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We extend our recent 2D trajectory (x–y plane) and diffusion coefficient data of ceria particles near a glass surface obtained at pH 3, 5, and 7 using evanescent wave microscopy and video imaging to 3D trajectories by analyzing the separation distance between the particles and the glass surface in the vertical z-direction. Mean squared displacement (MSD3D) of ceria particles was calculated to quantify 3D trajectories. Three-dimensional diffusion coefficients were obtained from the MSD3D curves and were compared with two-dimensional diffusion coefficients. By analyzing the MSD curves, we found that ceria particles exhibited only confined motion at pH 3 and 5, while both confined and Brownian motion were showed at pH 7. We also evaluated the cleaning ability of DI water adjusted to pH 10 and 12 to remove ceria particles from glass surfaces and related the results to the calculated trajectory, diffusion coefficient, and interaction potential data.
As the minimum feature size of integrated circuit elements has shrunk below 7 nm, chemical mechanical planarization (CMP) technology has grown by leaps and bounds over the past several decades. There has been a growing interest in understanding the fundamental science and technology of CMP, which has continued to lag behind advances in technology. This review paper provides a comprehensive overview of various chemical and mechanical phenomena such as contact mechanics, lubrication models, chemical reaction that occur between slurry components and films being polished, electrochemical reactions, adsorption behavior and mechanism, temperature effects, and the complex interactions occurring at the wafer interface during polishing. It also provides important insights into new strategies and novel concepts for next-generation CMP slurries. Finally, the challenges and future research directions related to the chemical and mechanical process and slurry chemistry are highlighted.
This paper deals with the adsorption of an essential oil (EO) on a kaolinite-rich clay and a smectite-rich clay. The two clays were modified with a quaternary alkyl ammonium surfactant to create a lipophilic environment for better adsorption of the EO. The preparation of the clay/EO hybrids avoided the use of a slurry and organic solvent. The selected EO was that of Lippia multiflora. This EO has insecticidal properties. The surfactant was trioctyl methylammonium (TOMA). The modified clays were characterized by X-ray diffraction (XRD) and infrared (IR) spectroscopy. The smectite-rich clay displayed greater adsorption of the L. multiflora EO compared to the kaolinite-rich clay. The interlayer space of the kaolinite-rich clay was not affected by the adsorption of the TOMA and/or EO molecules, which suggests that the adsorption in this clay took place on the external surface. By contrast, a significant increase in the interlayer space of the smectite-rich clay was observed, suggesting that the adsorption process of TOMA and/or EO took place on both the external and internal surfaces. The IR analysis showed that the surfactant loading in the interlayer space of the smectite-rich clay introduces a gauche conformation in the alkyl chains. A formulation mixing this local smectite-rich clay and the L. multiflora EO has potential for the manufacture of new biopesticides.
The adsorption and retention of phosphates in soil systems is of wide environmental importance, and understanding the surface chemistry of halloysite (a common soil clay mineral) is also of prime importance in many emerging technological applications of halloysite nanotubes (HNTs). The adsorption of phosphate anions on tubular halloysite (7 Å) has been studied to gain a greater understanding of the mechanism and kinetics of adsorption on the surface of HNTs. Two well-characterized tubular halloysites with differing morphologies have been studied: one polygonal prismatic and one cylindrical, where the cylindrical form has a greater surface area and shorter tube length. Greater phosphate adsorption of up to 42 μmol g–1 is observed on the cylindrical halloysite when compared to the polygonal prismatic sample, where adsorption reached a maximum of just 15 μmol g–1 compared to a value for platy kaolinite (KGa-2) of 8 μmol g–1. Phosphate adsorption shows strong pH dependence, and the differences in phosphate sorption between the prismatic and cylindrical morphologies suggest that phosphate absorption does not occur at the same pH-dependent alumina edge sites and that the lumen may have a greater influence on uptake for the cylindrical form.
In this investigation, Maghnia (Ma) and Mostaganem (Ms) bentonite clays, mined from west Algeria, with no prior affinity for anionic dyes, were modified by simple ion exchange with aqueous Fe3+ solutions, followed by calcination at 500°C. The resulting materials, Fe-Ma and Fe-Ms, respectively, were employed as adsorbents for methyl orange. The starting materials and the two adsorbents were characterized by X-ray diffraction, N2 adsorption–desorption isotherms, Brunauer–Emmett–Teller specific surface area and X-ray fluorescence and by determining the point of zero charge. The effects of various variables, such as initial dye concentration, contact time, adsorbent dose, initial pH and adsorption temperature, were studied. The kinetics were well described by the pseudo-second-order model and the mechanism was determined from the intraparticle diffusion model, while corresponding isotherms fitted better to the Freundlich model. Thermodynamic parameters showed that the adsorption process was endothermic, spontaneous and physical in nature, accompanied by an increase of entropy.
