Anthracite based activated carbon impregnated with HMTA as an effectiveness adsorbent could significantly uptake gasoline vapors.

In this study, we synthesized and employed the amine impregnated activated carbon as an efficacious adsorbent for uptaking gasoline vapor. For this regard, anthracite as activated carbon source and hexamethylenetetramine (HMTA) as amine were selected and utilized. Physiochemical characterization of made sorbents were evaluated and investigated using SEM, FESEM, BET, FTIR, XRD, zeta potential, and elemental analysis. The synthesized sorbents provided an excellent textural features as compared with the literature and other activated carbon based sorbents and impregnated with amine. Our findings also suggested that in addition to high surface area (up to 2150 m2 / g), the micro- meso pores created (Vmeso / V micro = 0.79 Cm 3 / g) surface chemistry may significantly affect the gasoline sorption capacity, which here the role of mesoporous is further highlighted. V meso for amine impregnated sample and free activated carbon was 0.89 and 0.31 Cm 3 / g, respectively. According to the results, the prepared sorbents have a potential capability in uptaking gasoline vapor and with line this, we report a high sorption capacity of 572.56 mg / g. After, four cycles used the sorbent had a high durability and about 99.11% of the initial uptake was maintained. Taking together the synthesized adsorbents as an activated carbon provided an excellent and unique features and enhanced gasoline uptake, therefore its applicability in uptaking gasoline vapor can be substantially considered.

Efficient DBT removal from diesel oil by CVD synthesized N-doped graphene as a nanoadsorbent: Equilibrium, kinetic and DFT study.

Adsorptive Dibenzothiophene (DBT) removal from diesel oil stream on nitrogen doped graphene (N-doped graphene) was considered. The N-doped graphene was synthesized by chemical vapor deposition (CVD) method at 1000 °C using camphor and urea. The adsorbent was characterized by Field Emission Scanning Electron Microscopy (FE-SEM), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR) and Nitrogen adsorption/desorption technique. Adsorption parameters such as temperature, time, concentration and mass loaded were optimized by experimental design method. Experimental kinetic data was fitted to Pseudo second order model successfully. Frendulich model was recommended for experimental isotherm data. However, Tempkin model was presented because of the importance of interaction between pyridinic nitrogen and DBT aromatic structure. The results indicate that not only the pore volume and surface area but also types of surface functionalities have an important role for DBT adsorption process, especially for the adsorbates with aromatic structures. The adsorption capacity was calculated up to 73.4 mg/g which is 1.25 times higher than the adsorption capacity of pristine. Thermal regeneration stability, fast adsorption kinetics and high adsorption capacity make N-G4 a potential promising adsorbent for DBT removal. Besides, density functional theory calculations revealed that an increase in the number of doped N atoms as well as the presence of a mono or divacancy defect in N-doped graphene can enhance the adsorption energy of DBT.

Adsorptive mercaptan removal of liquid phase using nanoporous graphene: Equilibrium, kinetic study and DFT calculations.

This research investigated the adsorption of tertiary butyl mercaptan (TBM) from liquid phases by using nanoporous graphene. Nanoporous graphene synthesized through chemical vapor deposition method was characterized using Brunauer-Emmett-Teller method, transmission electron microscopy, field-emission scanning microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy techniques. The TBM adsorption equilibrium was investigated by using Langmuir, Freundlich, and Tempkin models. The obtained results were in good agreement with the Freundlich isotherm. The adsorption kinetics of this process was modeled by the pseudo-first-order, pseudo-second-order, and intraparticle models. The adsorption rate was obtained according to the pseudo-second-order model. The satisfactory results indicated that nanoporous graphene can be used as a good carbon nanostructure sorbent in mercaptan removal. The process reduced the sulfur content from 300 ppm to less than 10 ppm which was the standard level in environmental regulations. The capacity for TBM removal was achieved at 4.4 gr S/gr adsorbent. The desulfurization efficiency was revealed about 96.3% for nanoporous graphene at 298 K and 24 h. Moreover, density functional theory calculations were used to determine the stable configuration, adsorption energy, and electronic structure of different configurations of TBM adsorbed onto a graphene surface. TBM physically adsorbed onto the graphene surface with adsorption energies of approximately - 25 kJ/mol was indicated from DFT calculations.

