Unravelling pH/pKa influence on pH-responsive drug carriers: Insights from ibuprofen-silica interactions and comparative analysis with carbon nanotubes, sulfasalazine, and alendronate.

This study employs density functional theory to explore the interaction between ibuprofen (IBU) and silica, emphasizing the influence of the trimethylsilyl (TMS) functional group for designing pH-responsive drug carriers. The surface (S) and drug (D) molecules' neutral (0) or deprotonated (-1) states were taken into consideration during the investigation. The likelihood of these states was determined based on the pKa values and the desired pH conditions. To calculate the pH-dependent interaction energy (EintpH), four different situations have been identified: S0D0, S0D-1, S-1D0, and S-1D-1.The electrostatic component of interaction energy aligns favorably with its theoretical value in both the Debye-Hückel and Grahame models. The investigation has gathered first-hand experimental data on the drug loading and release of pH-responsive mesoporous silica nanoparticles. Effective drug loading was observed in the acidic environment of the stomach (pH 2-5), followed by a release in the slightly basic to neutral pH of the small intestine (pH 7.4), These findings align with existing literature. The results revealed horizontal drug adherence on silica surfaces, improving binding capabilities. Comparisons were made with combinations involving carboxylated carbon nanotubes and ibuprofen, silica, and sulfasalazine, and silica and alendronate, exploring drug loading/release dynamics associated with positive/negative interaction energies. The investigation, supported by experimental data, contributes valuable insights into pH-responsive mesoporous silica nanoparticles, offering new design possibilities for drug carriers.

Graphitized mango seed as an effective 3D anode in batch and continuous mode microbial fuel cells for sustainable wastewater treatment and power generation.

Herein, we explored the utilization of graphitized mango seeds as 3D-packed anodes in microbial fuel cells (MFCs) powered by sewage wastewater. Mango seeds were graphitized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) and their effectiveness as anodes was evaluated. Surface morphology analysis indicated that the proposed anode was characterized by layered branches and micro-sized deep holes, facilitating enhanced biofilm formation and microorganism attachment. Maximum power densities achieved in the MFCs utilizing the mango seed-packed anodes graphitized at 1100 °C and 1000 °C were 2170.8 ± 90 and 1350.6 ± 125 mW m-2, respectively. Furthermore, the weight of the graphitized seed anode demonstrated a positive correlation with the generated power density and cell potential. Specifically, MFCs fabricated with 9 g and 6 g anodes achieved maximum power densities of 2170.8 ± 90 and 1800.5 ± 40 mW m-2, respectively. A continuous mode air cathode MFC employing the proposed graphitized mango anode prepared at 1100 °C and operated at a flow rate of 2 L h-1 generated a stable current density of approximately 12 A m-2 after 15 hours of operation, maintaining its stability for 75 hours. Furthermore, a chemical oxygen demand (COD) removal efficiency of 85% was achieved in an assembled continuous mode MFC. Considering that the proposed MFC was driven by sewage wastewater without the addition of external microorganisms, atmospheric oxygen was used as the electron acceptor through an air cathode mode, agricultural biomass waste was employed for the preparation of the anode, and a higher power density was achieved (2170.8 mW m-2) compared to reported values; it is evident that the proposed graphitized mango seed anode exhibits high efficiency for application in MFCs.

Nanoengineered, Pd-doped Co@C nanoparticles as an effective electrocatalyst for OER in alkaline seawater electrolysis.

Water electrolysis is considered one of the major sources of green hydrogen as the fuel of the future. However, due to limited freshwater resources, more interest has been geared toward seawater electrolysis for hydrogen production. The development of effective and selective electrocatalysts from earth-abundant elements for oxygen evolution reaction (OER) as the bottleneck for seawater electrolysis is highly desirable. This work introduces novel Pd-doped Co nanoparticles encapsulated in graphite carbon shell electrode (Pd-doped CoNPs@C shell) as a highly active OER electrocatalyst towards alkaline seawater oxidation, which outperforms the state-of-the-art catalyst, RuO2. Significantly, Pd-doped CoNPs@C shell electrode exhibiting low OER overpotential of ≈213, ≈372, and ≈ 429 mV at 10, 50, and 100 mA/cm2, respectively together with a small Tafel slope of ≈ 120 mV/dec than pure Co@C and Pd@C electrode in alkaline seawater media. The high catalytic activity at the aforementioned current density reveals decent selectivity, thus obviating the evolution of chloride reaction (CER), i.e., ∼490 mV, as competitive to the OER. Results indicated that Pd-doped Co nanoparticles encapsulated in graphite carbon shell (Pd-doped CoNPs@C electrode) could be a very promising candidate for seawater electrolysis.

