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At least 1,027 records · Page 57

Synthesis of Carboxyl-Rich Biosorbent by UV-Induced Graft Polymerization Method for High Efficiency Adsorption of Ce{sup 3+} from Aqueous Solution: Activation and Adsorption Mechanism

Developing a cost-effective and highly efficient sorbent for the recovery of rare-earth elements from aqueous solution is still an urgent need. In this study, a novel biosorbent, carboxyl-rich pine bark (CPB), was modified by UV-induced graft polymerization method to increase the carboxyl-containing functional groups and facilitate the adsorption of Ce{sup 3+}. The grafting process was examined by Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM), indicating that high-density carboxyl functional groups are present on the surface of pine bark and the grafting yield of surface polymer brushes reaches up to 128%. Interestingly, the maximum adsorption capacity of Ce{sup 3+} on CPB could reach up to 256.5 mg/g. The adsorption mechanism of Ce{sup 3+} by CPB has been determined by the adsorption models and x-ray photoelectron spectroscopy (XPS), which can be inferred from these results that the high performance of CPB is attributed to the surface coordination between Ce{sup 3+} and hydroxyl or carbonyl groups. This work suggests that engineered surface functional groups of biomass could have an opportunity for the development of high performance rare-earth element adsorbents.

54 ENVIRONMENTAL SCIENCES↗

Solubility Measurements of Crystalline Cu2O in Aqueous Solution as a Function of Temperature and pH

The equilibrium solubility of crystalline cuprous oxide, cuprite, was measured in liquid water and steam using two flow-through reactors and a conventional batch autoclave. These measurements were carried out from 20 to 400 C. Different batches of pretreated cuprite were thoroughly characterized prior to and following each set of experiments. Metallic copper beads were added to the inlet end of the reactors and to the solid charge in the autoclave to preserve the Cu(I) oxidation state, although one series of experiments produced some results which were only compatible with CuO(cr) as the solubility limiting phase. Comparison of the solubility data for Cu2O(cr) in aqueous solution with those from the only available high-temperature dataset (Var yash, Geochem. Int. 26:80 90, 1989) showed that in near-neutral solutions the new data are lower by about four orders of magnitude at 350 C. Moreover, the dominant species in solution at temperatures 100 C were found to be only Cu+ and Cu(OH) 2 with Cu(OH)0 occurring over a narrow pH range at 75 C rather than the reverse trend reported previously. Solubility equations were developed as a function of temperature and pH, based on these new results, which showed increased solubility with temperature in acidic and basic solutions. The solubility of Cu2O(cr) in steam decreased slightly with temperature and as expected increased with increasing pressure to supercritical conditions where limited, compatible data were available in the literature. The solubility at subcritical conditions was on the order of one to several parts per billion, ppb. A simple empirical fit was derived for the solubility in steam as a function of temperature and pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of a Hydrated Sulfonatotitanyl(IV) Complex in Aqueous Solution and the Dimethylsulfoxide Solvated Titanyl(IV) Ion in Solution and Solid State

The coordination chemistry of oxotitanium(IV) or titanyl(IV), TiO 2+ , has been studied in solution by X-ray methods. The titanyl(IV) ion hydrolyzes easily in aqueous systems to solid titanium dioxide as long as it is not stabilized through complexation. In this study the structures of the hydrated bissulfatotitanyl(IV) complex and the dimethylsulfoxide (DMSO) solvated titanyl(IV) ions have been determined. In isolated monomeric titanyl complexes titanium(IV) binds strongly to a doubly bound oxo group at ca. 1.64 Å, to four ligands in the equatorial plane almost perpendicular to the Ti=O bond at ca. 2.02 Å, and there is one weakly bound ligand, trans to the Ti=O bond, at ca. 2.22 Å, for oxygen donor ligands; the O=Ti–O eq bond angles are 95°–100°. The structure of the DMSO solvated titanyl(IV) ion in the solid state is maintained in DMSO solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum chemical modeling of possible reactions of mononuclear iron nitrosyl complex [Fe(SC(NH{sub 2}){sub 2}){sub 2}(NO){sub 2}]Cl•H{sub 2}O in an aqueous solution