Strong Tetrel Bonds: Theoretical Aspects and Experimental Evidence.

In recent years, noncovalent interactions involving group-14 elements of the periodic table acting as a Lewis acid center (or tetrel-bonding interactions) have attracted considerable attention due to their potential applications in supramolecular chemistry, material science and so on. The aim of the present study is to characterize the geometry, strength and bonding properties of strong tetrel-bond interactions in some charge-assisted tetrel-bonded complexes. Ab initio calculations are performed, and the results are supported by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches. The interaction energies of the anionic tetrel-bonded complexes formed between XF3M molecule (X=F, CN; M=Si, Ge and Sn) and A- anions (A-=F-, Cl-, Br-, CN-, NC- and N3-) vary between -16.35 and -96.30 kcal/mol. The M atom in these complexes is generally characterized by pentavalency, i.e., is hypervalent. Moreover, the QTAIM analysis confirms that the anionic tetrel-bonding interaction in these systems could be classified as a strong interaction with some covalent character. On the other hand, it is found that the tetrel-bond interactions in cationic tetrel-bonded [p-NH3(C6H4)MH3]⁺···Z and [p-NH3(C6F4)MH3]⁺···Z complexes (M=Si, Ge, Sn and Z=NH3, NH2CH3, NH2OH and NH2NH2) are characterized by a strong orbital interaction between the filled lone-pair orbital of the Lewis base and empty BD*M-C orbital of the Lewis base. The substitution of the F atoms in the benzene ring provides a strong orbital interaction, and hence improved tetrel-bond interaction. For all charge-assisted tetrel-bonded complexes, it is seen that the formation of tetrel-bond interaction is accompanied bysignificant electron density redistribution over the interacting subunits. Finally, we provide some experimental evidence for the existence of such charge-assisted tetrel-bond interactions in crystalline phase.

A Comparative Study of CO Oxidation on Nitrogen- and Phosphorus-Doped Graphene.

The geometry, electronic structure, and catalytic properties of nitrogen- and phosphorus-doped graphene (N-/P-graphene) are investigated by density functional theory calculations. The reaction between adsorbed O2 and CO molecules on N- and P-graphene is comparably studied via Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. The results indicate that a two-step process can occur, namely, CO+O2 →CO2 +Oads and CO+Oads →CO2 . The calculated energy barriers of the first step are 15.8 and 12.4 kcal mol(-1) for N- and P-graphene, respectively. The second step of the oxidation reaction on N-graphene proceeds with an energy barrier of about 4 kcal mol(-1) . It is noteworthy that this reaction step was not observed on P-graphene because of the strong binding of Oads species on the P atoms. Thus, it can be concluded that low-cost N-graphene can be used as a promising green catalyst for low-temperature CO oxidation.

Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation.

CONTEXT: First-principles calculations are performed to investigate the catalytic oxidation of methane by using N2O as an oxidizing agent over aluminum (Al)-doped Zn12O12 cluster and (Zn12O12)2 nanowire. The impact of Al impurity on the geometry, electronic structure, and surface reactivity of Zn12O12 and (Zn12O12)2 is thoroughly studied. Our study demonstrates that Al-doped ZnO systems have a better adsorption ability than the corresponding pristine counterparts. It is found that N2O molecule is initially decomposed on the Al site to provide the N2 molecule, and an Al-O intermediate which is an active species for the CH4 oxidation. The conversion of CH4 into CH3OH over AlZn11O12 and (AlZn11O12)2 requires an activation energy of 0.45 and 0.29 eV, respectively, indicating it can be easily performed at normal temperatures. Besides, the overoxidation of methanol into formaldehyde cannot take place over the AlZn11O12 and (AlZn11O12)2, due to the high energy barrier needed to dissociate C-H bond of the CH3O intermediate. METHOD: Dispersion-corrected density functional theory calculations were performed through GGA-PBE exchange-correlation functional combined with a numerical double-ζ plus polarization (DNP) basis set as implemented in DMol3. To include the relativistic effects of core electrons of Zn atoms, DFT-semicore pseudopotentials were adopted. The DFT + D scheme proposed by Grimme was used to involve weak dispersion interactions within the DFT calculations. The reaction energy paths were generated by the minimum energy path calculations using the NEB method.