Stearic Acid and CeO2 Nanoparticles Co-functionalized Cotton Fabric with Enhanced UV-Block, Self-Cleaning, Water-Repellent, and Antibacterial Properties.

Superhydrophobic cotton fabrics with multifunctional features are highly desired in domestic and outdoor applications. However, the short coating longevity and hazardous reagents significantly reduce their commercial-scale applications. Herein, we introduce CeO2 nanoparticles and stearic acid (SA) to develop a fluorine-free, durable superhydrophobic cotton fabric that mimics the lotus effect. The pristine cotton fabric is treated with APTES-functionalized CeO2 nanoparticles by immersion followed by a dip and drying treatment with a 2% myristic acid solution. This sequential process creates a stable superhydrophobic cotton fabric (SA/CeO2-cotton fabric) with a water contact angle of 158° and a water sliding angle of 5°. The results are attributed to the combined effect of CeO2 nanoparticles and stearic acid that enhances surface roughness and reduces surface sorption energy. APTES facilitates the durable attachment of CeO2 nanoparticles and stearic acid to the cotton fabric. The modified cotton fabric is characterized by advanced analytical tools, demonstrating enhanced superhydrophobicity, self-cleaning, and antiwater absorption properties. Additionally, it exhibits remarkable UV-blocking (UPF 542) and antibacterial properties. The designed superhydrophobic cotton fabric unveils good mechanical, thermal, and chemical durability. The proposed strategy is simple, green, and economical and can be used commercially for functional fabric preparation.

Solution Combustion Synthesis of Novel S,B-Codoped CoFe Oxyhydroxides for the Oxygen Evolution Reaction in Saline Water.

Green hydrogen presents itself as a clean energy vector, which can be produced by electrolysis of water by utilizing renewable energy such as solar or wind. While current technologies are sufficient to support commercial deployment of fresh water electrolyzers, there remain a few well-defined challenges in the path of commercializing direct seawater electrolyzers, predominantly related to the sluggish oxygen evolution reaction (OER) kinetics and the competing chlorine evolution reaction (CER) at the anode. Herein, we report the facile and swift fabrication of an S,B-codoped CoFe oxyhydroxide via solution combustion synthesis for the OER with apparent CER suppression abilities. The as-prepared S,B-(CoFe)OOH-H attained ultralow overpotentials of 161 and 278 mV for achieving current densities of 10 and 1000 mA cm-2, respectively, in an alkaline saline (1 M KOH + 0.5 M NaCl) electrolyte, with a low Tafel slope of 46.7 mV dec-1. Chronoamperometry testing of the codoped bimetallic oxyhydroxides showed very stable behavior in harsh alkaline saline and in neutral pH saline environments. S,B-(CoFe)OOH-H oxyhydroxide showed a notable decrease in CER production in comparison to the other S,B-codoped counterparts. Selectivity measurements through online FE calculations showed high OER selectivity in alkaline (FE ∼ 97%) and neutral (FE ∼ 91%) pH saline conditions under standard 10 mA cm-2 operation. Moreover, systematic testing in electrolytes at pH values of 14 to 7 yielded promising results, thus bringing direct seawater electrolysis at near-neutral pH conditions closer to realization.

Early Transition-Metal-Based Binary Oxide/Nitride for Efficient Electrocatalytic Hydrogen Evolution from Saline Water in Different pH Environments.

