Showing papers on "Chemisorption published in 2023"

Adsorptions of C5F10O decomposed compounds on the Cu-decorated NiS2 monolayer: a first-principles theory

Abstract: This study using the first-principles theory investigates the geometric and electronic properties of Cu-decorated NiS2 (Cu–NiS2) monolayer, and the adsorption and sensing performance of Cu–NiS2 monolayer upon five C5F10O decomposed species, in order to explore its potential to evaluate the operation status of C5F10O-based insulation devices. It is found that the Cu atom prefers to be trapped on the H1 site of the NiS2 monolayer with the formation energy of −3.09 eV without the cluster issue. The chemisorption is determined in the Cu–NiS2/C2F6O3 with an adsorption energy of −1.05 eV, while physisorption is identified in the C3F6, CF2O, C2F6 and CF4 systems. The analyses of electronic property and recovery property reveal the strong potential of Cu–NiS2 monolayer to be a reusable C3F6 or CF2O sensor at room temperature, to be a high-sensitive and one-shot C2F6O3 sensor instead and is not suitable for C2F6 and CF4 sensing due to the low sensitivity. This work is meaningful in terms of proposing novel sensing material for application in the power system to ensure the good operation of C5F10O-based insulation devices. Research Highlights Cu-decorating behaviours on a pristine NiS2 monolayer are studied. The sensing mechanisms of Cu–NiS2 monolayer upon five C5F10O decomposed species are expounded. The sensing potential of Cu–NiS2 monolayer as a resistance-type gas sensor is explored. GRAPHICAL ABSTRACT

Transition Metal-Decorated B12N12–X (X = Au, Cu, Ni, Os, Pt, and Zn) Nanoclusters as Biosensors for Carboplatin

Abstract: Theoretical studies on the adsorption, sensibility, and reactivity of a boron nitride nanocage decorated with Au, Cu, Ni, Os, Pt, and Zn metals as a biosensor material were carried out for the adsorption of carboplatin by applying the density functional theory computation at the B3LYP-GD3BJ/def2svp level of theory. All the optimized structures, as well as the calculations as regards the studied objective including electronic properties, geometry optimization parameters, adsorption energy studies, natural bond orbital analysis, topology studies, sensor mechanistic parameters, and thermodynamic properties (ΔG and ΔH), were investigated herein. As a result, the noticeable change in the energy gap of the studied surfaces when interacting with carboplatin accounted for the surfaces’ reactivity, stability, conductivity, work function, and overall adsorption ability, implying that the studied decorated surfaces are good sensor materials for sensing carboplatin. Furthermore, the negative adsorption energies obtained for interacting surfaces decorated with Cu, Ni, Os, and Zn suggest that the surface has a superior ability to sense carboplatin as chemisorption was seen. Substantially, the geometric short adsorption bond length after adsorption, thermodynamically spontaneous reactions, and acceptable sensor mechanism results demonstrate that the investigated surfaces have strong sensing characteristics for sensing carboplatin.

Powdered and beaded sawdust materials modified iron (III) oxide-hydroxide for adsorption of lead (II) ion and reactive blue 4 dye

Abstract: Abstract The problems of lead and reactive blue 4 (RB4) dye contamination in wastewater are concerns because of their toxicities to aquatic life and water quality, so lead and RB4 dye removals are recommended to remove from wastewater before discharging. Sawdust powder (SP), sawdust powder doped iron (III) oxide-hydroxide (SPF), sawdust beads (SPB), and sawdust powder doped iron (III) oxide-hydroxide beads (SPFB) were synthesized and characterized with various techniques, and their lead or RB4 dye removal efficiencies were investigated by batch experiments, adsorption isotherms, kinetics, and desorption experiments. SPFB demonstrated higher specific surface area (11.020 m 2 g −1 ) and smaller pore size (3.937 nm) than other materials. SP and SPF were irregular shapes with heterogeneous structures whereas SPB and SPFB had spherical shapes with coarse surfaces. Calcium (Ca) and oxygen (O) were found in all materials whereas iron (Fe) was only found in SPF and SPFB. O–H, C–H, C=C, and C–O were detected in all materials. Their lead removal efficiencies of all materials were higher than 82%, and RB4 dye removal efficiencies of SPB and SPFB were higher than 87%. Therefore, adding iron (III) oxide-hydroxide and changing material form helped to improve material efficiencies for lead or RB4 dye adsorption. SP and SPB corresponded to Langmuir model related to a physical adsorption process whereas SPF and SPFB corresponded to the Freundlich model correlated to a chemisorption process. All materials corresponded to a pseudo-second-order kinetic model relating to the chemical adsorption process. All materials could be reused more than 5 cycles with high lead removal of 63%, and SPB and SPFB also could be reused more than 5 cycles for high RB4 dye removal of 72%. Therefore, SPFB was a potential material to apply for lead or RB4 dye removal in industrial applications.

Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia

Abstract: Structurally ordered intermetallic nanocrystals (NCs) and single-atom catalysts (SACs) are two emerging catalytic motifs for sustainable chemical production and energy conversion. However, both have synthetic limitations which can lead to the aggregation of NCs or metal atoms. Single-atom alloys (SAAs), which contain isolated metal atoms in a host metal, can overcome the aggregation concern because of the thermodynamic stabilization of single atoms on host metal surfaces. Here we report a direct solution-phase synthesis of Cu/CuAu core/shell NCs with tunable SAA layers. This synthesis can be extended to other Cu/CuM (M = Pt, Pd) systems, in which M atoms are isolated in the copper host. Using this method, the density of SAAs on a copper surface can be controlled, resulting in both low and high densities of single atoms. Alloying gold into the copper matrix introduced ligand effects that optimized the chemisorption of *NO3 and *N. As a result, the densely packed Cu/CuAu material demonstrated a high selectivity toward NH3 from the electrocatalytic nitrate reduction reaction with an 85.5% Faradaic efficiency while maintaining a high yield rate of 8.47 mol h−1 g−1. This work advances the design of atomically precise catalytic sites by creating core/shell NCs with SAA atomic layers, opening an avenue for broad catalytic applications. Well-defined single-atom alloy (SAA) nanocrystals possess isolated atom centres and tunable electronic properties but are challenging to synthesize. Here, a direct solution-phase synthesis of Cu/CuAu core/shell nanocubes with tunable SAA layers is reported. The Cu/CuAu nanomaterial is highly active for the electrocatalytic conversion of nitrate into ammonia.

Eco-Friendly Anionic Surfactant for the Removal of Methyl Red from Aqueous Matrices

Abstract: This study aimed to evaluate the methyl red (MR) removal efficiency from aqueous matrices using an eco-friendly anionic surfactant (a calcium surfactant, or CaSF), obtained from frying oil residue. Data obtained by infrared spectroscopy revealed several functional groups that favor the capture of the dye by chemisorption by forming hydrogen bonds and covalent interactions. The kinetic testing results fit the pseudo-second order model, reaching equilibrium in 30 min. Adsorption was greatly influenced by temperature. The Langmuir isotherm was the one best fitting the process at 20 °C, while the Dubinin–Radushkevich isotherm fitted it better at higher temperatures. Under optimized conditions, the maximal MR adsorption capacity of CaSF reached 53.59 mg·g−1 (a removal rate of 95.15%), proving that the adsorbent at hand can be an excellent alternative for the removal of undesirable levels of MR present in aqueous matrices.

Atomic layer encapsulation of ferrocene into zeolitic imidazolate framework-67 for efficient arsenic removal from aqueous solutions.

Abstract: Arsenic (As(V))-contaminated water is a major global threat to human health and the ecosystem because of its enormous toxicity, carcinogenicity, and high distribution in water streams. Thus, As(V) removal in the environmental samples has received considerable attention. Till now, numerous metal-organic framework materials have been used for the As(V) removal from the aqueous medium, but low As(V) removal and instability of the adsorbents have severely cut off their practical applications. In this study, a ferrocene-encapsulated zeolitic imidazolate framework-67 (Fc-ZIF-67) material was synthesized for As(V) removal from an aqueous solution at neutral pH using a simple solution mixing process. The ferrocene encapsulation provides water-stable and structural defects to ZIF-67. Furthermore, the ferrocene molecule and imidazole linker can enhance As(V) adsorption via both chemisorption and physisorption. The novel Fc-ZIF-67 adsorbent exhibited superior As(V) adsorption performance with an adsorption capacity of 63.29 mg/g at neutral pH. The Langmuir and Freundlich isotherm models were also used to analyze adsorption behavior.

