Gas Graphene Research Articles

A DFT study of the oxygen reduction reaction mechanism on be doped graphene

Graphene despite its high surface area has very limited activity towards the oxygen reduction reaction (ORR), demonstrating selectivity towards the unfavorable two-electron mechanism. We have employed the spin polarized density functional theory method to investigate the oxygen reduction reaction activity of the heteroatom p-type beryllium (Be) doped graphene in gas and aqueous media. The preferred doping sites, active sites and reaction mechanisms available on the doped graphene surfaces were investigated with increasing Be concentrations of 0.03 ML, 0.06 ML and 0.09 ML. Our results reveal that oxygen is physisorbed on bare graphene, however, Be at the lattice sites provides site for oxygen adsorption and ORR. Generally, Be concentration increase in a single honey-comb of graphene from 1 to 2, increasing oxygen activation and dissociation on graphene, compared to their isolated defective counterparts. Considering the conjugated Be defective surfaces, oxygen binds dissociatively on the doped surfaces preferentially in the order 0.06 ML > 0.09 ML > 0.03 ML. Whereby strong binding at the 0.06 ML doped surface corresponds to least charge loss to oxygen. Surfaces with the least affinity for O*, OH* and H2O*, and can transfer the most charges to O2 leading to dissociation (as seen on the 0.03 ML surface), shows the highest reaction activity towards the ORR. From these results surfaces that bind O2 weakly and dissociatively could hold promise for the ORR reaction. Single atom catalyst of Be, based on graphene is promising for the ORR. Graphical abstract

Enhanced NO2 Sensing at Room Temperature with Graphene via Monodisperse Polystyrene Bead Decoration.

Graphene is a single layer of carbon atoms with a large surface-to-volume ratio, providing a large capacity gas molecule adsorption and a strong surface sensitivity. Chemical vapor deposition-grown graphene-based NO2 gas sensors typically have detection limits from 100 parts per billion (ppb) to a few parts per million (ppm), with response times over 1000 s. Numerous methods have been proposed to enhance the NO2 sensing ability of graphenes. Among them, surface decoration with metal particles and metal-oxide particles has demonstrated the potential to enhance the gas-sensing properties. Here, we show that the NO2 sensing of graphene can be also enhanced via decoration with monodisperse polymer beads. In dark conditions, the detection limit is improved from 1000 to 45 ppb after the application of polystyrene (PS) beads. With laser illumination, a detection limit of 0.5 ppb is determined. The enhanced gas sensing is due to surface plasmon polaritons excited by interference and charge transfer between the PS beads. This method opens an interesting route for the application of graphene in gas sensing.

Fe-doped graphene nanosheet as an adsorption platform of harmful gas molecules (CO, CO2, SO2 and H2S), and the co-adsorption in O2 environments

The adsorption of pollutant gases (CO, CO2, SO2 and H2S) onto Fe-doped graphene nanosheets (FeG) is studied on the basis of density functional theory calculations at the PBE/Def2-SVP level of theory. The most stable adsorption configurations, binding characteristics, electronic properties and stability at room temperature of the FeG–Gas interactions is fully analyzed. The gas molecules are chemisorbed onto FeG with adsorption energies in the range of 0.54–1.8eV, with an enhanced adsorption strength compared to intrinsic graphene. The stability of the FeG-Gas interactions is dominated by Lewis-acid-base interactions, and its strength is sorted as SO2>CO>H2S>CO2. The adsorption stability is also retained at room temperature (300K). Due to the strong interaction of SO2, CO, and H2S, FeG could catalyze or activate these gas molecules, suggesting the possibility of FeG as a catalyst substrate. The electron acceptor/donor character of CO, CO2, SO2 and H2S molecules when adsorbed onto FeG causes charge transfer processes that are responsible for the change in conductance of FeG; thus, the response of the HOMO-LUMO gap of FeG under gas adsorption could be useful for sensing applications. Furthermore, the analysis of the co-adsorption in O2 environments shows that the CO2 interaction turns unstable onto FeG, while the sensing response towards H2S is suppressed. Finally, these results give new insights into the emerging applications of Fe-doped graphene in gas capture/filtration devices, solid-state gas sensors or as a catalyst substrate.

Transport Properties and Sensing Responses of Platinum Nanoparticles/Graphene Structure Fabricated by Thermal Annealing Process

The effects of the annealing temperatures and thicknesses on the shapes, sizes and arrangement of platinum (Pt) nanoparticles (NPs) on graphene and their sensing performance for hydrogen (H2) detection were investigated. It shows strong dependency of the annealing temperatures and thicknesses on the properties of NPs. It was found that the proposed technique is able to form the NPs with good size controllability and uniformity even for thick deposited layer, thus eliminating the requirement of very thin layer of below 5 nm for the direct NP synthesis by evaporation or sputtering. The transport properties of Pt NPs/graphene structure and its sensing performance on H2 at room temperature under various H2 concentration were evaluated. The results showed an acceptable sensing response, indicating an innovative approach to fabricate Pt NPs embedded graphene for gas sensing application.

Adsorption of gas molecules on Ga-doped graphene and effect of applied electric field: A DFT study

Density functional theory calculations have been carried out to study the adsorption of varous gas molecules (H2O, NH3, CO, NO2 and NO) on pristine graphene and Ga-doped graphene in order to explore the feasibility of Ga-doped graphene based gas sensor. For each gas molecule, various adsorption positions and orientations were considered. The most stable configuration was determined and the adsorption energies with van der Waals interactions were calculated. Further, electronic properties such as electron density, density of states, charge transfer and band structure were investigated to understand the mechanism of adsorption. The results showed that the gas molecules studied were only weakly adsorbed on pristine graphene with small adsorption energies. On the other hand, the adsorption energies of all gas molecules on Ga-doped graphene increased by various amounts. Adsorption of gas molecules on Ga-doped graphene can open a relatively large band gap ranging from 0.267 to 0.397eV. NO2 was found to be very sensitive to Ga-doped graphene with adsorption energy of −1.928eV due to strong orbital hybridization and large charge transfer. Furthermore, our study suggests that the affinity and electronic properties of NO2 on Ga-doped graphene can be dramatically changed by an external electric field. A negative electric field enhances the adsorption of NO2 on Ga-doped graphene as reflected in the increase in adsorption energy. In contrast, the interaction will be weakened under a positive electric field. The results of the DFT calculation indicates the potential application of Ga-doped graphene in gas sensing for NO2 detection, and the advantage to use external electric field to tune the sensitivity for NO2.