Successive Adsorption Research Articles

Swelling Degree of Polyelectrolyte Layers Determined by an Electrochemical Quartz Crystal Microbalance.

Various polycations and polyanions were sequentially adsorbed onto the gold electrode of a quartz crystal microbalance with dissipation monitoring. The study focused on determining the adsorption kinetics, viscoelastic properties, and electroresponsivity of polyelectrolyte layers. For the first time, it was demonstrated that the structure (compact or expanded) of the layers can be determined by electroresponsivity. Viscoelastic modeling alone did not provide a conclusive answer as to whether the layers were compact or expanded. The study was further enriched by streaming potential and contact angle measurements, where polyelectrolyte multilayers were formed on mica. It was found that successive adsorption of layers led to periodic inversion of the zeta potential. Systematic differences were observed between the different top layers, which were explained by intermixing between layers. The presence or absence of interpenetration, as determined by the measurements of streaming potential and contact angles, correlated well with electroresponsivity.

Tailored large-particle quantum dots with high color purity and excellent electroluminescent efficiency.

High-quality quantum dots (QDs) possess superior electroluminescent efficiencies and ultra-narrow emission linewidths are essential for realizing ultra-high definition QD light-emitting diodes (QLEDs). However, the synthesis of such QDs remains challenging. In this study, we present a facile high-temperature successive ion layer adsorption and reaction (HT-SILAR) strategy for the growth of precisely tailored Zn1-xCdxSe/ZnSe shells, and the consequent production of high-quality, large-particle, alloyed red CdZnSe/Zn1-xCdxSe/ZnSe/ZnS/CdZnS QDs. The transitional Zn1-xCdxSe/ZnSe shells serve to effectively suppress heavy hole energy level splitting and weaken the exciton-longitudinal optical phonon coupling of QDs, thus facilitating the formation of highly luminescent QDs with a near-unity photoluminescence quantum yield of 97.8% and narrow emission with a full width at half maximum of 17.1nm. In addition, the introduction of transitional shells can extend the particle size of QDs to 19.0nm, which is beneficial for efficient carrier recombination and reduced Joule heating in QD-based LEDs. As a result, the fabricated QLEDs can achieve a record external quantum efficiency of 38.2%, luminance over 120,000cdm-2, and exceptional operational stability T95 (tested at 1,000cdm-2) of 24,100h. These findings provide new avenues for synthesizing high-quality QDs with high color purity.

Develop Reusable Carbon Sub-Micrometer Composites with Record-High Cd(II) Removal Capacity.

Cd(II)-induced pollution across diverse water bodies severely threatens ecosystems and human health. Nevertheless, achieving ultra-efficient and cost-effective treatment of trace amounts of heavy metals remains a major challenge. Herein, the novel carbon sub-micrometer composites (CSMCs) supported Fe0@γ-Fe2O3 core-shell clusters nanostructures are designed and synthesized through a series of universally applicable methods. Research data on adsorption behavior clearly revealed that resorcinol/formaldehyde 1.25-basic ferric acetate (RF-1.25BFA) and RF-1.25BFA-540 have surprising adsorption capacities. Employing the adsorbent dosage of 0.025gL-1, the adsorption capacities for 10mgL-1 Cd(II) reached 400.00mgg-1 with ultrafast adsorption kinetics, alongside theoretical maximum adsorption capacities for Cd(II) of 1108.87 and 1065.06mgg-1 using 0.025gL-1 adsorbent, respectively, setting a new record-high level. Additionally, they demonstrated exceptional stability and reusability, maintaining Cd(II) removal efficiency above 95% even after 15 adsorption-desorption cycles. Importantly, this study is the first to unveil a new ultrafast successive two-step enrichment-hydrolysis adsorption mechanism for Cd(II) removal, emphasizing the critical role played by iron clusters nanostructures in constructing a high-alkalinity adsorption microenvironment on the surface of the materials. The findings reported pioneered a new avenue for the rational design of high-performance environmental remediation materials, aiming to overcome the limitations of traditional mine drainage treatment.