Possible reactions of the mononuclear iron nitrosyl complex [Fe(SC(NH{sub 2}){sub 2}){sub 2}(NO){sub 2}]Сl•H{sub 2}O in an aqueous solution were studied using quantum chemical modeling. The electronic structures of the possible intermediates were examined by the NBO and AIM methods. The substitution of the thio ligand in the iron—sulfur nitrosyl complex by a water molecule and the formation of dimeric intermediate complexes were found to facilitate the NO-donation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural parameters of the nearest environment of ions in aqueous solutions of ytterbium chloride

The radial distribution functions (RDFs) of aqueous solutions of ytterbium chloride were calculated using previously collected X-ray diffraction data for a wide range of solution concentrations under ambient conditions. Different solution structure models were constructed. Theoretical RDFs were calculated for each model. The optimum models for all systems studied were chosen based on the best fit between the theoretical and experimental RDFs. Quantitative characteristics of the nearest environment of Yb{sup 3+} and Cl{sup –} ions in solutions, namely, the coordination number, interparticle distances, and types of ion pairs were determined. The average number of water molecules in the first coordination sphere of the cation decreases from 8.2 to 6.0 as the solution concentration increases. The structure of all systems investigated is governed by non-contact ion associates throughout the concentration range studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photochemistry of cis,trans-[Pt{sup IV}(en)(I){sub 2}(CH{sub 3}COO){sub 2}] complex in aqueous solutions

The photochemistry of aqueous solutions of the cis,trans-[Pt{sup IV}(en)(I){sub 2}(CH{sub 3}COO){sub 2}] complex (1) was studied by stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy in the time interval from hundreds of femtoseconds to minutes. It is shown that the multistage photolysis, including photochemical reactions of ligand exchange and photoreduction, involves in the fi rst step the formation of the cis-[{sup IV}(en)(I){sub 2}(CH{sub 3}COO){sub 2}] complex with a quantum yield of 0.3 (irradiation at 282 nm). The further ligand exchange and photoreduction reactions occur with much lower quantum yields. The photochemical exchange of the acetate ion occurs in a time interval of ~100 ps with the much slower final step, being probably the acidic dissociation of the product. The key intermediate of the first step of the process was detected in the picosecond time range. Depending on the interpretation of the key intermediate nature, two possible mechanisms of the primary photochemical process are proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Efficient Separation/Recycling Palladium(II) Ions from Aqueous Solutions by Silica Gel-Coated Graphene Oxide Modified with Mercapto Groups

The separation and recovery of precious metals from secondary resources is an extremely important and challenging task. Herein, a novel sorbent is successfully prepared by chemical grafting and utilized for the extraction and separation of Pd(II) ions from aqueous solutions. Various characterization techniques, including Fourier transform infrared spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller, X-ray photoelectron spectroscopy, and element analysis, are employed to study the structure, morphology, porous nature, and chemical composition of the as-prepared SiO{sub 2}@GO-SH nanocomposites. The adsorption of Pd(II) ions on the SiO{sub 2}@GO-SH can be described by the pseudo-second-order model and Langmuir isotherm model. The adsorption equilibrium has been attained within 90 min and the maximum adsorption capacity of 423.2 mg g{sup −1} was attained at pH 3.5 and T = 308 K. The results reveal that SiO{sub 2}@GO-SH exhibits an excellent adsorption performance towards Pd(II) ions. In addition, we have proposed the adsorption mechanism for Pd(II) ions on the SiO{sub 2}@GO-SH surface. The adsorption of Pd(II) in SiO{sub 2}@GO-SH is a chemisorption process, where partial adsorbed Pd(II) ions are reduced to Pd(0) by functional groups (-SH) in the SiO{sub 2}@GO-SH. The results indicate that SiO{sub 2}@GO-SH can serve as a promising sorbent for the efficient separation and recovery of palladium from the palladium-containing secondary resources.