Using abundant seawater can reduce reliance on freshwater resources for hydrogen production from electrocatalytic water splitting. However, seawater has detrimental effects on the stability and activity of the hydrogen evolution reaction (HER) electrocatalysts under different pH conditions. In this work, we report the synthesis of binary metallic core-sheath nitride@oxynitride electrocatalysts [Ni(ETM)]δ+-[O-N]δ-, where ETM is an early transition metal V or Cr. Using NiVN on a nickel foam (NF) substrate, we demonstrate an HER overpotential as low as 32 mV at -10 mA cm-2 in saline water (0.6 M NaCl). The results represent an advancement in saline water HER performance of earth-abundant electrocatalysts, especially under near-neutral pH range (i.e., pH 6-8). Doping ETMs in nickel oxynitrides accelerates the typically rate-determining H2O dissociation step for HER and suppresses chloride deactivation of the catalyst in neutral-pH saline water. Heterointerface synergism occurs through H2O adsorption and dissociation at interfacial oxide character, while adsorbed H* proceeds via Heyrovsky or Tafel step on the nitride character. This electrocatalyst showed stable performance under a constant current density of -50 mA cm-2 for 50 h followed by additional 50 h at -100 mA cm-2 in a neutral saline electrolyte (1 M PB + 0.6 M NaCl). Contrarily, under the same conditions, Pt/C@NF exhibited significantly low performance after a mere 4 h at -50 mA cm-2. The low Tafel slope of 25 mV dec-1 indicated that the reaction is Tafel limited, unlike commercial Pt/C, which is Heyrovsky limited. We close by discussing general principles concerning surface charge delocalization for the design of HER electrocatalysts in pH saline environments.

Author Correction: Surfactant/organic solvent free single-step engineering of hybrid graphene-Pt/TiO2 nanostructure: Efficient photocatalytic system for the treatment of wastewater coming from textile industries.

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Surfactant/organic solvent free single-step engineering of hybrid graphene-Pt/TiO2 nanostructure: Efficient photocatalytic system for the treatment of wastewater coming from textile industries.

In this study, hybrid graphene-Pt/TiO2 nanostructure were synthesized by single-step, inexpensive and surfactant/organic solvent free route; hydrothermal technique. The physicochemical properties of hybrid graphene-Pt/TiO2 nanostructure were carefully analyzed by multiple techniques, including X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). The synthesized hybrid nanostructures were utilized as photocatalyst for the degradation of methylene blue (MB) dye under natural environment at average ambient temperature and mean daily global solar radiation, of about 22-25 °C and 374.9 mWh/cm2, respectively. The activity performance indicated considerable degradation of methylene blue (MB) dye and was in the following order Gr (13%), TiO2 (60%) and hybrid graphene-Pt/TiO2 nanostructure (90%) over 21 min under the natural light illumination. The physiochemical characterization suggests that, the tightly attached metalized TiO2 nanoparticles (Pt-TiO2) on the high surface area graphene sheets improved utilization of visible light and increased separation and transfer of photo-excited electron (e) hole (h+) pairs. Notably, the hybrid graphene-Pt/TiO2 nanostructure exhibited an excellent cyclic stability for methylene blue (MB) dye removal. Finally, the kinetic behavior indicated that the photocatalytic degradation reaction of the dye obeyed the pseudo-first order (Langmuir-Hinshelwood) kinetics model.

Effective NiMn Nanoparticles-Functionalized Carbon Felt as an Effective Anode for Direct Urea Fuel Cells.

The internal resistances of fuel cells strongly affect the generated power. Basically, in the fuel cell, the anode can be prepared by deposition of a film from the functional electrocatalyst on a proper gas diffusion layer. Accordingly, an interfacial resistance for the electron transport is created between the two layers. Electrocatalyst-functionalized gas diffusion layer (GDL) can distinctly reduce the interfacial resistance between the catalyst layer and the GDL. In this study, NiMn nanoparticles-decorated carbon felt is introduced as functionalized GDL to be exploited as a ready-made anode in a direct urea fuel cell. The proposed treated GDL was prepared by calcination of nickel acetate/manganese acetate-loaded carbon felt under an argon atmosphere at 850 °C. The physiochemical characterizations confirmed complete reduction for the utilized precursors and deposition of pristine NiMn nanoparticles on the carbon felt fiber. In passive direct urea fuel cells, investigation the performance of the functionalized GDLs indicated that the composition of the metal nanoparticles has to be optimized as the GDL obtained from 40 wt % manganese acetate reveals the maximum generated power density; 36 mW/m² at room temperature and 0.5 M urea solution. Moreover, the electrochemical measurements proved that low urea solution concentration is preferred as utilizing 0.5 M solution resulted into generating higher power compared to 1.0 and 2.0 M solution. Overall, this study opens a new avenue toward functionalization of the GDL as a novel strategy to overcome the interfacial resistance between the electrocatalyst and the GDL.