Photoanode/Electrolyte Interface Modification for Efficient Hydrogen Evolution in Cu2SnS3 Dots-Sensitized Solar PEC Cells.

It is proven through transmission electron microscope (TEM) analysis that solar sensitizer Cu2SnS3 (CTS) dots prepared via the hot-injection route are nonspherical, polyhedral nanocrystals with the size of ∼11 nm. CTS dots were deposited into a porous TiO2 layer to form CTS/TiO2, an effective type II heterojunction in photoanodes. The electronic and energy band structures of TiO2 and CTS were studied by the plane-wave ultrasoft pseudopotential method based on density functional theory (DFT) and verified by ultraviolet-visible (UV-vis) spectroscopy. UV-vis and Photoluminescence (PL) spectra show that the CTS/TiO2 photoanode exhibits wider visible-light absorption as well as lower charge recombination. ZnS quantum dots (QDs) deposited on the CTS/TiO2 photoanode through the in situ successive ion layer adsorption and reaction (SILAR) method as the passivation layer can inhibit the reverse carrier transfer and increase the photocurrent density by building a potential barrier on the CTS/TiO2 photoanode and electrolyte interface. When 2-layer ZnS QDs are deposited, the maximum photocurrent density of the photoelectrochemical (PEC) cell composed of a ZnS/CTS/TiO2 photoanode, a Pt counter electrode, and Na2SO4 solution electrolyte is 8.43 mA/cm2 and the maximum applied bias photon-to-current efficiency (ABPE) is 7.79%. Under 1 sun (AM 1.5, 100 mW/cm2) with 0.6 V bias, its hydrogen yield reached 125.7 μmol·cm-2 after 4 h with the rate of 31.4 μmol·cm-2·h-1 in contrast to the yield of 107.86 μmol·cm-2 with the rate of 21.3 μmol·cm-2·h-1 for the CTS/TiO2 photoanode.

Enhanced VOCs adsorption over ZSM-5 nanosheets with different thicknesses along the b-axis

A systematic study was conducted on the effect of the b-axis thickness on the adsorption/desorption properties of representative VOCs (toluene and dichloromethane) by varying the diffusion resistance over ZSM-5 nanosheets. ZSM-5 nanosheets with about 30 nm thickness along the b-axis (Z5-3) presented a 1.3-fold higher adsorption capacity (83.9 mg/g) and 27 % enhancement in breakthrough times for toluene (38 min) compared with conventional ZSM-5 (Z5-4). Dichloromethane adsorption capacity on Z5-3 (micropore volume of 0.12 cm3/g) was approximately 53 % higher than that on Z5-4 (micropore volume of 0.08 cm3/g) and only weekly correlated to the b-axis thickness due to its small molecular size. The adsorption isotherms and molecular dynamic simulations indicated that a shorter b-axis thickness enhanced the diffusion of toluene (3.9 × 10-5 cm2/s) and dichloromethane (7.2 × 10-5 cm2/s), as well as the toluene adsorption capacities over ZSM-5 samples. The toluene and dichloromethane physisorption mechanism was verified by adsorption kinetics. Additionally, the toluene and dichloromethane adsorption capacities of all samples decreased by about 33 % and 21 % at a relative humidity (RH) of 50 % at 298 K, respectively. This indicated that the structure of ZSM-5 samples did not significantly affect their hydrophobicity. Moreover, according to the competitive adsorption test results, toluene and dichloromethane underwent successive co-adsorption, competitive adsorption, and equilibrium adsorption. These findings are useful for designing high-performance and cost-effective zeolite adsorbents to efficiently remove volatile organic compounds from industrial sources.