Ab initio calculations are performed to investigate the structural, vibrational, electronic, and piezoelectric properties of functionalized single layers of TaS2. We find that single-layer TaS2 is a suitable host material for functionalization via fluorination and hydrogenation. The one-side fluorinated (FTaS2) and hydrogenated (HTaS2) single layers display indirect gap semiconducting behavior in contrast to bare metallic TaS2. On the other hand, it is shown that as both surfaces of TaS2 are saturated anti-symmetrically, the formed Janus structure is a dynamically stable metallic single layer. In addition, it is revealed that out-of-plane piezoelectricity is created in all anti-symmetric structures. Furthermore, the Janus-type single-layer has the highest specific heat capacity to which longitudinal and transverse acoustical phonon modes have contribution at low temperatures. Our findings indicate that single-layer TaS2 is suitable for functionalization via H and F atoms that the formed, anti-symmetric structures display distinctive electronic, vibrational, and piezoelectric properties.
This work demonstrates a double-step method, a simple chemical bath deposition and an in situ polymerization process, to synthesize the stable structure of a composite of Polyaniline/BiVO4/cellulose aerogel (PBC) in wastewater treatment. The poor stability of the carrier catalyst was improved significantly by forming a dense film of polyaniline (PANI) through polymerization on BiVO4/cellulose aerogel (BC). The developed three-dimensional porous structure enhanced photocatalytic stability. For instance, photocatalytic degradation of a dye, methylene blue, reached to 91.67% under the eight times successive irradiation of the visible light. The resulted fine performance could be owed to the strong adsorption of cellulose aerogel, uniform spreading of BiVO4, and the speedy electron separation efficiency of PBC. Moreover, the photocatalytic mechanisms including the role of the free radicals (•OH and •O2−) of the developed PBC were also discussed. The novel structure may present a new insight into the development of the carrier catalyst.
Clay often has severe detrimental impacts on cement-based materials. Therefore, it is necessary to investigate the mechanism causing the deterioration to improve the service life of cement-based materials. Based on accurate dimensional analysis, a mechanism that influences clay is proposed: the intercalation of the side chains of superplasticizer molecules in the interlayer space of the clay. To lessen this harmful effect, a new clay-resistant admixture (CRA) possessing cationic groups of small molecular size was synthesized through a novel dimensional design. The length and width of the side chains of this superplasticizer molecule were 9.50–17.50 and 0.25–0.40 nm, respectively, with a radius of ~3.74 nm in solvent, which is larger than the interlayer spacing of montmorillonite (i.e. 1.09–2.14 nm). The longitudinal and latitudinal lengths of the CRA molecule were 0.468 and 9.456 nm, respectively, ensuring intercalation in the interlayer of montmorillonite. The increase in interlayer spacing of the clay was 0.364 nm following addition of polycarboxylate superplasticizer (PCE) plus CRA and 0.632 nm following addition of PCE, which suggests that the CRA plays the role of a ‘sacrificial agent’ that is preferentially intercalated into the interlayer space of clay to further prevent the side chains of the superplasticizer molecules from entering the interlayer. The aim of this study was to propose a suitable means of synthesizing a new CRA to address the impact of clay through dimensional design and mechanism analysis, which contributes to the theoretical study and technological improvement of cement-based materials.
Sodium smectite clays were enriched with ferric ions (Argel-Fe and Volclay-Fe) to convert the surface charge of the clays from negative to positive and to use the clays in the discolouration of a synthetic effluent composed of seven anionic dyes (mixed from tartrazine, Brilliant Blue FCF and amaranth). The iron content increased from 5.99% to 11.02% for Argel-Fe and from 5.39% to 10.54% for Volclay-Fe. The efficiency of the discolouration of the anion dye mixture was evaluated by measuring the absorbance of the mixture at 562 nm, where the band with the greatest intensity was found. The contact time required for the system to reach equilibrium was ~5 min for both adsorbents. The kinetic adsorption data supported a pseudo-second-order kinetic model. The experimental data support the dual-site Langmuir–Freundlich isotherm model. The maximum adsorption capacities were 88.68 mg g–1 for Argel-Fe and 392.21 mg g–1 for Volclay-Fe. The enrichment of clays with Fe(III) added functionality to the clays and generated adsorbents with rapid adsorption abilities and high discolouration capacities.
