can reduce the potential barrier energy in target gas molecules, thus enhancing the absorption energy and charge transfer. Taking the paramagnetic NO2 gas molecules as a representative, a stable response magnitude of 2.11 to 100 ppb NO2 is achieved for 80 days, which is far larger than the initial responses of most BP-based materials. A practical gas sensing system is also developed to demonstrate its real-world implementation. This work provides a promising demonstration of 0D noble metal within 2D BP-based vdW heterostructure for simultaneously improving the long-term stability and room-temperature reversible gas sensing.

Exploring the gas-sensing properties of MOF-derived TiN@CuO as a hydrogen sulfide sensor.

In an effort to develop a long-lasting gas sensor, this article presents titanium nitride (TiN) as a potential substitute sensitive material in conjunction with (copper(II) benzene-1,3,5-tricarboxylate) Cu-BTC-derived CuO. The work focused on the gas-sensing characteristics of TiN/CuO nanoparticles in detecting H2S gas at various temperatures and concentrations. XRD, XPS, and SEM were utilized to analyze the composites with varied Cu molar ratios. The responses of TiN/CuO-2 nanoparticles to 50 and 100 ppm H2S gas at 50 °C and 250 °C are 34.8 and 60.0, respectively. The related sensor had high selectivity and stability towards H2S, and the response of TiN/CuO-2 is still 2.5-5 ppm H2S. The gas-sensing properties as well as the mechanism are fully explained in this study. TiN/CuO might be a choice for the detection of H2S gas, opening up new avenues for applications in industries, medical facilities, and homes.

Metal-organic frameworks-derived In2O3/ZnO porous hollow nanocages for highly sensitive H2S gas sensor.

The detection of hydrogen sulfide (H2S) is critical because of its potential harm and widespread presence in the oil and gas sectors. The zeolitic imidazolate framework-8 (ZIF-8) derived ZnO nanostructures manufactured as gas sensors have exceptional sensitivity and selectivity for H2S gas. In/Zn-ZIF-8 template material was synthesized by a simple one-step co-precipitation method followed by thermal annealing in air. The heat treatment resulted in In2O3/ZnO nanostructures with mixed heterostructures. The crystal structure (XRD), morphology (SEM/TEM), chemical state (XPS), surface area (BET), etc were investigated to ascertain the nature of the as-prepared material. SEM imagery revealed that the as-prepared In2O3/ZnO sensitive material had a microstructure of porous hollow nanocages with an average particle size of about 200 nm, which is beneficial to the diffusion and adsorption of gas molecules. The gas sensing performance test results of the In2O3/ZnO hollow nanocages show that their response to H2S gas is significantly improved 67.5 @50 ppm H2S (about 11 times that of pure ZnO nanocages) at an optimal temperature of 200 °C, better selectivity, lower theoretical detection limit and good linearity between gas concentration and response values. The enhanced gas sensing feat to H2S gas is mainly attributed to the formation of n-n heterojunction and the wide surface area of the newly formed In2O3/ZnO porous hollow nanocages.

Facile fabrication of nanoflower-like WO3/WS2 heterojunction for highly sensitive NO2 detection at room temperature.

Realizing efficient detection of ultra-low concentrations of hazardous gases contributes to air pollution monitoring, ecosystem and human health protection. Herein, we firstly fabricated the nanoflower-like WO3/WS2 composites by a facile process to highly sensitively detect NO2 at room temperature. The WO3 content in the WO3/WS2 composites can be adjusted by altering the calcination temperature, and the WO3 nanoparticles disperse uniformly on the WS2 surface, forming the WO3/WS2 heterojunction. The room-temperature responses of WO3/WS2 composites gradually climb with the NO2 concentration increasing from 0.005 to 5 ppm, and the WW-280 and WW-300 composites possess the optimal gas sensitivity when the NO2 concentrations are lower and higher than 100 ppb, respectively. In particular, the two WO3/WS2 composites present the limitation of detection (LOD) of ≤ 5 ppb, and they exhibit the excellent selectivity, good reproducibility and long-term stability towards NO2. A possible gas sensing mechanism was also proposed from the point of views of gas adsorption, redox reactions and electron transfer. The appropriate WO3 content and molar ratio of hexagonal to monoclinic WO3, and the formation of WO3/WS2 p-n heterojunction can contribute to the high sensitivity of WO3/WS2 composite to various concentrations of NO2. This work offers a promising gas sensing material for room-temperature detection to low concentrations of NO2.