Poly (acrylic acid-co-2-hydroxyethyl methacrylate)-grafted gum ghatti hydrogel for capturing heavy metal ions

In this work, a facile route is explored for the synthesis of a novel polymer composite-based hydrogel (PC-hydrogel). The ratio of 2-(Hydroxyethyl) methacrylate (HEMA) and acrylic acid (AA) is optimized first based on Fourier transform infra-red spectroscopy, swelling ratio (SR%) and surface negative charge (PZC). Results indicate that PC-hydrogel composed of copolymer of HEMA: AA in 1:4 ratio is optimized, for grafting on Gum ghatti (Gg) during free-radical graft copolymerization process. Among all other possible combination of HEMA: AA, 1:4 ratio grafted Gg is termed as PC-hydrogel [Poly (AA-co-HEMA)-g-Gg]. PC-hydrogel exhibited negative surface charge over a wide range of pH owing to increase in AA. The swelling (g/g) and water retention ratio (%) of the prepared hydrogel have been found to be 342.6, 385 & 412.6 g/g and 74.83, 65.30 & 57.86 % in grey, tap and distilled water respectively. Furthermore, PC-hydrogel is applied for capturing Cu2+ and Co2+ ions in aqueous phases. Experimental results showed that adsorption process was pH-dependent, and the maximum capturing of Cu2+ and Co2+ was observed at neutral pH 7. Among different adsorption isotherms models like Langmuir, Freundlich, and Temkin models, experimental data fitted closely with the Langmuir adsorption model showing a maximum adsorption capacity of 381.67 and 328.94 mg/g for Cu2+ and Co2+ respectively. The capturing of metal ion followed pseudo-second-order rate model [rate constant k = 1.7 x 10−4 for Cu2+ and 1.5 x 10−4 for Co2+ g/(mg.min)]. The PC-hydrogel property retained its uptake capacity of metal ions up to the three successive adsorption−desorption cycles, and exhibited higher selectivity towards Cu2+ and Co2+ and other (NaCl, MgCl2, CaCl2) coexisting ions.

Investigation of the double layer structure of 1-butyl-3-methylimidazolium thiocyanate at the air-water interface using sum-frequency generation vibrational spectroscopy.

The interfacial structure and adsorption behavior of 1-butyl-3-methylimidazolium thiocyanate ionic liquids (ILs) aqueous solutions were investigated using sum-frequency generation vibrational spectroscopy (SFG-VS) and surface tension measurements. Polarization-dependent measurements revealed a dramatic increase in the SFG signal for both CH and CN stretching modes with increasing ILs concentration, reaching a maximum at a mole fraction of 0.01. This concentration dependence was accompanied by a dramatic drop in surface tension. Upon further increasing the concentration, surface tension varied slightly and reached a constant value, while the SFG signal decreased significantly. Quantitative polarization analysis showed that as the bulk concentration increased, the apparent molecular orientation of the SCN- transition dipole at the interface changed from 51° to 46°, and the tilt angle of CH3 group of the butyl chain attached to the imidazole cationic ring changed from 18° to 32°. The decrease in the SFG signal can be explained by the formation of a double layer adsorption structure at the air/water interface. It was also demonstrated that the anions were adsorbed at the interface simultaneously with the cationic group, rather than by successive adsorption as proposed in a previous study. Using the Shereshefsky model, the thermodynamic Gibbs free energy of adsorption deduced from surface tension data was compared with SFG results.

Seed-assisted two-step ZIF-67 growth on CS/PVA nanofibers for high-efficiency cadmium and tetracycline adsorption