The safe and efficient capture of radioactive iodine is highly necessary, but still remains an ongoing challenge. Herein, because of its special layer structure, CuBi–CO3-layered double hydroxides (CuBi–CO3-LDHs) are used to serve as a generic platform, and 3D hierarchical flowerlike ZIF-67/CuBi–CO3-LDH composites are synthesized by a simple coprecipitation method. After immobilization, the flowerlike morphology of CuBi–CO3-LDHs can be completely preserved and proved by scanning electron microscope. Various affecting factors on adsorption performance are investigated, including adsorbent dose, initial concentration of iodine, and temperature. The experimental and modeling results manifest that iodine adsorption is accurately elucidated by pseudo-second-order model, and the equilibrium isotherm is accordant with the Freundlich model. Moreover, the regeneration experiment indicates that ZIF-67/CuBi–CO3-LDH composites possess good stability and reusability for the removal of iodine. The possible adsorption mechanisms of iodine on ZIF-67/CuBi–CO3-LDHs involve particular layer structure and the strong interaction between nitrogen of imidazole ring and iodine, which were investigated by X-ray diffraction, energy-dispersive X-ray, and X-ray photoelectron spectroscopy spectra. The good performance for the iodine adsorption indicates that ZIF-67/CuBi–CO3-LDHs may be identified as a promising adsorbent in the field of iodine capture.
Using evanescent wave (EW)–based optical detection methods coupled with video microscopy, we investigated in situ trajectories, diffusion, and interaction energies of ∼140 nm ceria particles near a glass surface at pH 3, 5, and 7. Trajectories of a single ceria particle in a 2D (x–y) plane were obtained by linking its time-sequenced positions. Diffusion coefficients of several single ceria particles were calculated from their respective mean-square displacement (MSD) versus time curves, and the results were interpreted based on the interaction potential energy curves obtained from Boltzmann statistics of the EW scattering intensity fluctuations of the particles. The types and characteristics of particle motions were determined by analyzing the MSD curves. Whereas both confined or subdiffusive and Brownian motions of the particles were observed at pH 7, only confined motion was seen at pH 3 and 5, and their corresponding diffusion coefficients are similar to those reported by several authors.
Detailed report on MOFs for CO2 adsorption on the basis of ligands employed, OMSs, and structures. Systematic report on the high- and low-pressure CO2 capture. Report on the mechanism of CO2 capture.
A review on the promising field of MOF-based carbon capture and storage is presented. We discuss here the main features of MOFs applicable for CO2 capture and separation, the linker functionalization role, and the most important CO2-binding sites as also the most efficient and significant technologies, and a systematic report on the high- and low-pressure CO2 capture.
Role of MOFs in CO2 chemical conversion; Photocatalytic and electrocatalytic CO2 reduction; Role of linkers and metals in CO2 chemical conversion; and MOF composites and films in CO2 conversion.
In this review, we analyze the emerging field of metal–organic frameworks (MOFs) as catalysts for chemical conversion of CO2, with examples ranging from heterogeneous CO2 organic transformation to heterogeneous CO2 hydrogenation, from photocatalytic to electrocatalytic CO2 reduction. We also discuss the role of MOF composites and films in CO2 transformation. Our goal is to have an instrument useful to identify the best MOFs for CO2 conversion.
The deficient disposition of the pruning waste, from grass (Poaceae), has been converted into a considerable environmental problem since it is discarded in common garbage dumps. As a result, gases and lixiviates are generated producing a negative impact on the environment. This project takes advantage of these residues to isolate their chloroplasts, with the aim of subsequently developing bioreactors that absorb CO2. The encapsulation of grass chloroplasts into silica monolith with a hierarchical texture, using high internal phase emulsion (HIPE) method was carried out. The isolated chloroplasts were analysed by UV-Vis spectroscopy to estimate the amount of chlorophylls a and b present in the grass. Moreover, the synthesized samples were characterized by fluorescence spectroscopy for monitoring their photosynthetic activity, having an activity up to at least 90 days.
The initial steps of the thermal chemistry of Cu(I)-2-(tert-butylimino)-5,5-dimethyl-pyrrolidinate on metal surfaces were characterized using temperature-programmed desorption experiments and density functional theory (DFT). The relative stability of the initial dimer relative to its dissociation on metal surfaces was evaluated. Several molecular desorption temperatures were identified on Ni(110), but all correspond to dimers, either containing the initial Cu ions or after their removal; no monomer was ever detected. DFT calculations also indicated preferential bonding on Cu(110) as a dimer, albeit with a distorted configuration, via the Cu atoms and in registry with the lattice of the substrate. A potential dissociation pathway of the adsorbed dimer was identified involving the partial detachment of the ligands via the scission of one Cu–N bond at the time and migration to adjacent surface sites. This process is accompanied by the reduction of the Cu centers of the metal–organic complex, indicating that it may be the rate-limiting reaction that leads to further fragmentation of the ligands.
