Insights on metal doped graphene in the adsorption of arsenic Via dft calculation

Graphene materials and their derivatives have shown promising capabilities in removing anionic and cationic dyes from wastewater. The present study aims at the synthesis of graphene-based material with a high specific surface area and evaluates its use as an adsorbent for removing toluidine blue and methyl violet from aqueous solutions. The physicochemical characterization of the adsorbent before and after dye adsorption is made by XRD, Raman spectroscopy, SEM, TEM, nitrogen physisorption, TG-DTA, and XPS. The influence of the solution's pH, contact time, dye concentration, and temperature on the adsorption efficiency is investigated. The adsorbent demonstrated high adsorption capacity towards toluidine blue (265.2 mg.g-1) and methyl violet (200.4 mg.g-1) dyes from water. The adsorption process for both dyes follows the Langmuir model and involves physical rather than chemical interactions. Kinetic parameters were also determined. The adsorption of the studied cationic dyes can be attributed to a combination of mechanisms, including electrostatic interactions, hydrogen bonding, and π-π interactions between the dye molecules and the aromatic structure of reduced graphene oxide. The findings in the present work highlight the possibilities for enhancing graphene-based materials' adsorption capabilities.

Enhanced VOCs adsorption on Group VIII transition metal-doped MoS2: A DFT study

As2O3 adsorption enhancement over Ni-modified γ-Al2O3 in complex flue gas constituents

(1) Background: The development of highly efficient methods for removing hazardous substances from the environment attracts increasing attention. Understanding the basic principles of the removal processes using graphene materials is equally essential to confirm their application efficiency and safety. (2) Methods: In this contribution, adsorption of pesticide dimethoate (DMT) on graphene-based materials has been investigated on the molecular level. (3) Results: The experimental results’ analysis revealed a cooperative binding mechanism of the DMT on the adsorption sites of investigated materials—graphene oxide (GO) and industrial graphene (IG). The adsorption data were analyzed using various adsorption isotherms to determine the thermodynamics of the adsorption process. The experimental results were correlated with Density Functional Theory (DFT) calculations of DMT adsorption on the model surfaces that appropriately describe the graphene materials’ reactive features. (4) Conclusions: Considering experimental results, calculated adsorption energies, optimized adsorption geometries, and electronic structure, it was proposed that the dispersive interactions determine the adsorption properties of DMT on plain graphene sites (physisorption). Additionally, it was shown that the existence of vacancy-type defect sites on the surfaces could induce strong and dissociative adsorption (chemisorption) of DMT.

Based on density-functional theory (DFT), the effects of metal dopants in HfO2-based RRAM are studied by the Vienna ab initio simulation package (VASP). Metal dopants are classified into two types (interstitial and substitutional) according to the formation energy when they exist in HfO2 cell. Several conductive channels are observed through the isosurface plots of the partial charge density for HfO2 doped with interstitial metals, while this phenomenon cannot be found in HfO2 doped with substitutional metals. The electron density of states (DOS) and the projected electron density of states (PDOS) are calculated and analyzed; it is found that the conduction filament in HfO2 is directly formed by the interstitial metals and further, that the substitutional metals cannot directly generate conduction filament. However, all the metal dopants contribute to the formation of the oxygen vacancy (VO) filament. The formation energy of the VO and the interaction between metal dopants and VO are calculated; it is revealed that the P-type substitutional metal dopants have a strong enhanced effect on the VO filament, the interstitial metal dopants have a minor assistant effect, while Hf-like and N-type substitutional metal dopants have the weakest assistant effect.

First principles insights into the electronic and magnetic properties of [formula omitted] doped with VIII-group transition metal single atom

This work analyses the comparative effects of period-four transition metal (TM) dopants for CO molecular adsorption on the monolayer Graphene (Gr) supercell using the density functional theory (DFT) based ab initio method for the first time. Ten different TM dopant species (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cr, Zn) have been incorporated and extensively studied in the context of Carbon Monoxide (CO) adsorption. The study elaborates on the effects of metallic doping in Gr on structural stability, electronic properties, adsorption strength, transduction efficacy, and CO recovery time. The study reveals that introducing each period-four TM dopant in the Gr lattice changes the semi-metallic nature, wherein distinct modulations in the energy band structure and the total density of state profiles can be observed after CO adsorption in each doped Gr matrix. The C atom of the polar CO molecule preferentially adsorbed on the doped TM, forming physical C-X (X: metal) bonds and resulting in slight vertical displacement of the dopant towards adsorbed CO. The results exhibit that depending on the strength of CO adsorption, the metallic dopants can be placed in the following order: Ti > V > Cr > Mn > Fe > Co > Ni > Cu > Zn > Sc, with a significant improvement in charge transfer during CO adsorption after Sc, Co, Ni, V, and Zn doping in Gr. Specifically, the Ni, Zn, and Sc-doped Gr ensures an efficient trade-off between adsorption stability and recovery time with high selectivity in CO2 and N2 environments.