Herein, novel ZIF-67/CS/PVA (CNF-2) nanofiber composites using a two-step seed-assisted in situ electrospinning method, with cobalt-based zeolitic imidazolate framework (ZIF-67) as the precursor was prepared. SEM, EDX, AFM, FTIR, and XRD analyses revealed the optimal formation of ZIF-67 nanoparticles both inside and on the surface of CS/PVA nanofibers without compromising the structure of these electrospun nanofibers. The unique porous structure and heterointerfaces of the ZIF-67/CS/PVA (CNF-2) nanofiber composites demonstrated remarkable adsorption capacities for cadmium (Cd) and tetracycline hydrochloride (TCH), achieving 1137.94 and 1029.5 mg/g, respectively. The adsorption effectiveness for Cd and TCH was 94.83 % and 85.79 %, respectively, under optimal adsorption conditions: pH 8, adsorbent dosage of 0.01 g, initial Cd and TCH concentration of 80 mg/L, and a contact time of 120 min. The study of coexisting Cd and TCH adsorption on CNF-2 under varying pH conditions (4–8) reveals a significant enhancement in Cd adsorption efficiency, increasing from 41.91 % to 97.49 %. Conversely, TCH exhibits a more modest improvement, with its adsorption efficiency rising from 72.53 % to 85.96 %. Kinetic and equilibrium studies revealed that the adsorption followed pseudo-second-order kinetics and the Langmuir isotherm. The prepared nanofiber adsorbed 60 % of Malachite green dye. The engineered adsorbent demonstrated impressive regeneration potential, maintaining its efficiency over three successive adsorption–desorption cycles.

Hydrogen storage capacity on vanadium decorated graphene

In the present study we performed Density Functional Theory (DFT) calculations to study the decorated Vanadium (V) on graphene sheet (Gr-V) as well. We adsorbed 6H2 molecules on V decorated graphene surface. The calculated total energy (Etotal) for pristine graphene and complex system Gr-V found –223.718 Ry and −368.95557 Ry respectively. After successive adsorption of molecular hydrogen, the total energy found in the range of −371.308 Ry to −382.523 Ry. We investigated the Fermi energy in increasing order within the range of 0.898 eV to 3.135 eV, The evaluated binding and Fermi energies confirms the Vanadium candidate is more suitable for hydrogen storage capacity of the studied system. On the basis of the extracted results, we can infer that the decorated hydrogen molecule (1H2-6H2) has the sufficient gravimetric capacity of V decorated graphene. The density of states (DOS) confirms the weak interaction between σ bonding electrons of H2 molecule (1H2-6H2) with the vanadium (V) decorated graphene complex system. Our reported complex system (Gr-V-1H2-6H2) is feasible for a promising material to store hydrogen molecules (H2) moreover.

Performance evaluation of SILAR deposited Rb-Doped ZnO thin films for photodetector applications

ZnO-based photodetectors (PDs) compose a remarkable optoelectronic device field due to their high optical transmittance, electrical conductivity, wide band gap, and high binding energy. This study examined the visible light photodetector performance of the pristine and Rubidium (Rb)-doped ZnO thin films. The influence of Rb doping amount (2, 4, and 6 wt% in solution) on the electrical, optical, and structural properties of the ZnO-based thin films produced by the Successive Ion Layer Adsorption and Reaction (SILAR) technique was analyzed. Structural analyses showed that all peaks correspond to hexagonal wurtzite structure with no other peak from Rb-based phases, suggesting the high quality of the crystalline pristine and Rb-doped ZnO thin films. The morphology of the thin films shows homogenous layers formed of nanoparticles where particle size was first decreased and then increased with the increasing Rb doping according to Scanning Electron Microscope (SEM) morphology analysis. Besides that, Raman spectroscopy analyses indicate that the phonon lifetimes of the ZnO-based thin films slightly increased due to the improvement of the crystal quality with the increasing amount of Rb in the SILAR solution. Photosensor measurements of the nanostructured pristine and Rb-doped ZnO thin films were measured at different light power intensities under the visible light environment. Photosensor properties were examined depending on the doping amount and light power density. In light of the literature review, our study is the first to produce Rb-doped ZnO thin films via the SILAR method, which has a promising potential for photosensor applications.Graphical

Effects of Rapid Heat Treatments on the Properties of Cu2O Thin Films Deposited at Room Temperature Using an Ammonia-Free SILAR Technique