Prolonged corrosion protection via application of 4-ferrocenylbutyl saturated carboxylate ester derivatives with superior inhibition performance for mild steel.

A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters.

Enhanced VOCs adsorption with UIO-66-porous carbon nanohybrid from mesquite grain: A combined experimental and computational study.

In this study, adsorption of volatile organic compounds (VOCs) (here just gasoline vapor) by activated carbon- modified UIO-66 was investigated. First, activated carbon prepared from mesquite grain (ACPMG) and then UIO/ACPMG nanohybrid was synthesized by the solvothermal method. In following, the effect of main key parameters which effect on the surface and adsorption capacity such as the ratio of ACPMG to UIO-66 was studied. Physiochemical changes of as- synthesized samples were investigated by TGA, HR-TEM, PSD, SEM, EDX/MAP, BET, FT-IR, XRD, and XPS. It was found the UIO/ACPMG20% nanohybrid had the highest adsorption capacity (391.304 mg/g) for VOCs compared with the other samples, while the adsorption capacity of UIO-66, UIO/ACPMG10% nanohybrid, and UIO/ACPMG30% nanohybrid was 298.871, 309.523, and 320 mg/g respectively. UIO/ACPMG20% nanohybrid desorbed 285.71 mg/g of the adsorbed gasoline, which is an excellent result in desorption. So, the sample of UIO/ACPMG20% nanohybrid was selected as the optimum nano-adsorbent. In other hand, all the nano-adsorbent showed a rapid kinetic behavior for gasoline vapor adsorption and the maximum time for reaching a high adsorption capacity approximately was obtained in 20 min. Density functional theory calculations also performed to understand the adsorption characteristics of gasoline vapor on activated carbon-modified UIO-66.

Diphenylamine-based hole-transporting materials for excessive-overall performance perovskite solar cells: Insights from DFT calculations.

Density functional theory calculations were employed to identify the ability of some diphenylamine-based hole-transporting materials (HTMs) for use in top-performance perovskite solar cells. The effects of donor/acceptor electron groups and the new π-bridge section in the three-part of structures were investigated thoroughly. The results indicated that adding electron-withdrawing functional groups such as CN in the phenylazo-indol moiety and substituting electron donor groups such as CH3 in the NH2 hydrogen atoms of the diphenylamine section can cause higher power conversion light-harvesting efficiency in new HTMs. Also, the replacement of thieno [3,2-b] benzothiophene as a part of the π bridge with the phenyl group according to the optical and electronic structure properties improves the efficiency of the new phenylazoindole derivatives.

Efficient delivery of anticancer 5-fluorouracil drug by alkaline earth metal functionalized porphyrin-like porous fullerenes: A DFT study.

Finding and developing effective targeted drug delivery systems has emerged as an attractive approach for treating a wide range of diseases. In the present study, the potential of alkaline earth metal functionalized porphyrin-like porous C24N24 fullerenes for delivering 5-fluorouracil (5FU) anticancer drug is assessed using density functional theory calculations. The goal is to evaluate how the addition of alkaline earth metals to C24N24 enhances the adsorption capabilities of this system towards 5FU drug. The adsorption energies and charge transfers are determined in order to evaluate the strength of the interaction between the 5FU and fullerene surfaces. According to the results, adding alkaline earth metals increases the drug's adsorption energy on the C24N24 fullerene. In all cases, the drug molecule interacts with the metal atom through its CO group. Furthermore, the adsorption strength of the 5FU increases with metal atom size (Ca > Mg > Be), which is connected to the polarizability of these atoms. The adsorption energies of 5FU are shown to be highly sensitive on solvent effects and the acidity of the environment. The adsorption strength of 5FU decreases within the solvent (water), allowing it to be released more easily. The moderate adsorption energies and short desorption times of 5FU imply that it is reversibly adsorbed on the functionalized fullerenes.

