Unmasking the Electrochemiluminescence Properties of Ternary Mn/Fe/Co Metals Doped Porous g-C3N4 Fiber-like Nanostructure.

Graphitic-phase carbon nitride (g-C3N4) materials have exhibited increasingly remarkable performance as emerging electrochemiluminescence (ECL) emitters, owing to their unique optical and electronic properties; however, the ECL merits of porous g-C3N4 nanofibers doped with ternary metals are not yet explored. Deciphering the ECL properties of trimetal-doped g-C3N4 nanofibers could provide an exquisite pathway for ultrasensitive sensing and imaging with impressive advantages of minimal background signal, great sensitivity, and durability. Herein, we rationally synthesized g-C3N4 nanofibers doped atomically with Mn, Fe, and Co elements (Mn/Fe/Co/g-C3N4) in a one-pot via the protonation in ethanol and annealing process driven by the rolling up mechanism. The ECL performance of g-C3N4 with and without metal dopants was investigated and compared with standard Ru(bpy)32+ in the presence of potassium persulfate (K2S2O8) as the coreactant. Notably, g-C3N4 nanofibers doped with metal ions exhibited an ECL efficiency of 483% that was 4.83 times higher than that of Ru(bpy)32+. Mechanistic investigations unveiled that the g-C3N4 nanofibers possess a large surface area and, as a result, exhibit a reduced interfacial impedance within the porous microstructure. These factors contribute to the acceleration of charge transfer rates and the stabilization of charge carriers and excitons, ultimately facilitating the ECL process. This research endeavor may pave the way for a new hot research area and serves as a powerful tool for elucidating fundamental inquiries of ECL on one-dimensional g-C3N4 nanostructures.

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol.

The interfacial engineering of Pd-based alloys (i.e., PdM with distinct morphologies, compositions, and strain defects) is an efficient way for enhanced catalytic activity; however, it remains a grand challenge to fabricate such alloys in aqueous solutions without heating, organic solvents, and multiple reaction steps. Herein, we present a simple, aqueous-phase, one-step, and ultrafast approach for the interfacial engineering of surfactant-free porous PdM (M = Cu, Au, and Mn) nanocrystals with well-controlled spongy-like morphology and compositions. The electronic interaction in PdM nanocrystals and their effect on the alkaline electrochemical ethanol oxidation reaction (EOR) are investigated using XRD, XPS, and electrochemical tests. Notably, integrating M metals into Pd atoms results in upshifting the d-band center of Pd and subsequently modulating the EOR activity and stability substantially. The EOR mass activity (10.78 A/mgPd (6.93 A/mgPdCu)) of PdCu was 1.83, 3.09, 4.51, and 53.90 times higher than those of AuPd (5.90 A/mgPd (3.27 A/mgAuPd)), PdMn (3.48 A/mgPd (3.19 A/mgPdMn)), Pd (2.39 A/mgPd), and Pd/C (0.20 A/mgPd), respectively, besides substantial durability after 1000 cycles. This is due to the porous two-dimensional morphology, a low synergetic effect, higher interfacial interaction, and greater active surface area of PdCu, besides a high Cu content with more oxophilicity that facilitates activation/dissociation of H2O to generate -OH species needed for quick EOR electrocatalysis. The electrochemical impedance spectroscopy (EIS) reveals better electrolyte/electrode interfacial interaction and lower charge transfer resistance on PdCu. The EOR activity of PdCu porous sponge-like nanocrystals was superior to all previously reported Pd-based alloys for electrochemical EOR. This study indicates that binary Pd-based catalysts with less synergetic effect are preferred for boosting the EOR activity, which could help in manipulating the surface properties of Pd-based alloys to optimize EOR performance.

Self-Standing Pd-Based Nanostructures for Electrocatalytic CO Oxidation: Do Nanocatalyst Shape and Electrolyte pH Matter?