Dual‐element‐doped graphene has been widely used in the counter electrode due to its enhanced catalytic activity. However, experiments lack a fundamental understanding of the doping effects accounting for the enhanced catalytic activity of dual‐element‐doped graphene. Here, we selected heteroatoms with different electronegativity (e. g., N: 3.0, P: 2.1, Se: 2.4, O: 3.5) based on the C atom with electronegativity of 2.5, then N atoms and heteroatoms co‐doped graphene (N/X‐G, X=P, Se, O) were constructed to investigate the effects of the electronegativity, the doping configuration and position of heteroatoms, the edge structure of graphene on iodine reduction reaction by density functional theory. After a detailed analysis of the electronic structure of N/X‐G, it revealed that the doping of dual‐element could lead to more electrons transfer to the area near heteroatoms, and thus providing more electrons for iodine species. The results of this study indicated that the effects of the dual‐element doping could be divided into three categories, and these principles provide theoretical guidance for further design of the dual‐element‐doped graphene.

Arsenic contamination for drinking water is still a great health hazardous issue for both developed and developing countries. Numerous techniques have been implemented for removing arsenic from drinking water. However, more emphasis has been given on the removal technique related to carbon nanotube absorbent. This study was aimed to investigate the adsorption as well as removal of arsenic using multiwall carbon nanotube as adsorbent or removing material. Arsenic contaminated water was treated in two ways: 1) Batch adsorption and 2) Column feeding system. Removal of arsenic in column technique was found better for each sample. Independent variables including carbon nanotubes dosage, contact time etc. were varied to determine the influence of these parameters on the removal capability of the arsenic from water. From this investigation it was evident that multiwall carbon nanotubes has the capability of adsorption or removal of arsenic. Moreover, it is possible to get water under safe limit using certain amount of nano materials and up to a certain level of contaminated water.

Due to the severity of arsenic contamination of soil and water resources around the world, finding new adsorbents for arsenic removal from the water is of high importance. The present study investigates the possible use and effectiveness of starch-stabilized Fe/Cu nanoparticles for adsorption of arsenic from aqueous solutions. First, Fe/Cu nanoparticles at various starch concentrations of 0, 0.02, 0.04 and 0.06 wt% were synthesized and characterized by X-ray diffraction, transmission electron microscopy and zeta potential/particle size analyzer. Then 0.04 wt% stabilized Fe/Cu nanoparticles were tested for the sorption of As(III) and As(V) from synthetic arsenic-contaminated water. To have an understanding about the arsenic adsorption mechanism of nanoparticles, X-ray photoelectron spectroscopy (XPS) was performed before and after adsorption. The results showed that starch provides nanoparticles with a neutral surface and stabilization of nanoparticles is possible with 0.04 wt% or higher concentrations of starch. For 0.04 wt% starch-stabilized Fe/Cu nanoparticles, the adsorption isotherms fit well within the Langmuir equation, with maximum sorption capacities of 90.1 mg/g for As(III) and 126.58 mg/g for As(V) at a pH of 7.0 from the aqueous arsenic solutions. Examining the XPS spectra of nanoparticles before and after adsorption showed that arsenic adsorption by this nanoparticle can be due to the formation of inner-sphere arsenic complexes on the particle surface, and the surface oxygen-containing functional groups involved in adsorption. The high sorption capacity suggests the potential for applying starch-stabilized Fe/Cu nanoparticles to the contaminated waters for removal of arsenic.