Stable N-doped & FeNi-decorated graphene non-precious electrocatalyst for Oxygen Reduction Reaction in Acid Medium.

NiFe nanoparticles-decorated & N-doped graphene is introduced as an effective and stable non-precious electrocatalyst for ORR in the acid medium. Compared to conventional Pt/C electrodes under the same conditions, the proposed nanocatalyst shows closer onset potential and current density. Typically, the observed onset potentials and current densities for the synthesized and Pt/C electrodes are 825 and 910 mV (vs. NHE) and -3.65 and -4.31 mA.cm-2 (at 5 mV.s-1), respectively. However, the most important advantage of the introduced metallic alloy-decorated graphene is its distinct stability in acid medium; the retention in the electrocatalytic performance after 1,000 successive cycles is approximately 98%. This finding is attributed to the high corrosion resistance of the NiFe alloy. The kinetic study indicates that the number of the transferred electrons is 3.46 and 3.89 for the introduced and Pt/C (20 wt%) electrodes, respectively which concludes a high activity for the proposed nanocomposite. The suggested decorated graphene can be synthesized using a multi-thermal method. Typically, nickel acetate, iron acetate, graphene oxide and urea are subjected to MW heating. Then, sintering with melamine in an Argon atmosphere at 750 °C is required to produce the final electrocatalyst. Overall, the introduced NiFe@ N-doped Gr nanocomposite shows remarkable electrochemical activity in the acid medium with long-term stability.

ZnO@C (core@shell) microspheres derived from spent coffee grounds as applicable non-precious electrode material for DMFCs.

Although numerous reports have introduced non precious electrocatalysts for methanol oxidation, most of those studies did not consider the corresponding high onset potential which restricts utilization in real fuel cells. In this study, an -90 mV [vs. Ag/AgCl] onset potential non-precious electrocatalyst is introduced as an applicable anode material for the direct methanol fuel cells. Moreover, the proposed material was prepared from a cheap and abundantly existing resource; the spent coffee grounds. Typically, the spent coffee grounds were facilely converted to core@shell (ZnO@C) microspheres through a two-step approach, involving chemical activation and a subsequent calcination at temperature of 700 °C. Activation of the carbon derived from the spent coffee grounds was performed with ZnCl2 which acts as pore-forming agent as well as a precursor for the ZnO. The structure and morphology were characterized by (XRD), (SEM), and (TEM) analyses while the electrochemical characterizations was evaluated by cyclic voltammetry (CV) technique. Besides the comparatively very low onset potential, the introduced microspheres exhibited relatively high current density; 17 mA/cm2. Overall, based on the advantages of the green source of carbon and the good electrocatalytic activity, the spent coffee grounds-derived carbon can be considered a promise anode material for the DMFCs.

Amorphous SiO2 NP-Incorporated Poly(vinylidene fluoride) Electrospun Nanofiber Membrane for High Flux Forward Osmosis Desalination.