Aminosilane-Modified Ordered Hierarchical Nanostructured Silica for Highly-Selective Carbon Dioxide Capture at Low Pressure

Abstract: Ordered hierarchical nanostructured silica (OHNS) adsorbents were prepared, and their surface was controllably modified by aminosilanization using two different aminosilanes, one bearing one primary amine unit per molecule (4-aminobutyltriethoxysilane, ABTS) and the other bearing both a primary and a secondary amine (N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, AAMS). Following physicochemical, structural, morphological, and porosity characterization, the CO2 adsorption performance was evaluated at low pressures (up to 100 mbar) and at different temperatures (25, 45, and 60 °C), including determination of CO2 adsorption–desorption, kinetics, CO2/N2 selectivity, regeneration/cycling, heat of adsorption, and CO2 adsorption under humid conditions. The unique hierarchical silica framework together with the aminosilanization scheme applied resulted in enhanced kinetics and CO2 uptake, the latter being increased with temperature, thus revealing a dominant chemisorption mechanism, which was further evidenced by the increase in the enthalpy of adsorption of the modified materials compared to the pristine OHNS. Among the tested adsorbents, at 100 mbar and 25 °C, the OHNS modified by AAMS yielded the highest CO2 uptake under dry (1.3 mmol/g) and wet (1.9 mmol/g) conditions. Notably, at very low pressure (1 mbar), the CO2 capacity of OHNS-AAMS reached >40% of the material’s total uptake at 1 bar. Compared to the unmodified OHNS, the CO2 capacity of the OHNS-AAMS and OHNS-ABTS increased by approximately 21- and 16-fold, respectively, at 1 mbar and 25 °C. At even lower pressure (0.4 mbar), a capacity of 0.55 mmol/g was evidenced for OHNS-AAMS in dry CO2. A very high CO2/N2 selectivity of the AAMS-modified analogue at low pressure was also obtained, i.e., 13,854 at 50 mbar, confirming the significant increase in CO2-philicity via aminosilanization with aminosilanes bearing combined primary and secondary amine groups. Furthermore, the water affinity of the aminosilane-modified OHNS adsorbents was found to decrease, which is beneficial for capture from humid mixtures. Cyclic stability was confirmed by performing 10 thermal pressure swing adsorption (TPSA) cycles up to 100 mbar. The hierarchical nanostructured silica-based framework and the functionalization scheme presented here render these robust systems promising for selective CO2 capture at low pressures in industrial applications and direct air capture.

Synthesis of novel magnetic activated carbon for effective Cr(VI) removal via synergistic adsorption and chemical reduction

Abstract: The removal of a toxic contaminant like Cr(VI) from the water via green adsorbents like biochar and activated carbon is an eco-friendly technique. In this paper, using commercial activated carbon as a raw material, magnetic ferric oxide/activated carbon (Fe3O4@AC) was prepared by the chemical co-precipitation method, and Cr(VI) adsorption in water was applied. The synthesized materials were characterized by advanced characterization techniques including XRD, BET, FT-IR, and XPS. The effects of initial Cr(VI) concentration, temperature, and adsorption time on the adsorption effect of Cr(VI) were evaluated. Results illustrated that the maximum Cr(VI) adsorption achieved by Fe3O4@AC was 45.3 mg/g, with a removal rate of 88.8% at the optimum pH of 2.0 and an adsorption time of 12 h. Under these conditions, Cr(VI) adsorption by Fe3O4@AC fits the pseudo-second-order kinetic model (PSO) and Langmuir isotherm model and is a spontaneous, endothermic, and irreversible process. The results of BET, XRD, FT-IR, and XPS characterization analysis of Cr(VI) before and after adsorption suggested that the adsorption mechanism of Fe3O4@AC is mainly based on chemisorption, supplemented by physical adsorption, accompanied by electrostatic attraction and complexation.