We report herein the analysis of the properties of copper(I) oxide thin films deposited by an optimized ammonium-free successive ion layer adsorption and reaction (SILAR) technique. The Cu2O thin film deposition process was carried out at room temperature using copper acetate monohydrate, sodium citrate as complexing agent, and hydrogen peroxide as precursors of copper and oxygen ions, respectively. The harmless and easy-to-handle sodium citrate replaces the volatile NH4OH commonly employed as complexing agent in the SILAR technique for the deposition of metal oxide thin films. The optical, structural, morphological, and electrical properties of the as-deposited Cu2O thin films were studied as a function of the number of cycles during deposition, as well as their modifications produced by the effect of rapid thermal annealing (RTA) in vacuum in a temperature range of 200–250°C for 1 min, 3 min, and 5 min. The as-deposited thin films had cubic crystalline structure corresponding to the Cu2O phase as determined by x-ray diffraction (XRD), with a direct energy bandgap of 2.43–2.51 eV depending on the number of cycles, and electrical resistivity of the order of 103 Ω cm. The XRD and x-ray photoelectron spectroscopy (XPS) analysis of the Cu2O thin films treated by RTA demonstrated an increase of the crystal size with time and temperature of the RTA and reduction effects from Cu2+ to Cu1+ oxidation states. On the other hand, the RTA treatments also decreased their energy bandgap to 2.38 eV and electrical resistivity to 102 Ω cm. The high energy bandgap values of the Cu2O thin films were attributed to quantum confinement effects produced by their small crystal size in the range of 3.6–8.6 nm.Graphical

Effect of Precursors Concentration on The Optical and Photoelectrochemical Properties of Bi₂S₃/TiO₂ Nanotubes Arrays Photoanode Synthesized by the SILAR Technique

The use of robust solar energy-driven photocatalysis materials to address the global energy and environmental crisis has gained significant attention in recent years. However, the wide band gaps in many robust semiconductor photocatalysts hinder their absorption of visible light from the solar spectrum. To address this issue, the modification of the large band gap semiconductor with the lower band gap material using the Successive Ionic Layers Adsorption and Reaction (SILAR) technique has emerged as an economical, accessible, and reproducible method for depositing nanoscale materials onto semiconductor substrates. This research aims to know how the concentration variation of cation and anion precursors in the SILAR technique affects the optical and photoelectrochemical properties of the resulting composite materials. Bi₂S₃ serves as a modifier for TiO₂ nanotube arrays (NTAs). The result shows that the cation-anion concentration ratio of 1:1.5 mM with five SILAR cycles gives the best photoelectrochemical performance, with a stable current density of 0.12 mA/cm², compared to pristine TiO₂ NTAs the current density of Bi₂S₃/TiO₂ NTAs is 15-fold. In addition, at each variation, the concentration ratio of cation and anion precursors decreases bandgap energy with each increase in the SILAR cycle.

Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures.

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100ps) and electron (∼1ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Synthesis and application of dual-functional sorbent SBA-15-Fe3O4-PDA-ODA for removing both water soluble and insoluble pollutants

In this study, inorganic-organic hybrid sorbent SBA-15-Fe3O4-PDA-ODA with functional groups having affinity for both water-soluble and insoluble pollutants was synthesized for treatment of wastewater where Malachite Green (MG) dye and motor oil coexist. In order to enhance the specific interactions between the sorbent and dye via functional groups of polydopamine (PDA), Fe3O4 nanoparticles were encapsulated with SBA-15 and surface functionalization with PDA was accomplished and then the surface of Fe3O4-SBA-15-PDA was modified with octadecylamine (ODA) to remove the oil present in the same environment with dye. While the SBA-15-Fe3O4-PDA-ODA directed to the aqueous phase by magnet provided MG removal thanks to the hydrophilic groups of PDA, it provided motor oil removal thanks to hydrophobicity of ODA when directed to the oil phase. 99.20 % dye removal and 9.24 g/g oil adsorption capacity were achieved from the environment where oil and dye were present together. Besides, the adsorption of MG on Fe3O4-SBA-15-PDA was searched at various pH, dye concentration, adsorbent dosage, and temperature in order to propose optimum experimental conditions for removal of dye and maximum adsorption capacity was determined as 95.83 mg g−1 at optimum conditions (10 mg adsorbent, 10 mg L−1 MG concentration, pH 9). Interaction mechanism between dye and Fe3O4-SBA-15-PDA was explained by studying the adsorption behavior of sorbent derived from the isotherm and kinetic results. The sorbents were characterized by FT-IR, XRD, SEM, N2-adsorption/desorption, water-contact-angle, and VSM measurements. SBA-15-Fe3O4-PDA-ODA sorbent was tested for three successive adsorption cycles for both dye and oil and eventuated insignificant loss in activity when they were recycled. Easy and low-cost fabrication protocol, controllable removal ability of dye and oil will facilitate its versatility in environmental cleanup process for water soluble and insoluble pollutants.