Exploring the potential use of Fe-decorated B40 borospherene as a prospective catalyst for oxidation of methane to methanol.

First-principles calculations based on density functional theory were utilized to evaluate whether an iron atom decorated B40 borospherene can be employed as a catalyst for converting methane (CH4) to methanol (CH3OH) in the presence of N2O or O2 molecule. Geometry optimizations indicated that N2O and O2 are both chemisorbed on the Fe atom of the catalyst, whereas CH4 is physisorbed. Using N2O as the oxidant, the oxidation of CH4 begins with N2O decomposition on the catalyst, which has an activation barrier of 0.50 eV. The CH4 molecule then combines with the activated O atom remained on the Fe to form the CH3OH molecule. However, the oxidation of CH4 with O2 requires an activation barrier as high as 1.91 eV, implying that this process is unlikely to occur under normal conditions. These novel results are anticipated to help in the design and modeling of noble-metal free catalysts for CH4 oxidation.

Hollow nano-CaCO3's VOC sensing properties: A DFT calculation and experimental assessments.

Air is the most critical and necessary for life, and air quality significantly impacts people's health. Both indoor and outdoor pollution frequently contain volatile organic compounds (VOCs). Such contaminants provide immediate or long-term health risks to the living system. The present study investigates sorption characteristics of VOCs on hollow nano calcite (CaCO3) particles with 250 nm and 40 nm pore sizes to remove from the air ambient using the quartz crystal microbalance (QCM) technique at room temperature both experimentally and theoretically. The results were supported by density functional theory (DFT), and adsorption-desorption characteristics were studied with Langmuir adsorption isotherms. The QCM measurements showed a stable signal without having hysteresis, and the response of polar VOCs on hollow nano-CaCO3 particles such as ethanol, propanol, and humidity with higher polarity was less compared to solvents such as chloroform and dichloromethane, which revealed that the surfaces of CaCO3 particles have mostly non-polar properties. CaCO3 surface and VOC molecule interactions overlap with the Langmuir model. With DFT calculations, VOC and water molecule adsorption changes the CaCO3 Egap. Our findings show that the ΔEgap values increase as chloroform > dichloromethane > propanol > ethanol > water. This order suggests that the sensing response of the hollow CaCO3 structure is linearly proportional to the adsorption energies of VOC and water. The linear adsorption characteristics, high sensing response, and short recovery time illustrated that the newly synthesized nano-CaCO3 could be implemented as a new VOC adsorbent material for health, environmental sustainability, and in vitro microbiome cultures.

Sc-functionalized porphyrin-like porous fullerene for CO2 storage and separation: A first-principles evaluation.

In recent years, there has been a lot of interest in capturing and storing carbon dioxide (CO2) on porous materials as an efficient method for decreasing the adverse effects of this greenhouse gas on the environment and climate change. The current work introduces a Sc-decorated porphyrin-like porous fullerene (Sc6@C24N24) as an efficient material for CO2 capture, storage, and separation using density functional theory calculations. While CO2 is physisorbed over pristine C24N24, the addition of Sc atoms on the N4 sites of C24N24 greatly enhances CO2 adsorption energy. Each Sc atom in Sc6@C24N24 may adsorb up to three CO2 molecules, resulting in a gravimetric density of 48%. Moreover, temperature may be used to modulate CO2 adsorption/desorption over the substrate. The Sc-decorated C24N24 fullerene exhibits a lower affinity for adsorbing N2, CH4, and H2 molecules than CO2. As a consequence, this material might be considered for purifying CO2 molecules from CO2/N2, CO2/CH4, and CO2/H2 mixtures. This study also sheds light on the nature of the Sc-CO2 interaction as well as the underlying mechanism of selective CO2 adsorption on Sc decorated C24N24.