36 MATERIALS SCIENCE↗

CO{sub 2} Corrosion Behavior of Calcite-Covered API 5L X52 Carbon Steel in Aqueous Solutions

The CO{sub 2} corrosion of API 5L X52 steel in the presence and absence of calcite scale has been investigated. The scale was precipitated from a supersaturated solution at temperatures of 25 and 80 °C. The crystalline phase, cross section and surface morphologies of scale were studied by x-ray diffraction and scanning electron microscopy, respectively. It was found that the scale deposit mostly consisted of calcite. The corrosion behavior of bare and calcite-covered samples was investigated by electrochemical impedance spectroscopy and cyclic polarization techniques in aqueous CO{sub 2} solutions at 30, 50 and 70 °C. The presence of calcite scale on carbon steel surface decreased the adsorption of intermediate corrosion products as the scale uniformly covered the bare surface which resulted in reduction of general CO{sub 2} corrosion rate. The results of cyclic polarization tests revealed that the bare and calcite-covered samples were not susceptible to localized CO{sub 2} corrosion under conditions studied in this research.

36 MATERIALS SCIENCE↗

Shale gas and non-aqueous fracturing fluids: Opportunities and challenges for supercritical CO₂

Hydraulic fracturing of shale formations in the United States has led to a domestic energy boom. Currently, water is the only fracturing fluid regularly used in commercial shale oil and gas production. Industry and researchers are interested in non-aqueous working fluids due to their potential to increase production, reduce water requirements, and to minimize environmental impacts. Using a combination of new experimental and modeling data at multiple scales, we analyze the benefits and drawbacks of using CO₂ as a working fluid for shale gas production. We theorize and outline potential advantages of CO₂ including enhanced fracturing and fracture propagation, reduction of flow-blocking mechanisms, increased desorption of methane adsorbed in organic-rich parts of the shale, and a reduction or elimination of the deep re-injection of flow-back water that has been linked to induced seismicity and other environmental concerns. We also examine likely disadvantages including costs and safety issues associated with handling large volumes of supercritical CO₂. The advantages could have a significant impact over time leading to substantially increased gas production. In addition, if CO₂ proves to be an effective fracturing fluid, then shale gas formations could become a major utilization option for carbon sequestration.

03 NATURAL GAS↗

Microbial electrolysis using aqueous fractions derived from Tail-Gas Recycle Pyrolysis of willow and guayule

Here, this study investigated microbial electrolysis of two aqueous phase waste products derived from guayule and willow generated from Tail Gas Recycle Pyrolysis (TGRP). The highest average current density achieved was 5.0 ± 0.7 A/m 2 and 1.8 ± 0.2 A/m 2 for willow and guayule respectively. Average hydrogen productivity was 5.0 ± 1.0 L/L-day from willow and 1.5 ± 0.2 L/L-day for guayule. Willow also generated higher coulombic efficiency, anode conversion efficiency, and hydrogen recovery than guayule at most organic loading conditions. Compounds investigated exceeded 80% degradation, which included organic acids, sugar derivatives, and phenolics. Mass spectrometric analysis demonstrated the accumulation of a long chain amine not present in either substrate before treatment, and the persistence of several peptide residues resulting from the TGRP process. Lastly, new biorefineries may one day capitalize on this otherwise discarded byproduct of TGRP, further improving the potential applications and value of microbial electrolysis towards energy production.

09 BIOMASS FUELS↗

ROLE OF TUNGSTEN IN THE AQUEOUS PHASE HYDRODEOXYGENATION OF ETHYLENE GLYCOL ON TUNGSTATED ZIRCONIA SUPPORTED PALLADIUM

The focus of the present work was specifically on the elucidation of the role played by tungsten on the catalytic activity and selectivity of tungstated zirconia supported palladium (Pd-mWZ) for the aqueous phase hydrodeoxygenation (APHDO) of ethylene glycol (EG). Zirconia supported palladium (Pd-mZ) was used as reference. The catalysts were prepared via incipient wet impregnation and characterized using X-ray diffraction (XRD), temperature-programmed reduction (TPR), CO pulse chemisorption, CO-DRIFTS, ammonia temperature-programmed desorption (NH3-TPD) and pyridine adsorption. The presence of W results in larger Pd particles on supported Pd catalysts, i.e., 0.9 and 6.1 nm Pd particles are for Pd-mZ and Pd-mWZ, respectively. For comparison purposes, the activity of the catalytic materials used in this work was obtained using a well-defined set of operating conditions. The catalytic activity measurements show that the overall intrinsic activity of Pd particles on mWZ is 1.9 times higher than on mZ. APHDO process appears to be highly favored on Pd-mWZ whereas Pd-mZ exhibits a higher selectivity for reforming. This difference in terms of selectivity seems to be related to the high concentration of Brønsted acid sites and electron-deficient Pd species present on Pd-mWZ.