Complex interactions between antibiotics and graphene-based materials determine both the adsorption performance of graphene-based materials and the transport behaviors of antibiotics in water. In this work, such interactions were investigated through adsorption experiments, instrumental analyses and theoretical DFT calculations. Three typical antibiotics (norfloxacin (NOR), sulfadiazine (SDZ) and tetracycline (TC)) and different graphene-based materials (divided into two groups: graphene oxides-based ones (GOs) and reduced GOs (RGOs)) were employed. Optimal adsorption pHs for NOR, SDZ, and TC are 6.2, 4.0, and 4.0, respectively. At corresponding optimal pHs, NOR favored RGOs (adsorption capability: ∼50 mg/g) while SDZ preferred GOs (∼17 mg/g); All adsorbents exhibited similar uptake of TC (∼70 mg/g). Similar amounts of edge carboxyls of both GOs and RGOs wielded electrostatic attraction with NOR and TC, but not with SDZ. According to DFT-calculated most-stable-conformations of antibiotics-adsorbents complexes, the intrinsic distinction between GOs and RGOs was the different amounts of sp(2) and sp(3) hybridization regions: π-π electron donor-acceptor effect of antibiotic-sp(2)/sp(3) and H-bonds of antibiotic-sp(3) coexisted. Binding energy (BE) of the former was larger for NOR; the latter interaction was stronger for SDZ; two species of TC at the optimal pH, i.e., TC(+) and TC(0), possessed larger BE with sp(3) and sp(2) regions, respectively.

Density functional theory study of CO2 adsorption on metal (M=Li, Al, K, Ca) doped MgO

The substitution of Fe with metal dopants shows potential for enhancing the wastewater remediation performance of nanoscale zero-valent iron (nZVI). However, the specific roles and impacts of these dopants remain unclear. To address this knowledge gap, we employed density functional theory (DFT) to investigate metal-doped nZVI on stepped surfaces. Four widely used metal dopants (Ag, Cu, Ni, and Pd) were investigated by replacing Fe atoms at the edge of the stepped surface. Previous research has indicated that these Fe atoms exhibit chemical reactivity and are vulnerable to water oxidation. Our DFT calculations revealed that the replacement of Fe atoms on the edge of the stepped surface is energetically more favorable than that on the flat Fe(110) surface. Our results shed light on the effects of metal dopants on the surface properties of nZVI. Notably, the replacement of Fe atoms with a metal dopant generally led to weaker molecular and dissociated water adsorption across all systems. The results from this study enhance our understanding of the complex interplay between dopants and the surface properties of nZVI, offering theoretical guidance for the development and optimization of metal-doped nZVI for efficient and sustainable wastewater remediation applications.

9 - Graphene-based materials and their potential applications: A theoretical study

Accurate detection and analysis of arsenic pollutants are an important means to enhance the ability to manage arsenic pollution. Infrared (IR) spectroscopy technology has the advantages of fast analysis speed, high resolution, and high sensitivity and can be monitored by real-time in situ analysis. This paper reviews the application of IR spectroscopy in the qualitative and quantitative analysis of inorganic and organic arsenic acid adsorbed by major minerals such as ferrihydrite (FH), hematite, goethite, and titanium dioxide. The IR spectroscopy technique cannot only identify different arsenic contaminants but also obtain the content and adsorption rate of arsenic contaminants in the solid phase. The reaction equilibrium constants and the degree of reaction conversion can be determined by constructing adsorption isotherms or combining them with modeling techniques. Theoretical calculations of IR spectra of mineral adsorbed arsenic pollutant systems based on density functional theory (DFT) and analysis and comparison of the measured and theoretically calculated characteristic peaks of IR spectra can reveal the microscopic mechanism and surface chemical morphology of the arsenic adsorption process. This paper systematically summarizes the qualitative and quantitative studies and theoretical calculations of IR spectroscopy in inorganic and organic arsenic pollutant adsorption systems, which provides new insights for accurate detection and analysis of arsenic pollutants and arsenic pollution control. PRACTITIONER POINTS: This paper reviews the application of infrared spectroscopy in the qualitative and quantitative analyses of inorganic and organic arsenic acid adsorbed by major minerals such as ferrihydrite, hematite, goethite, and titanium dioxide, which can help identify and evaluate the type and concentration of arsenic pollutants in water bodies. In this paper, theoretical calculations of infrared spectra of mineral adsorbed arsenic pollutant systems based on density functional theory reveal the adsorption mechanism of arsenic pollutants in water at the solid-liquid interface and help to develop targeted arsenic pollution control technologies. This paper provides a new and reliable analytical detection technique for the study of arsenic contaminants in water bodies.