Tailoring the shape of Pd nanocrystals is one of the main ways to enhance catalytic activity; however, the effect of shapes and electrolyte pH on carbon monoxide oxidation (COOxid) is not highlighted enough. This article presents the controlled fabrication of Pd nanocrystals in different morphologies, including Pd nanosponge via the ice-cooling reduction of the Pd precursor using NaBH4 solution and Pd nanocube via ascorbic acid reduction at 25 °C. Both Pd nanosponge and Pd nanocube are self-standing and have a high surface area, uniform distribution, and clean surface. The electrocatalytic CO oxidation activity and durability of the Pd nanocube were significantly superior to those of Pd nanosponge and commercial Pd/C in only acidic (H2SO4) medium and the best among the three media, due to the multiple adsorption active sites, uniform distribution, and high surface area of the nanocube structure. However, Pd nanosponge had enhanced COOxid activity and stability in both alkaline (KOH) and neutral (NaHCO3) electrolytes than Pd nanocube and Pd/C, attributable to its low Pd-Pd interatomic distance and cleaner surface. The self-standing Pd nanosponge and Pd nanocube were more active than Pd/C in all electrolytes. Mainly, the COOxid current density of Pd nanocube in H2SO4 (5.92 mA/cm2) was nearly 3.6 times that in KOH (1.63 mA/cm2) and 10.3 times that in NaHCO3 (0.578 mA/cm2), owing to the greater charge mobility and better electrolyte-electrode interaction, as evidenced by electrochemical impedance spectroscopy (EIS) analysis. Notably, this study confirmed that acidic electrolytes and Pd nanocube are highly preferred for promoting COOxid and may open new avenues for precluding CO poisoning in alcohol-based fuel cells.

Pt-Based Nanostructures for Electrochemical Oxidation of CO: Unveiling the Effect of Shapes and Electrolytes.

Direct alcohol fuel cells are deemed as green and sustainable energy resources; however, CO-poisoning of Pt-based catalysts is a critical barrier to their commercialization. Thus, investigation of the electrochemical CO oxidation activity (COOxid) of Pt-based catalyst over pH ranges as a function of Pt-shape is necessary and is not yet reported. Herein, porous Pt nanodendrites (Pt NDs) were synthesized via the ultrasonic irradiation method, and its CO oxidation performance was benchmarked in different electrolytes relative to 1-D Pt chains nanostructure (Pt NCs) and commercial Pt/C catalyst under the same condition. This is a trial to confirm the effect of the size and shape of Pt as well as the pH of electrolytes on the COOxid. The COOxid activity and durability of Pt NDs are substantially superior to Pt NCs and Pt/C in HClO4, KOH, and NaHCO3 electrolytes, respectively, owing to the porous branched structure with a high surface area, which maximizes Pt utilization. Notably, the COOxid performance of Pt NPs in HClO4 is higher than that in NaHCO3, and KOH under the same reaction conditions. This study may open the way for understanding the COOxid activities of Pt-based catalysts and avoiding CO-poisoning in fuel cells.

Fabrication and Characterization of Nanocomposite Flexible Membranes of PVA and Fe3O4.

Composite polymer membranes of poly(vinyl alcohol) (PVA) and iron oxide (Fe3O4) nanoparticles were produced in this work. X-ray diffraction measurements demonstrated the formation of Fe3O4 nanoparticles of cubic structures. The nanoparticles were synthesized by a coprecipitation technique and added to PVA solutions with different concentrations. The solutions were then used to generate flexible membranes by a solution casting method. The size and shape of the nanoparticles were investigated using scanning electron microscopy (SEM). The average size of the nanoparticles was 20±9 nm. Raman spectroscopy and Fourier-transform infrared spectroscopy (FTIR) were utilized to investigate the structure of the membranes, as well as their vibration modes. Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated the thermal stability of the membranes and the crystallinity degree. Electrical characteristics of the thin membranes were examined using impedance spectroscopy as a function of the nanoparticles' concentrations and temperatures. The resistivity of the fabricated flexible membranes was possible to adjust by controlled doping with suitable concentrations of nanoparticles. The activation energy decreased with the nanoparticles' concentrations due to the increase in charge carriers' concentrations. Therefore, the fabricated membranes may be applied for practical applications that involve the recycling of nanoparticles for multiple application cycles.

Scalable One-Pot Fabrication of Carbon-Nanofiber-Supported Noble-Metal-Free Nanocrystals for Synergetic-Dependent Green Hydrogen Production: Unraveling Electrolyte and Support Effects.