Theoretical Study on P-coordinated Metal Atoms Embedded in Arsenene for the Conversion of Nitrogen to Ammonia.

The conversion of gaseous N2 to ammonia under mild conditions by artificial methods has become one of the hot topics and challenges in the field of energy research today. Accordingly, based on density function theory calculations, we comprehensively explored the d-block of metal atoms (Ti, V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ru, Rh, W, and Pt) embedded in arsenene (Ars) for different transition systems of phosphorus (P) coordination as potential electrocatalysts for N2 reduction reaction (NRR). By adopting a "two-step" strategy with stringent NRR catalyst screening criteria, we eventually selected Nb@P3-Ars as a research object for a further in-depth NRR mechanism study. Our results show that Nb@P3-Ars not only maintains the thermodynamic stability at mild temperatures but also dominates the competition with the hydrogen evolution reaction when used as the electrochemical NRR (e-NRR) catalyst. In particular, while the NRR process occurs by the distal mechanism, Nb@P3-Ars has a low overpotential (0.36 V), which facilitates the efficient reduction of N2. Therefore, this work predicts the possibility of Nb@P3-Ars as an e-NRR catalyst for reducing N2 from a theoretical perspective and provides significant insights and theoretical guidance for future experimental research.

Single atom-doped arsenene as electrocatalyst for reducing nitrogen to ammonia: a DFT study.

Due to the wide application of NH3 in the energy and chemical industry, the rational design of a highly efficient and low-cost electrocatalyst for nitrogen fixation at moderate conditions is highly desirable to meet the increasing demand for sustainable energy production in the modern society. Herein, we have systematically studied the catalytic performance of transition metal (TM) atom (i.e., V, Cr, Fe, Co, Cu, Ru, Pd, Ag, Pt, Au)-doped arsenene nanosheet, a new two-dimensional (2D) nanomaterial in VA group, as a heterogeneous catalyst for nitrogen reduction reaction (NRR). By density functional theory (DFT) calculation and systematic theoretical screening, our study predicts that the systems of V-, Fe-, Co- and Ru-doped arsenene have promising potentials as NRR electrocatalysts with high-loading TM and highly stable adsorption of N2 molecule. Particularly, the V-doped system exhibits two feasible configurations for N2 adsorption and an ultralow overpotential (0.10 V) via the enzymatic pathway, which is very competitive among similar reported electrocatalysts. This theoretical study not only extends the electrocatalyst family for nitrogen fixation, but also further deepens our physical insights into catalytic improvement, which can be expected to guide the rational design of novel NRR catalysts.

Influence of Interaction Components on the NOx Adsorption Properties of Cu-Ba-Ce Composite Catalysts.

For further investigating the role of components in copper-cerium-barium composite oxide catalysts, a series of noble metal-free catalysts with different barium contents were synthesized by citric acid method. The prepared catalysts were characterized by X-ray diffraction, Brunauer-Emmett- Teller method, scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy. Catalysts were evaluated by NO oxidation, NOx adsorption, and NOx temperature-programmed desorption. The results showed that barium content significantly affected the catalysts' properties. With barium addition, interactions among components considerably changed; hence, the microstructure and performance of catalysts were distinctly different. In general, the interactions of barium-copper and barium-cerium were not conducive to catalyst adsorption. Adsorption performance derived from barium carbonate was superior to those of the other two components.