MOF Structure engineering to synthesize core-shell heterostructures with controllable shell layer thickness: Regulating gas selectivity and sensitivity

Abstract: Metal-organic framework (MOF)-derived metal oxide semiconductors have received significant attention for gas sensing applications. Herein, we reported core-shell In2O3@ZnO n-n heterostructures by depositing ZIF-8 derivative onto wrinkled In2O3 sphere, realizing the control of ZnO shell thickness (12.6–72.4 nm) through controlling MOF growth time. Due to the formation of n-n heterojunction at the core-shell interface, the tuning of shell thickness can lead to the radial modulation of the electron-accumulation layer in ZnO, and realizing the control of free charge carrier concentration that participated in gas sensing reaction. What’s more, the MOF-derived ZnO shell with rich oxygen vacancies is beneficial for oxygen chemisorption. Accordingly, compared with the In2O3 based sensor, the In2O3@ZnO based sensor exhibits higher sensitivity to trace-level acetone (100 ppb), faster response time (2 s vs. 100 ppm), better selectivity, and stronger anti-humidity capacity at operating temperature 300 °C, while the thickness of ZnO shell is 55.3 nm. In addition, the increase of ZnO shell thickness can lead to the selectivity change from ethanol to acetone of In2O3@ZnO owing to the inherent catalytic oxidation activity. Thus, the remarkable performance of the In2O3@ZnO sensor mainly relies on ZnO shell layer.

Boosting dual function material Ni-Na/Al2O3 in the CO2 adsorption and hydrogenation to CH4: joint presence of Na/Ca and Ru incorporation.

Abstract: ICCU-methanation is a promising technology that would approach a carbon neutral cycle. In this paper, the feasibility of boosting the activity of the dual function material (DFM) 10Ni-16Na/Al2O3 through the joint presence of Na/Ca and the Ru incorporation is studied. Four DFMs are prepared by sequential wetness impregnation and are extensively characterized by N2 adsorption/desorption, XRD, H2 chemisorption, TEM, STEM-HAADF and temperature-programmed techniques (H2-TPD, CO2-TPD, TPSR, and H2-TPR). The catalytic behaviour of DFMs in the cyclic process of CO2 adsorption and hydrogenation to CH4 is evaluated. The joint presence of Na/Ca improves CH4 production at intermediate-high temperatures by boosting the CO2 adsorption capacity. On the other hand, the Ru incorporation promotes CH4 production at low-intermediate temperatures by presenting synergistic aspects with nickel that lead to a greater number of exposed metal atoms. The Ru incorporation increases the metallic dispersion and the Ni reduction. Finally, the joint presence of Na/Ca and the simultaneous Ru incorporation presents the best activity results. It is concluded that both positive effects are added. Specifically, the DFM 1Ru10Ni-NaCa produces 298 μmol g−1 at 440 °C with a CH4 selectivity of 98.4 %. Furthermore, it is also the most active and selective DFM after hydrothermal aging in the presence of O2.

Transition from chemisorption to physisorption of H2 on Ti functionalized [2,2,2]paracyclophane: A computational search for hydrogen storage

Abstract: In this work, we studied the hydrogen adsorption-desorption properties and storage capacities of Ti functionalized [2,2,2]paracyclophane (PCP222) using density functional theory and molecular dynamic simulation. The Ti atom was bonded strongly with the benzene ring of PCP222 via Dewar interaction. Subsequently, the calculation of the diffusion energy barrier revealed a significantly high energy barrier of 5.97 eV preventing the Ti clustering over PCP222 surface. On adsorption of hydrogen, the first H2 molecule was chemisorbed over PCP222 with a binding energy of 1.79 eV with the Ti metals. Further addition of H2 molecules, however, exhibited their adsorption over PCP222-Ti through the Kubas-type H2 interaction. Charge transfer mechanism during the hydrogen adsorption was explored by the Hirshfeld charge analysis and electrostatic potential map, and the PDOS, Bader's topological analysis revealed the nature of the interaction between Ti and H2. The PCP222 functionalized with three Ti atoms showed a maximum hydrogen uptake capacity of up to 7.37 wt%, which was fairly above the US-DOE criterion. The practical H2 storage estimation revealed that at ambient conditions, the gravimetric density of up to 6.06 wt% H2 molecules could be usable, and up to 1.31 wt% of adsorbed H2 molecules were retained with the host. The ADMP molecular dynamics simulations assured the reversibility by desorption of adsorbed H2 and the structural integrity of the host material at sufficiently above the desorption temperature (300 K and 500 K). Therefore, the Ti-functionalized PCP222 can be considered as a thermodynamically viable and potentially reversible H2 storage material.