Drastic Improvement in Gas-Sensing Characteristics of Phosphorene Nanosheets under Vacancy Defects and Elemental Functionalization

Efficient chemical gas detection is of great importance for various functionalities (such as leakage detection of hazardous and explosive gases in industrial safety systems). The recent discovery of 2D black phosphorene (BlackP) has created intensive interests toward nanosensors because of its maximized surface-to-volume ratio and exceptional carrier mobility that potentially deliver the superior performance than the conventional transition-metal oxides sensors. In this work, we have performed first-principles DFT calculations coupled with the statistical analysis to unravel the structural, electronic, and gas-sensing characteristics of pristine, defected, and metal-substituted BlackP toward toxic H2S and SO2 gas molecules. Our findings have revealed that pristine BlackP weakly interacts with both H2S and SO2 by van der Waals (vdW) forces characterized by the small binding energies. The analysis of electronic properties via the density of states (DOS) indicates that there is a negligible change in DOS after gas exposure, which confirms insensitive sensing. To intensify the binding energies, we have considered defects (mono-, di-, tri-, and quad-vacancy) and substitutional impurities (Ti, Si, Mn, and Fe) as the incentives. The presence of mono- and divacancies remains less energetically sensitive to both gas species because of the low adsorption energies. Meanwhile, tri- and quad-vacancies induce the dissociative adsorption, not suitable for the reversible adsorption-desorption cycles. Substitutional doping by Fe atoms is found to be a feasible approach to enhance the sensing resolution of SO2 detection because of the remarkable adsorption energy incorporated with the substantial variation in DOS after gas exposure. This modification in electronic properties is facilitated by the charge transfer mechanism from Fe 3d to P 3p which can generate the measurable electrical signal detected by the external circuit of the sensor

Drastic Improvement in Gas-Sensing Characteristics of Phosphorene Nanosheets under Vacancy Defects and Elemental Functionalization

Efficient chemical gas detection is of great importance for various functionalities (such as leakage detection of hazardous and explosive gases in industrial safety systems). The recent discovery of 2D black phosphorene (BlackP) has created intensive interests toward nanosensors because of its maximized surface-to-volume ratio and exceptional carrier mobility that potentially deliver the superior performance than the conventional transition-metal oxides sensors. In this work, we have performed first-principles DFT calculations coupled with the statistical analysis to unravel the structural, electronic, and gas-sensing characteristics of pristine, defected, and metal-substituted BlackP toward toxic HS and SO gas molecules. Our findings have revealed that pristine BlackP weakly interacts with both HS and SO by van der Waals (vdW) forces characterized by the small binding energies. The analysis of electronic properties via the density of states (DOS) indicates that there is a negligible change in DOS after gas exposure, which confirms insensitive sensing. To intensify the binding energies, we have considered defects (mono-, di-, tri-, and quad-vacancy) and substitutional impurities (Ti, Si, Mn, and Fe) as the incentives. The presence of mono- and divacancies remains less energetically sensitive to both gas species because of the low adsorption energies. Meanwhile, tri- and quad-vacancies induce the dissociative adsorption, not suitable for the reversible adsorption-desorption cycles. Substitutional doping by Fe atoms is found to be a feasible approach to enhance the sensing resolution of SO detection because of the remarkable adsorption energy incorporated with the substantial variation in DOS after gas exposure. This modification in electronic properties is facilitated by the charge transfer mechanism from Fe 3d to P 3p which can generate the measurable electrical signal detected by the external circuit of the sensor

Novel green phosphorene as a superior chemical gas sensing material

Green phosphorus and its monolayer variant, green phosphorene (GreenP), are the recent members of two-dimensional (2D) phosphorus polymorphs. The new polymorph possesses the high stability, tunable direct bandgap, exceptional electronic transport, and directionally anisotropic properties. All these unique features could reinforce it the new contender in a variety of electronic, optical, and sensing devices. Herein, we present gas-sensing characteristics of pristine and defected GreenP towards major environmental gases (i. e., NH3, NO, NO2, CO, CO2, and H2O) using combination of the density functional theory, statistical thermodynamic modeling, and the non-equilibrium Green’s function approach (NEGF). The calculated adsorption energies, density of states (DOS), charge transfer, and Crystal Orbital Hamiltonian Population (COHP) reveal that NO, NO2, CO, CO2 are adsorbed on GreenP, stronger than both NH3 and H2O, which are weakly physisorbed via van der Waals interactions. Furthermore, substitutional doping by sulfur can selectively intensify the adsorption towards crucial NO2 gas because of the enhanced charge transfer between p orbitals of the dopant and the analyte. The statistical estimation of macroscopic measurable adsorption densities manifests that the significant amount of NO2 molecules can be practically adsorbed at ambient temperature even at the ultra-low concentration of part per billion (ppb). In addition, the current-voltage (I-V) characteristics of S-doped GreenP exhibit a variation upon NO2 exposure, indicating the superior sensitivity in sensing devices. Our work sheds light on the promising application of the novel GreenP as promising chemical gas sensors

Ecofriendly alkali metal cations diffusion improves fabrication of mixed-phase titania polymorphs on fixed substrate by chemical vapor deposition (CVD) for photocatalytic degradation of azo dye

Controlling the nanoscale synthesis of semiconductor TiO2 on a fixed substrate has fascinated the curiosity of academics for decades. Synthesis development is required to give an easy-to-control technique and parameters for TiO2 manufacture, leading to advancements in prospective applications such as photocatalysts. This study, mixed-phase TiO2(B)/other titania thin films were synthesized on a fused quartz substrate utilizing a modified Chemical vapor depodition involving alkali-metal ions (Li+, Na+, and K+) solution pre-treatment. It was discovered that different cations promote dramatically varied phases and compositions of thin films. The films had a columnar structure with agglomerated irregular-shaped particles with a mean thickness of 800–2000 nm. Na+ ions can promote TiO2(B) more effectively than K+ ions, however Li+ ions cannot synthesize TiO2(B). The amounts of TiO2(B) in thin films increase with increasing alkali metal (K+ and Na+) concentration. According to experimental and DFT calculations, the hypothesized TiO2(B) production mechanism happened via the meta-stable intermediate alkaline titanate transformation caused by alkali-metal ion diffusion. The mixed phase of TiO2(B) and anatase TiO2 on the fixed substrate (1 × 1 cm2) obtained from Na+ pre-treated procedures showed significant photocatalytic activity for the degradation of methylene blue. K2Ti6O12, Li2TiO3, Rutile TiO2, and Brookite TiO2 phase formations produced by K+ and Li + pretreatment are low activity photocatalysts. Photocatalytic activities were more prevalent in NaOH pre-treated samples (59.1% dye degradation) than in LiOH and KOH pre-treated samples (49.6% and 34.2%, respectively). This revealed that our developed CVD might generate good photocatalytic thin films of mixed-phase TiO2(B)/anatase TiO2 on any substrate, accelerating progress in future applications