Highly efficient photoelectrochemical aptasensor based on CdS/CdTe QDs co-sensitized TiO2 nanoparticles designed for thrombin detection.

A photoelectrochemical (PEC) sensor for the sensitive detection of thrombin (TB) was established. Co-sensitized combination of TiO2 nanoparticles combined with modified cadmium sulfide and cadmium telluride quantum dots (CdS/CdTe QDs) was utilized as a photoactive material. Successful growth of CdS/CdTe quantum dots on mesoporous TiO2 films occuredby successive ion-layer adsorption and reaction. This interesting formation of co-sensitive structure is conducive to enhancing the photocurrent response by improving the use rate of light energy. Additionally, the step-level structure of CdS/CdTe QDs and TiO2 NPs shows a wide range of visible light absorption, facilitating the dissociation of excitons into free electrons and holes. Consequently, the photoelectric response of the PEC analysis platform is significantly enhanced. This constructed PEC aptasensor shows good detection of thrombin with a low detection limit (0.033pM) and a widelinear range (0.0001-100nM) in diluted actual human serum samples. In addition, this PEC aptasensor also has the characteristics of good stability and good reproducibility, which provides a novel insight for the quantitative measurement of other similar analytes.

Synthesis of the Ag2S/PANI@PES Composite Membrane and Its Antipollution Properties.

Membrane separation technology offers a sustainable and efficient solution to wastewater management; however, membrane fouling significantly impedes its application. Photocatalytic membranes, integrating photocatalytic and membrane separation technologies, enhance membrane separation efficacy while effectively mitigating organic and biological contaminations. In this work, Ag2S/PANI@PES composite membranes were prepared via a facile in situ polymerization and successive layer adsorption technique. The modified poly(ether sulfone) (PES) membrane demonstrated improved hydrophilicity and separation performance, and its heterostructure between polyaniline (PANI), Ag0, and Ag2S effectively addressed organic fouling issues. Moreover, Ag2S/PANI@PES exhibited outstanding antimicrobial properties, as well as chemical and mechanical stability.

A Photoelectrochemical Sensor for the Sensitive Detection of Cysteine Based on Cadmium Sulfide/Tungsten Disulfide Nanocomposites.

In this work, a CdS-nanoparticle-decorated WS2 nanosheet heterojunction was successfully prepared and first used to modify ITO electrodes for the construction of a novel photoelectrochemical sensor (CdS/WS2/ITO). The thin-film electrode was fabricated by combining electrophoretic deposition with successive ion layer adsorption and reaction techniques. The results indicated that the synthesized heterojunction nanomaterials displayed excellent photoelectrochemical performance which was much better than that of pristine CdS nanoparticles and 2D WS2 nanosheets. Owing to the formation of the surface heterojunction and the effective interfacial electric field, the enhanced separation of photogenerated electron-hole pairs led to a remarkable improvement in the photoelectrochemical activity of CdS/WS2/ITO. This heterojunction architecture can protect CdS against photocorrosion, resulting in a stable photocurrent. Based on the specific recognition between cysteine and CdS/WS2/ITO, through the specificity of Cd-S bonds, a visible-light-driven photoelectrochemical sensor was fabricated for cysteine detection. The novel photoelectrochemical biosensor exhibited outstanding analytical capabilities in detecting cysteine, with an extremely low detection limit of 5.29 nM and excellent selectivity. Hence, CdS-WS2 heterostructure nanocomposites are promising candidates as novel advanced photosensitive materials in the field of photoelectrochemical biosensing.