Novel amorphous silica nanoparticle-incorporated poly(vinylidine fluoride) electrospun nanofiber mats are introduced as effective membranes for forward osmosis desalination technology. The influence of the inorganic nanoparticle content on water flux and salt rejection was investigated by preparing electrospun membranes with 0, 0.5, 1, 2, and 5 wt % SiO2 nanoparticles. A laboratory-scale forward osmosis cell was utilized to validate the performance of the introduced membranes using fresh water as a feed and different brines as draw solution (0.5, 1, 1.5, and 2 M NaCl). The results indicated that the membrane embedding 0.5 wt % displays constant salt rejection of 99.7% and water flux of 83 L m(-2) h(-1) with 2 M NaCl draw solution. Moreover, this formulation displayed the lowest structural parameter (S = 29.7 µm), which represents approximately 69% reduction compared to the pristine membrane. Moreover, this study emphasizes the capability of the electrospinning process in synthesizing effective membranes as the observed water flux and average salt rejection of the pristine poly(vinylidine fluoride) membrane was 32 L m(-2) h(-1) (at 2 M NaCl draw solution) and 99%, respectively. On the other hand, increasing the inorganic nanoparticles to 5 wt % showed negative influence on the salt rejection as the observed salt flux was 1651 mol m(-2) h(-1). Besides the aforementioned distinct performance, studies of the mechanical properties, porosity, and wettability concluded that the introduced membranes are effective for forward osmosis desalination technology.

Effective photocatalytic efficacy of hydrothermally synthesized silver phosphate decorated titanium dioxide nanocomposite fibers.

Hierarchical Ag3PO4/TiO2 nanocomposite fibers were prepared by combining electrospinning technique and hydro-thermal growth method. As-synthesized samples were characterized by using field-emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Photoluminescence (PL), and Fourier transform infra-red (FT-IR) spectroscopy. The FE-SEM image revealed a uniform decoration of Ag3PO4 nanoparticles without aggregation on primary TiO2 nanofibers. The photocatalytic and antibacterial studies were performed and results were shown that the Ag3PO4/TiO2 nanocomposite fibers show an enhanced photocatalytic and antibacterial activity toward the degradation of dye methylene blue and bacteria (Escherichia coli, Staphylococcus aureus) respectively. Our results can provide new insights of Ag3PO4/TiO2 nanocomposite fibers for the potential applications in antibacterial and waste water treatment.

Influence of copper content on the electrocatalytic activity toward methanol oxidation of Co(χ)Cu(y) alloy nanoparticles-decorated CNFs.

In this study, CoCu alloy nanoparticles-incorporated carbon nanofibers are introduced as effective non precious electrocatalyst for methanol oxidation in alkaline medium. The introduced electrocatalyst has been synthesized by simple and effective process; electrospinning. Typically, calcination, in nitrogen atmosphere, of electrospun nanofibers composed of cobalt acetate, copper acetate and poly (vinyl alcohol) leads to form carbon nanofibers decorated by CoCu nanoparticles. The nanofibrous morphology and alloy structure have been confirmed by SEM, TEM and XRD analyses. Investigation of the electrocatalytic activity indicates that copper content has strong influence, the alloy nanoparticles having the composition Cu5%Co95% showed distinct high performance; 100 times higher than other formulations. Overall, the introduced study revealed the veil about the distinct role of copper in enhancing the electrocatalytic activity of cobalt-based materials.

Facile synthesis of luminescent and amorphous La2O3-ZrO2:Eu³âº nanofibrous membranes with robust softness.

Novel luminescent and amorphous La2O3-ZrO2:Eu(3+) (LZE) nanofibrous membranes with robust softness are fabricated for the first time via a facile electrospinning technique. By incorporating zirconium oxide, the as-prepared lanthanum oxide nanofibrous membranes can be dramatically changed from extreme fragility to robust softness. Meanwhile, the softness and luminescent performance of LZE nanofibrous membranes can be finely controlled by regulating the doping concentration of zirconium oxide and europium in lanthanum oxide nanofibers. Additionally, the crystal structure analysis using X-ray diffractometer and high resolution transmission electron microscopy measurements have confirmed the correlation between the amorphous structure and softness. Furthermore, LZE membranes show the characteristic emission of Eu(3+) corresponding to (5)D(0, 1, 2)-(7)F(0, 1, 2, 3, 4) transitions due to an efficient energy transfer from O(2-) to Eu(3+). The LZE nanofibrous membranes with the optimum doping Eu(3+) concentration of 3 mol% exhibit excellent softness and luminescent properties, which make the materials to have potential applications in fluorescent lamps and field emission displays.