Detecting and monitoring air-polluting gases such as carbon monoxide (CO), nitrogen oxides (NO_x), and sulfur oxides (SO_x) are critical, as these gases are toxic and harm the ecosystem and the human health. Therefore, it is necessary to design high-performance gas sensors for toxic gas detection. In this sense, graphene-based materials are promising for use as toxic gas sensors. In addition to experimental investigations, first-principle methods have enabled graphene-based sensor design to progress by leaps and bounds. This review presents a detailed analysis of graphene-based toxic gas sensors by using first-principle methods. The modifications made to graphene, such as decorated, defective, and doped to improve the detection of NO_x, SO_x, and CO toxic gases are revised and analyzed. In general, graphene decorated with transition metals, defective graphene, and doped graphene have a higher sensibility toward the toxic gases than pristine graphene. This review shows the relevance of using first-principle studies for the design of novel and efficient toxic gas sensors. The theoretical results obtained to date can greatly help experimental groups to design novel and efficient graphene-based toxic gas sensors.

Various technologies have been developed for the safe and efficient storage of hydrogen. Hydrogen storage in its solid form is an attractive option to overcome challenges such as storage and cost. Specifically, hydrogen storage in carbon-based structures is a good solution. To date, numerous theoretical studies have explored hydrogen storage in different carbon structures. Consequently, in this review, density functional theory (DFT) studies on hydrogen storage in graphene-based structures are examined in detail. Different modifications of graphene structures to improve their hydrogen storage properties are comprehensively reviewed. To date, various modified graphene structures, such as decorated graphene, doped graphene, graphene with vacancies, graphene with vacancies-doping, as well as decorated-doped graphene, have been explored to modify the reactivity of pristine graphene. Most of these modified graphene structures are good candidates for hydrogen storage. The DFT-based theoretical studies analyzed in this review should motivate experimental groups to experimentally validate the theoretical predictions as many modified graphene systems are shown to be good candidates for hydrogen storage.

Portland cement (PC) is a material that is indispensable for satisfying recent urban requirements, which demands infrastructure with adequate mechanical and durable properties. In this context, building construction has employed nanomaterials (e.g., oxide metals, carbon, and industrial/agro-industrial waste) as partial replacements for PC to obtain construction materials with better performance than those manufactured using only PC. Therefore, in this study, the properties of fresh and hardened states of nanomaterial-reinforced PC-based materials are reviewed and analyzed in detail. The partial replacement of PC by nanomaterials increases their mechanical properties at early ages and significantly improves their durability against several adverse agents and conditions. Owing to the advantages of nanomaterials as a partial replacement for PC, studies on the mechanical and durability properties for a long-term period are highly necessary.

Nitrogen oxides (NO_x) are among the main atmospheric pollutants; therefore, it is important to monitor and detect their presence in the atmosphere. To this end, low-dimensional carbon structures have been widely used as NO_x sensors for their outstanding properties. In particular, carbon nanotubes (CNTs) have been widely used as toxic-gas sensors owing to their high specific surface area and excellent mechanical properties. Although pristine CNTs have shown promising performance for NO_x detection, several strategies have been developed such as surface functionalization and defect engineering to improve the NO_x sensing of pristine CNT-based sensors. Through these strategies, the sensing properties of modified CNTs toward NO_x gases have been substantially improved. Therefore, in this review, we have analyzed the defect engineering and surface functionalization strategies used in the last decade to modify the sensitivity and the selectivity of CNTs to NO_x. First, the different types of surface functionalization and defect engineering were reviewed. Thereafter, we analyzed experimental, theoretical, and coupled experimental–theoretical studies on CNTs modified through surface functionalization and defect engineering to improve the sensitivity and selectivity to NO_x. Finally, we presented the conclusions and the future directions of modified CNTs as NO_x sensors.

CO₂ adsorption on bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on pyridinic N₃-doped graphene (PNG) was investigated by employing the density functional theory. First, the interaction of Co₁₃ and Cu₁₃ with PNG was analyzed by spin densities, interaction energies, charge transfers, and HUMO-LUMO gaps. According to the interaction energies, the Co₁₃ nanocluster was adsorbed more efficiently than Cu₁₃ on the PNG. The charge transfer indicated that the Co₁₃ nanocluster donated more charges to the PNG nanoflake than the Cu₁₃ nanocluster. The HUMO-LUMO gap calculations showed that the PNG improved the chemical reactivity of both Co₁₃ and Cu₁₃ nanoclusters. When the CO₂ was adsorbed on the bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on the PNG, it experienced a bond elongation and angle bending in both systems. In addition, the charge transfer from the nanoclusters to the CO₂ molecule was observed. This study proved that Co₁₃/PNG and Cu₁₃/PNG composites are adequate candidates for CO₂ adsorption and activation.

Graphene with defects is a vital support material since it improves the catalytic activity and stability of nanoparticles. Here, a density functional theory study was conducted to investigate the stability, energy, and reactivity properties of Ni_nPd_n (n = 1–3) clusters supported on graphene with different defects (i.e., graphene with monovacancy and pyridinic N-doped graphene with one, two, and three N atoms). On the interaction between the clusters and graphene with defects, the charge was transferred from the clusters to the modified graphene, and it was observed that the binding energy between them was substantially higher than that previously reported for Pd-based clusters supported on pristine graphene. The vertical ionization potential calculated for the clusters supported on modified graphene decreased compared with that calculated for free clusters. In contrast, vertical electron affinity values for the clusters supported on graphene with defects increased compared with those calculated for free clusters. In addition, the chemical hardness calculated for the clusters supported on modified graphene was decreased compared with free clusters, suggesting that the former may exhibit higher reactivity than the latter. Therefore, it could be inferred that graphene with defects is a good support material because it enhances the stability and reactivity of the Pd-based alloy clusters supported on PNG.