To What Extent Do Iodomethane and Bromomethane Undergo Analogous Reactions?

Iodomethane and bromomethane (CH3I/CH3Br) are common chemicals, but their chemistry on nanometals is not fully understood. Here, we analyze the reactivity of Rhn+ (n = 3-30) clusters with halomethanes and unveil the spin effect and concentration dependence in the C-H and C-X bond activation. It is found that the reactions under halomethane-rich conditions differ from those under metal-rich conditions. Both CH3I and CH3Br undergo similar dehydrogenation on the Rhn+ clusters in the presence of small quantity reactants; however, different reactions are observed in the presence of sufficient CH3I/CH3Br, showing dominant Rh(CH3Br)x+ (x = 1-4) products but a series of RhnCxHyIz+ species (x = 1-4, y = 1-12, and z = 1-5) pertaining to H2, HI, or CH4 removal. Density functional theory calculations reveal that the dehydrogenation and demethanation of CH3Br are relatively less exothermic and will be deactivated by sufficient gas collisions if helium cooling takes away energy immediately; instead, the successive adsorption of CH3Br gives rise to a series of Rh(CH3Br)x+ species with accidental C-Br bond dissociation.

Evolution of structural features in GO/CdS multilayer films for advanced optoelectronic devices

In this work graphene oxide/cadmium sulphide [GO/CdS]n multilayer films were obtained onto FTO/SLG substrates by cyclic electrophoretic deposition (EPD) and successive ion layer adsorption and reaction (SILAR) methods, with 3, 5, 7 and 10 cycles. The optical characterization for 3 cycles sample exhibits an optical band gap of ∼2.9 eV due the nanocrystalline nature of CdS, from 5 to 10 cycles a blue shift is observed in the band gap around ∼2.15 eV by the electronic disorder induced by graphene oxide intercalation and the mixture of hexagonal/cubic phases of CdS. Raman spectra shows the longitudinal optical modes LO, 2LO and 3LO, the LO peak position shows a blue shift in comparison to the bulk CdS. The multilayer films of 3 and 5 cycles shows a wide range of photoluminescence emission from 350 to 700 eV, for samples of 7 and 10 cycles a quenching and red shift is observed attributed to the CdS crystals growth with a peak emission at 615 eV from bulk CdS, which make the materials suitable for photovoltaic solar cells and UV-Vis diodes for optoelectronic devices.

An ultra-sensitive photoelectrochemical biosensing platform based on the AgVO3/BiOI heterojunction for an enzyme activity inhibition reaction.

An ultra-sensitive photoelectrochemical sensing platform for profenofos detection based on the inhibition of catalase activity was prepared in this work. First, the novel functional nanocomposite material AgVO3/BiOI was prepared by a hot solvent method and successive ion layer adsorption reaction. Then, chitosan was employed as a dispersion medium to disperse and immobilize the catalase. Under visible light irradiation, the prepared CAT/CS/AgVO3/BiOI/ITO nanocomposite electrode generates a stable low photocurrent in hydrogen peroxide solution. When this electrode is immersed in a phosphate buffer solution containing profenofos, the activity of the catalase is inhibited, resulting in an increase in the photocurrent. Under the optimized experimental conditions, the profenofos concentration and increase in photocurrent are linearly related in the concentration range of 1 × 10-10 to 5.0 × 10-8 mol L-1, and the limit of detection is 1.0 × 10-11 mol L-1. This biosensor shows good selectivity for detecting profenofos in fruits and vegetables, and the determination results of profenofos are satisfactory.