Electrocatalytic hydrogen evolution reactions (HER) are envisaged as the most promising sustainable approach for green hydrogen production. However, the considerably high cost often associated with such reactions, particularly upon scale-up, poses a daunting challenge. Herein, a facile, effective, and environmentally benign one-pot scalable approach is developed to fabricate MnM (M═Co, Cu, Ni, and Fe) nanocrystals supported over in situ formed carbon nanofibers (MnM/C) as efficient noble-metal-free electrocatalysts for HER. The formation of carbon nanofibers entails impregnating cellulose in an aqueous solution of metal precursors, followed by annealing the mixture at 550 °C. During the impregnation process, cellulose acts as a reactor for inducing the in situ reductions of MnM salts with the assistance of ether and hydroxyl groups to drive the mass production (several grams) of ultralong (5 ± 1 µM) carbon nanofibers ornamented with MnM nanoparticles (10-14 nm in size) at an average loading of 2.87 wt %. For better electrocatalytic HER benchmarking, the fabricated catalysts were tested over different working electrodes, i.e., carbon paper, carbon foam, and glassy carbon, in the presence of different electrolytes. All the fabricated MnM/C catalysts have demonstrated an appealing synergetic-effect-dependent HER activity, with MnCo/C exhibiting the best performance over carbon foam, close to that of the state-of-the-art commercial Pt/C (10 wt % Pt), with an overpotential of 11 mV at 10 mA cm-2, a hydrogen production rate of 2448 mol g-1 h-1, and a prolonged stability of 2 weeks. The HER performance attained by MnCo/C nanofibers is among the highest reported for Pt-free electrocatalysts, thanks to the mutual alloying effect, higher synergism, large surface area, and active interfacial interactions over the nanofibers. The presented findings underline the potential of our approach for the large-scale production of cost-effective electrocatalysts for practical HER.

Unveiling the effect of shapes and electrolytes on the electrocatalytic ethanol oxidation activity of self-standing Pd nanostructures.

Morphologically controlled Pd-based nanocrystals are the most efficient strategies for improving the electrocatalytic ethanol oxidation reaction (EOR) performance; however, their morphological-EOR activity relationship and effect of electrolytes at a wide pH range are still ambiguous. Here, we have synthesized porous self-standing Pd clustered nanospheres (Pd-CNSs) and Pd nanocubes (Pd-NCBs) for the EOR in acidic (H2SO4), alkaline (KOH), and neutral (NaHCO3) electrolytes compared to commercial spherical-like Pd/C catalysts. The fabrication process comprises the ice-cooling reduction of Pd precursor by sodium borohydride (NaBH4) and l-ascorbic acid to form Pd-CNSs and Pd-NCBs, respectively. The EOR activity of Pd-CNSs significantly outperformed those of Pd-NCBs, and Pd/C in all electrolytes, but the EOR activity was better in KOH than in H2SO4 and NaHCO3. This is due to the 3D porous clustered nanospherical morphology that makes Pd active centers more accessible and maximizes their utilization during EOR. The EOR specific/mass activities of Pd-CNSs reached (8.51 mA/cm2/2.39 A/mgPd) in KOH, (2.98 mA/cm2/0.88 A/mgPd) in H2SO4, and (0.061 mA/cm2/0.0083 A/mgPd) in NaHCO3, in addition to stability after 1000 cycles. This study affirms that porous 3D spherical Pd nanostructures are preferred for the EOR than those of 0D spherical-like and multi-dimensional cube-like nanostructures.

Breast-Feeding Protects Infantile Diarrhea Caused by Intestinal Protozoan Infections

This study investigated the effect of breast-feeding in protection against protozoan infection in infants with persistent diarrhea. Infants were classified into 2 groups; 161 breast-fed infants and the same number of non-breast-fed infants. Microscopic examinations of stool were done for detection of parasites and measuring the intensity of infection. Moreover, serum levels of IgE and TNF-alpha were measured by ELISA. Cryptosporidium spp., Entamoeba histolytica/Entamoeba dispar, Giardia lamblia, and Blastocystis sp. were demonstrated in infants with persistent diarrhea. The percentage of protozoan infections was significantly lower in breast-fed infants than that in the non-breast-fed infants. The levels of IgE and TNF-alpha were significantly lower in the breast-fed group than in the non-breast-fed group. There were significant positive associations between the serum levels of IgE and TNF-alpha and the intensity of parasite infection in the breast-fed group. It is suggested that breast-feeding has an attenuating effect on the rate and intensity of parasite infection.