Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Nano fibrillated cellulose-based foam by Pickering emulsion: Preparation,characterizations, and application as dye adsorbent

An ecofriendly and biodegradable porous structure was prepared from drying aqueous foams based on nano fibrillated cellulose (NFC), extracted from softwood pulp by subcritical water/CO₂ treatment (SC-NFC). The primary aim of this work was to use the modified SC-NFC as stabilizer for a water-based Pickering emulsion which upon drying, yielded porous cellulosic materials, a good dye adsorbent. In order to exploit the carboxymethylated SC-NFC (CMSC-NFC, with a degree of substitution of 0.35 and a charge density of 649 μeqv/g) as a stabilizer for water-based Pickering emulsion in subsequent step, an optimized quantity of octyl amine (30 mg/g of SC-NFC) was added to make them partially hydrophobic. A series of dry foam structures were prepared by varying the concentrations of treated CMSC-NFCs and 4 wt% was found to be the optimum concentration to yield foam with high porosity (99%) and low density (0.038 g/cc) along with high compression strength (0.24 MPa), superior to the conventionally extracted NFC. The foams were applied to capture as high as 98% of methylene blue dyes, making them a potential green candidate for treating industrial effluent. In addition, the dye adsorption kinetics and isotherms were found to be well suited with second order kinetics and Langmuir isotherm models.     

Hydrophobic Cross-Linked Poly(dimethylsiloxane)-Based Sorbents for Oil Spill Applications

With the increase of industrialization and urbanization, humankind faces massive oil-based pollution due to tanker accidents, human error, and natural disasters. For this, hydrophobic sorbents are fabricated and their applications for the removal of oil from polluted water sources are investigated. These hydrophobic sorbents are prepared by the condensation reaction of poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]isocyanurate cross-linker via bulk polymerization. The obtained sorbents exhibit high oil sorption capacity, fast absorption–desorption kinetics, and great reusability. Moreover, they can selectively absorb oil from the water surface, thus making them practical for water clean-up applications.     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

Investigation into adsorption equilibrium and thermodynamics for water vapor on montmorillonite clay

The isothermal adsorption curves for water vapor on montmorillonite were measured by a gravimetric adsorption system. Dent's model was employed to estimate the adsorption behaviors of water vapor on primary adsorption sites and secondary adsorption sites. The thermodynamics analysis of water vapor adsorption was performed. At low vapor pressure region, primary adsorption predominates, and with increasing vapor pressure, secondary adsorption becomes notable. Primary adsorption sites have an evidently stronger adsorption affinity than secondary adsorption sites. With increasing vapor pressure, Gibbs free energy variation rapidly increases and then reduces slowly. Although increasing vapor pressure raises adsorption spontaneity on primary adsorption sites, the enhancement in vapor pressure decreases the spontaneity of water vapor adsorption on secondary adsorption sites. As adsorbed loading increases, isosteric heat of adsorption and entropy loss decrease first and then increase quickly. The gradually growing water clusters are responsible for the increase of entropy loss at late stage.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Preparation of magnetic zeolite/chitosan composite using silane as modifier for adsorption of Cr(VI) from aqueous solutions

This study aimed to prepare an efficient, cost-effective, and separable magnetic zeolite/chitosan composite (MZFA/CS) adsorbent from solid waste to deal with the water pollution of Cr(VI). The MZFA/CS was characterized by X-ray fluorescence (XRF), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and vibrating sample magnetometer (VSM) techniques. Then, the effect of pH, temperature, initial concentration of Cr(VI) ions, and contact time was considered in the study. For a sorbent dose of 0.1 g in 50 mL of a Cr(VI) solution, at a contact time of 30 min, temperature of 30°C, and a pH of 3, an adsorption capacity (q_e) of 16.96 mg g⁻¹ was achieved. Adsorption kinetics and isotherm data obtained for all adsorption systems were well-fitted by pseudo-second-order and Langmuir models, respectively. The thermodynamic study suggested that the adsorption process is spontaneous and endothermic in nature. In summary, the adsorbent with better separability (Ms = 16.83 emu g⁻¹) and adsorbability was successfully fabricated.