AQUEOUS PHASE HYDRODEOXYGENATION↗

Oxadiazole derivatives as stable anolytes for >3 V non-aqueous redox flow battery

Effective utilization of energy from renewable sources such as wind and solar requires the development of long duration energy storage (LDES) systems that can accommodate intermittent energy accrual. One option under investigation is the use of a redox flow battery (RFB). A significant amount of work has explored aqueous RFB systems with a variety of inorganic and organic carriers. However, moving to a nonaqueous solvent such as acetonitrile (MeCN) for RFB provides a much larger electrochemical window, which could lead to increased energy density if properly utilized. Here, in this work, we investigate a series of 2,5-diphenyl-1,3,4-oxadiazole (DiPhenOx) derivatives as anolytes for a redox flow battery. DiPhenOx has a low voltage redox event that, while reversible by cyclic voltammetry, was determined to be irreversible during bulk electrolysis. To improve cycling performance, we introduced various ester and cyano groups to the phenyl rings of DiPhenOx using molecular engineering. We characterized these derivatives spectroscopically and electrochemically to assess their feasibility for flow battery applications. The ester derivatives with the best cycling performance were tested in a flow cell vs. ferrocene, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) and thianthrene, which resulted in ~2 V, ~3 V and ~3 V redox flow batteries, respectively.

25 ENERGY STORAGE↗

Effects of anionic and nonionic surfactants on the dispersion and stability of nanoSiO2 in aqueous and cement pore solutions

It has been well recognized that the benefits and effectiveness of nanoparticles in cement-based materials could not be maximized if these are not well dispersed. To address this issue, in this study, different anionic (SDS and PCE) and nonionic surfactants (Tweens and Tritons) were used to disperse nanosilica (NS) in aqueous solution and cement pore solution. The results show that the dispersibility of NS in cement pore solution was improved, and the compressive strength of the cement-NS pastes increased linearly with critical micelle concentration (CMC) of nonionic surfactants. Among all surfactants studied, Triton X-405 led the paste to the highest increase in strength (33% at 1-day and 41% at 3-days) since it had the highest CMC. TEM and EDS analysis evidenced that this strength increase might be attributed to the nucleation of outer product CSH gel and its densification with calcite nanocrystals, attributed to Triton X-405 addition.

36 MATERIALS SCIENCE↗

Modeling swelling behavior of hydrogels in aqueous organic solvents

Hydrogel, a three-dimensional elastic structure of cross-linked polymer chains, swells or deswells when immersed in aqueous organic solutions. The swelling of hydrogels depends on temperature, solvent composition, and hydrogel structure as the thermodynamic driving forces for hydrogel swelling are due to solvent – hydrogel interactions and expansion of elastic network. Here in this work, polymer Nonrandom Two-Liquid activity coefficient model is used to account for the solvent – hydrogel interactions and a semi-empirical expression for rubber elasticity is used to describe the expansion of elastic network. The model successfully correlates data for both swelling and equilibrium phase compositions for n-isopropyl acrylamide hydrogels in water – ethanol, water – acetone, water – n-butanol, and water – methyl isobutyl ketone mixed solvents.

42 ENGINEERING↗

Effect of pinholes in Nb 4 C 3 MXene sheets on its electrochemical behavior in aqueous electrolytes

Two-dimensional (2D) niobium carbide, Nb 4 C 3 T x (T x : O, OH, and F), a representative member of the 43 MXene structural motif, has shown promising electrochemical performance in acidic electrolytes. The capacitive performance of Nb 4 C 3 T x in neutral aqueous electrolytes has been reported as moderate, but little effort has been made to improve it. In this paper, we report a method to introduce nanopores (pinholes) in Nb 4 C 3 T x MXene flakes by adjusting the etching time. The pinholes generated during the etching process improve ion diffusion pathways, which are otherwise hindered by the restacking of the 2D flakes. The “holey Nb 4 C 3 T x ” shows a 50 % improved rate capability at charge/discharge time scales of 1–2 s in 1 M Li 2 SO 4 , Na 2 SO 4 , and (NH 4 ) 2 SO 4 electrolytes. Our strategy of controlling the permeability of Nb 4 C 3 T x sheets can potentially be applied to other MXenes, providing guidance for improving the capacitance and rate capability of 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical stability and long-term cell performance of low-cobalt, Ni-Rich cathodes prepared by aqueous processing for high-energy Li-Ion batteries