Oxidation of methane and ethylene over Al incorporated N-doped graphene: A comparative mechanistic DFT study.

It is generally recognized that developing effective methods for selective oxidation of hydrocarbons to generate more useful chemicals is a major challenge for the chemical industry. In the present study, density functional theory calculations are conducted to examine the catalytic partial oxidation of methane (CH4) and ethylene (C2H4) by nitrous oxide (N2O) over Al-incorporated porphyrin-like N-doped graphene (AlN4-Gr). Adsorption energies for the most stable configurations of CH4, C2H4, and N2O molecules over the AlN4-Gr catalyst are determined to be -0.25, -0.64, and -0.40 eV, respectively. According to our findings, N2O can be efficiently split into N2 and Oads species with a negligible activation energy on the AlN4-Gr surface. Meanwhile, CH4 and C2H4 molecules compete for reaction with the activated oxygen atom (Oads) that stays on the surface. The energy barriers for partial methane oxidation through the CH4 + Oads → CH3° + HOads and CH3° + HOads → CH3OH reaction steps are 0.16 eV and 0.27 eV, respectively. Furthermore, the produced CH3OH may be overoxidized by Oads to give formaldehyde and water molecules by overcoming a relatively low activation barrier. The activation barriers for C2H4 epoxidation are small and comparable to those for CH4 oxidation, implying that AlN4-Gr is highly active for both reactions. The high energy barrier for the 1,2-hydrogen shift in the OCH2CH2 intermediate, on the other hand, makes the production of acetaldehyde impossible under normal conditions. According to the population analysis, the AlN4-Gr serves as a strong electron donor to aid in the charge transfer between the Al atom and the Oads moiety, which is necessary for the activation of CH4 and C2H4. The findings of the present study may pave the way for a better understanding of the catalytic oxidation the CH4 and C2H4, as well as for the development of highly efficient noble-metal free catalysts for these reactions.

Electrochemical reduction of NO catalyzed by boron-doped C60 fullerene: a first-principles study.

The electrochemical reduction of nitrogen monoxide (NO) is one of the most promising approaches for converting this harmful gas into useful chemicals. Using density functional theory calculations, the work examines the potential of a single B atom doped C60 fullerene (C59B) for catalytic reduction of NO molecules. The results demonstrate that the NO may be strongly activated over the B atom of C59B, and that the subsequent reduction process can result in the formation of NH3 and N2O molecules at low and high coverages, respectively. Based on the Gibbs free energy diagram, it is inferred that the C59B has excellent catalytic activity for NO reduction at ambient conditions with no potential-limiting. At normal temperature, the efficient interaction between the *NOH and NO species might lead to the spontaneous formation of the N2O molecule. Thus, the findings of this study provide new insights into NO electrochemical reduction on heteroatom doped fullerenes, as well as a unique strategy for fabricating low-cost NO reduction electrocatalysts with high efficiency.

Alkali metal decorated C60 fullerenes as promising materials for delivery of the 5-fluorouracil anticancer drug: a DFT approach.

The development of effective drug delivery vehicles is essential for the targeted administration and/or controlled release of drugs. Using first-principles calculations, the potential of alkali metal (AM = Li, Na, and K) decorated C60 fullerenes for delivery of 5-fluorouracil (5FU) is explored. The adsorption energies of the 5FU on a single AM atom decorated C60 are -19.33, -16.58, and -14.07 kcal mol-1 for AM = Li, Na, and K, respectively. The results, on the other hand, show that up to 12 Li and 6 Na or K atoms can be anchored on the exterior surface of the C60 fullerene simultaneously, each of which can interact with a 5FU molecule. Because of the moderate adsorption energies and charge-transfer values, the 5FU can be simply separated from the fullerene at ambient temperature. Furthermore, the results show that the 5FU may be easily protonated in the target cancerous tissues, which facilitates the release of the drug from the fullerene. The inclusion of solvent effects tends to decrease the 5FU adsorption energies in all 5FU-fullerene complexes. This is the first report on the high capability of AM decorated fullerenes for delivery of multiple 5FU molecules utilizing a C60 host molecule.