This work examines a tuff from the Tinebdar deposit located in Sidi Aich (east Algeria) for possible use as an alternative material for the adsorption of Asucryl red (a textile dye). Natural tuff represents an economic and environmentally friendly alternative compared to synthetic zeolites. The starting materials were characterized by means of powder X-ray diffraction, Brunauer–Emmett–Teller-specific surface area and pore diameter analysis. Batch experiments were performed and various parameters that have an effect on the adsorption process (i.e. pH, clay amount, contact time and initial concentration) were investigated. The <125 μm grain-size fraction of the tuff contains 45 wt.% mordenite. The adsorption equilibrium was established in 10 min and the adsorption kinetics were better described by the second-order kinetic model. The adsorption isotherm of the results obtained fits better to the Langmuir and Timkin models. The adsorption capacity qt varies from 60 to 70 mg g–1 with temperature increasing from 293 to 333 K. The thermodynamic nature of the adsorption process was determined by calculating ΔH°, ΔS° and ΔG° values. The positive value for ΔH° confirms that the adsorption is endothermic.
Polypropylene plastic (PP) was chosen as additives for the preparation of activated carbon (AC), considering that PP promotes pore formation during the preparation of AC. When the addition ratio of PP was 20%, AC having a maximum specific surface area of 1916.1 m2/g was prepared. Fourier transform–infrared spectroscopy (FT-IR) analysis exhibited the types of functional groups on the surface of AC, such as–OH, C=O, C–C, and –CH. The SEM analysis revealed the formation of disordered pores over the AC. Furthermore, iodine value of the AC is 1460 mg/g. Additionally, adsorption test revealed the AC is suitable for adsorbing methylene blue (MB). The adsorption equilibrium data of MB onto AC were most suitable for Redlich–Peterson model. The maximum adsorption capacity of the single layer was 476.88 mg/g, indicating that AC has high adsorption capacity. The kinetic data fitted well with the pseudo-second-order model.
Biochar conversion from corn stover was evaluated under various process conditions, and the absorption capacity of biochar was investigated for the removal of oxytetracycline in wastewater. Biochar was prepared at lower carbonization temperatures (200–500 °C) and was used in three different concentrations of chemical oxygen wastewater. The results showed that the biochar prepared at the temperature range of 200–500 °C had a faster sorption rate and shorter sorption equilibrium time compared to biochar produced at higher temperatures. The longest time to reach sorption equilibrium was 9 h for biochar obtained at 200 °C. However, the biochar prepared at 500 °C required only 0.5 h to reach the sorption equilibrium. The corn stover-biochar had the highest sorption capacity of 246.3 mg/g for oxytetracycline at 30 °C. The adsorption kinetics was consistent with pseudo–second-order kinetics. This study provides a theoretical basis for the conversion of corn stover into biochar as efficient sorbents.
The present work describes the removal of Direct Red 81, Methyl Orange, Methylene Blue and Crystal Violet from aqueous solution using halloysite nanotubes. The clay mineral was physicochemically characterized using various methods. The influences of pH, interaction time, initial dye concentration, adsorbent amount and temperature on adsorption were monitored and interpreted. Although previous work has shown that acidic pH conditions favour the adsorption of pollutants from aqueous systems by clay materials, in this study maximum removal was possible over a wide range of pH conditions (pH ≥2–12). Adsorption was very rapid, and equilibrium was attained within 30 min. For all four dyes studied, chemical reaction seemed significant in the rate-controlling step, and the pseudo-second-order chemical reaction kinetics provided the best correlation of the experimental data. Thermodynamically, the process was spontaneous, with Gibbs energy decreasing with increasing temperature. Halloysite would be suitable for removing dyes from aqueous solution. This was further tested by using the halloysite nanotubes for the removal of complex dyes from printing and ink industry effluents.
Nano/mesoporous carbon was prepared from pine wood sawdust via the pretreatment of acid and hydrothermal process, followed by potassium hydroxide (KOH) activation. This study proposed the enhancement of activated carbon (AC) adsorption capacity by utilizing the vacant sites and phenomena of opposite charge attraction via multilayer adsorption of Cr(VI) ions and dyes with positive and negative charges. On the first layer, the maximum adsorption capacities for Cr(VI) ions, methylene blue (MB) molecules, and acid red 18 (AR18) molecules onto AC were found to be 7.91 mg/g, 476.19 mg/g, and 434.78 mg/g, respectively. For multiple adsorption, after Cr(VI) ions uptake saturation, the sequential adsorption of MB and AR18 on the second layer, the maximum adsorption capacity, reached 322.58 mg/g and 333.33 mg/g. After MB and AR18 uptake saturation, the maximum Cr(VI) adsorption capacity reached 2.92 mg/g and 4.39 mg/g.