Cobalt content in Li-ion battery cathodes has become a top concern due to its price volatility and limited source availability. Low-cobalt, Ni-rich active materials are promising candidates for next-generation cathodes due to their high capacities, and water-based processing of these materials can further reduce both cost and environmental impact. We systematically evaluated the water compatibility of four different LiNi x Mn 1-x-y Co y O 2 (NMC) powders with increasing nickel contents. Comprehensive characterization verified there is no major change to their bulk structures, and only slight surface modifications related to the removal of contaminant species. For the first time, we demonstrate that LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811) cathodes can be formulated in water and cycled 1000 times in full pouch cells with excellent capacity retention (~70% compared to ~76% for NMP-processed cells). When implemented in future battery production lines, aqueous processing of Ni-rich NMC will simultaneously enable cost reductions and higher cell energy densities.

25 ENERGY STORAGE↗

A mechanistic study on Decontamination of Methyl Orange Dyes from Aqueous Phase by Mesoporous Pulp Waste and Polyaniline

The dispersion-corrected density functional theory (DFT-D3) is used to investigate the mechanism of mesoporous pulp waste (MPW) and polyaniline (PANI) adsorptive removal methyl orange (MO) dye from their aqueous solutions. The results are absolutely reliable because of the sufficiently accurate method although such big systems are studied. It is demonstrated that hydrogen bond and Van Der Waals interactions play a significant role in MO adsorption by MPW and PANI. For MO adsorption by MPW, hydrogen bond and Van Der Waals interactions are both weakened in S{sub 1} state. In contrast, hydrogen bond and Van Der Waals interactions between PANI and MO are both enhanced in S{sub 1} state. The thermodynamic parameters such as enthalpy and free energy change reveal that the MO adsorption by MPW and PANI are spontaneous and exothermic. The adsorption of MO on MPW is less favorable in S{sub 1} state and the adsorption of MO on PANI is more favorable in S{sub 1} state. Therefore, the photoexcitation should be controlled during the MO adsorption by MPW and applied for MO adsorption by PANI. - Highlights: • The hydrogen bond and Van Der Waals interactions play a significant role in MO adsorption by MPW and PANI. • The influence of photoexcitation on adsorption has been studied firstly in our work. • The adsorption of MO on MPW is less favorable in S{sub 1} state and the adsorption of MO on PANI is more favorable in S{sub 1} state. • The MO adsorption by MPW and PANI are spontaneous and exothermic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computationally efficient models for aqueous organic redox flow batteries

The rising usage of intermittent energy has garnered the need for large scale energy storage systems. Redox flow batteries (RFB) based energy storage system shows promising potential. Numerical simulations and machine learning approaches have been widely used to study RFB performance. The development of autonomous material discovery framework and digital twin of energy storage system usually needs to query cell performance through fast response models. In this study, two computationally efficient models are introduced: a physics-based analytical flow battery model (EZBattery), and a machine learning operator model (Deep Operator Network, denoted by DeepONet). Both models can provide cell performance near instantly, and prediction accuracy was systematically examined on an application of evaluating the performances of a 780 cm 2 aqueous organic redox flow battery (AORFB), using potential anolyte candidates in dihydroxyphenazine (DHP)-based family of organic materials. A validated computationally expansive 3-dimensional multi-physics finite element model by COMSOL was used as the ground truth and provided the training data set for the DeepONet. 1280 samples were generated with 10 properties to mimic the different possible anolyte candidates, and the cell performances were evaluated under 10 different combined operating conditions. The accuracy comparisons for the two computationally efficient models show that both models can provide comparable accuracy in predicting cell charging/discharging voltage curves. DeepONet can provide slightly higher overall accuracy than EZBattery with faster calculation speed, but highly relies on the training dataset. EZBattery does not need a training dataset and can provide interpretable physics-based explanations of the results, while being more flexible to adjust to adapt any different cell designs, flow battery architectures, and electrolyte materials.

Analytical model↗