A DFT investigation into the effects of As-doping on the electronic structure and electrochemical activity of pyrite (FeS2).

Pyrite (FeS2) is a semiconductor mineral with electronic structural properties that are heavily influenced by trace elements in its composition. It has been demonstrated experimentally that the reduction of Fe3+ ions is significantly enhanced in the presence of trace arsenic (As) atoms in FeS2. Using density functional theory calculations, we compare the geometric and electronic structural properties of pure and As-doped (110) pyrite surfaces. The interaction of the Fe3+ ion, a common oxidant of sulfides in acidic solution and acid mine drainage, with the aforementioned surfaces is thoroughly investigated. The findings reveal that the addition of an As atom alters the electronic structure of pyrite and decreases its band gap. The adsorption energy of the Fe3+ ion on As-doped pyrite is greater than that on pure pyrite. The calculated Gibbs free energy changes show that the reduction of Fe3+ to Fe2+ ion on the As-modified surface is thermodynamically more favorable than on pure pyrite.

Silicon-doped boron nitride graphyne-like sheet for catalytic N2O reduction: A DFT study.

In this work, spin-polarized density functional theory calculations are conducted to evaluate the possible applicability of a single Si atom doped boron nitride graphyne-like nansoheet (Si@BN-yne) for reduction of nitrous oxide (N2O). The calculations show that Si-doping in BN graphene is energetically favorable, and the resulting Si@BN-yne is both dynamically and thermodynamically stable. According to our findings, N2O spontaneously dissociates when it interacts with the Si@BN-yne from its O site without the need for an energy barrier, releasing 2.89 eV of energy. The adsorption energy of CO molecule on the Si@BN-yne is less negative than that of N2O, implying that N2O will predominately occupy the catalyst surface. The CO + Oad reaction is used to remove the remaining oxygen atom (Oad) from the Si@BN-yne surface. The calculations show that the reaction proceeds through a low energy barrier of 0.05 eV, which is much lower than the previously reported catalysts. This demonstrates the high catalytic activity of Si@BN-yne nanosheet. Furthermore, the adsorption of H2O and O2 species on the Si@BN-yne nanosheet is investigated. The results show that the presence of these species has no effect on the catalytic activity of the Si@BN-yne for N2O reduction. These results show that the proposed novel Si@BN-yne catalyst can be regarded as an efficient material in the development of promising active catalysts for N2O elimination from the environment.

Ca functionalized N-doped porphyrin-like porous C60 as an efficient material for storage of molecular hydrogen.

It is widely known that decorating metal atoms on defective carbon nanomaterials is a useful approach to enhance the hydrogen storage capacity of these systems. Herein, density functional theory calculations are used to determine the H2 storage capacity of Ca functionalized nitrogen incorporated defective C60 fullerenes (Ca6C24N24). The strong binding, uniform distribution, and significant positive charges of the Ca atoms make this system effective material for storage of H2. Ca6C24N24 may adsorb a maximum of 6 hydrogen molecules per Ca atom, yielding a total gravimetric density of 7.7 wt %.

Catalytic CO oxidation reaction over N-substituted graphene nanoribbon with edge defects.

Density functional theory calculations, including dispersion effects, are used to demonstrate how substitutional nitrogen atoms can improve the catalytic reactivity of graphene nanoribbons (GNR) with edge defects in the CO oxidation process. It is demonstrated that the addition of nitrogen impurities significantly enhances O2 adsorption on GNR. Carbon atoms near the edges of defects are the most active sites for capturing O2 molecules. The lower adsorption energy of CO relative to O2 implies that the N-modified GNR is resistant to CO poisoning. The Eley-Rideal (E-R) mechanism has activation energies as low as 0.38 eV, making it the most energetically relevant pathway for the CO + O2 reaction. The findings of this study might help in the design of catalysts for metal-free catalysis of CO oxidation.