Co/Ce-MOF-Derived Oxygen Electrode Bifunctional Catalyst for Rechargeable Zinc-Air Batteries.

Improving the practicality of rechargeable zinc-air batteries relies heavily on the development of oxygen electrode catalysts that are low-cost, durable, and highly efficient in performing dual functions. In the present study, a catalyst with atomic Ce and Co distribution on a nitrogen-doped carbon substrate was prepared by doping the rare earth elements Ce and Co into a metal-organic framework precursor. Rare earth element Ce, known for its unique structure and excellent oxygen affinity, was utilized to regulate the catalytic activity. The catalyst prepared in this study demonstrated an exceptional electrocatalytic performance. At a current density of 10 mA cm-2, the catalyst exhibited an overpotential of 340 mV for the oxygen evolution reaction (OER), which was lower than that of commercial IrO2 (370 mV), while achieving a half-wave potential of 0.79 V for the process of oxygen reduction reaction (ORR), exhibiting a similar level of effectiveness as commercially accessible Pt/C catalysts (0.8 V). The catalyst's porous structure, interconnected three-dimensional carbon network, and large specific surface area are the factors contributing to the significant improvement in catalytic performance. Furthermore, in comparison to commercial Pt/C+IrO2, the catalyst exhibited good cycling stability and high efficiency in rechargeable zinc-air batteries.

Xerogel-Derived Manganese Oxide/N-Doped Carbon as a Non-Precious Metal-Based Oxygen Reduction Reaction Catalyst in Microbial Fuel Cells for Energy Conversion Applications.

Current study provides a novel strategy to synthesize the nano-sized MnO nanoparticles from the quick, ascendable, sol-gel synthesis strategy. The MnO nanoparticles are supported on nitrogen-doped carbon derived from the cheap sustainable source. The resulting MnO/N-doped carbon catalysts developed in this study are systematically evaluated via several physicochemical and electrochemical characterizations. The physicochemical characterizations confirms that the crystalline MnO nanoparticles are successfully synthesized and are supported on N-doped carbons, ascertained from the X-ray diffraction and transmission electron microscopic studies. In addition, the developed MnO/N-doped carbon catalyst was also found to have adequate surface area and porosity, similar to the traditional Pt/C catalyst. Detailed investigations on the effect of the nitrogen precursor, heat treatment temperature, and N-doped carbon support on the ORR activity is established in 0.1 M of HClO4. It was found that the MnO/N-doped carbon catalysts showed enhanced ORR activity with a half-wave potential of 0.69 V vs. RHE, with nearly four electron transfers and excellent stability with just a loss of 10 mV after 20,000 potential cycles. When analyzed as an ORR catalyst in dual-chamber microbial fuel cells (DCMFC) with Nafion 117 membrane as the electrolyte, the MnO/N-doped carbon catalyst exhibited a volumetric power density of ~45 mW m2 and a 60% degradation of organic matter in 30 days of continuous operation.

Evaluating the Oxygen Electrode Reactions of La Single-Atom Catalysts with the N/C Coordination Effect.

There is a growing demand for bifunctional electrocatalysts for oxygen electrodes in rechargeable metal-air batteries. This article investigates the bifunctional activity of La single-atom catalysts with N/C coordination (LaNxC6-x@Gra) using density functional theory (DFT). The augmentation of N coordination will result in enhanced synthetic stability. The coordination between nitrogen and carbon (N/C) has a significant influence on the working stability of the system under consideration. In the context of active atoms, the coordination between nitrogen and carbon (N/C coordination) has a significant impact on the electronic structure. This, in turn, influences the adsorption performance and catalytic activity of the catalysts. In the case of stable coordination environments, a correlation exists between the f-orbital center (εf) and the overpotential (η) via the adsorption free energy of intermediates (ΔG*ads). This correlation serves as a useful tool for predicting catalytic performance. The LaNxC6-x@Gra exhibits remarkable bifunctional activity due to its complementary performance, with an overpotential for the oxygen reduction reaction (ηORR) of 0.66 V and an overpotential for the oxygen evolution reaction (ηOER) of 0.43 V. This makes it a promising candidate for use as a bifunctional electrocatalyst in oxygen electrodes.

Investigating the Performance of a Zinc Oxide Impregnated Polyvinyl Alcohol-Based Low-Cost Cation Exchange Membrane in Microbial Fuel Cells.

The current study investigated the development and application of lithium (Li)-doped zinc oxide (ZnO)-impregnated polyvinyl alcohol (PVA) proton exchange membrane separator in a single chambered microbial fuel cell (MFC). Physiochemical analysis was performed via FT-IR, XRD, TEM, and AC impedance analysis to characterize thus synthesized Li-doped ZnO. PVA-ZnO-Li with 2.0% Li incorporation showed higher power generation in MFC. Using coulombic efficiency and current density, the impact of oxygen crossing on the membrane cathode assembly (MCA) area was evaluated. Different amounts of Li were incorporated into the membrane to optimize its electrochemical behavior and to increase proton conductivity while reducing biofouling. When acetate wastewater was treated in MFC using a PVA-ZnO-Li-based MCA, the maximum power density of 6.3 W/m3 was achieved. These observations strongly support our hypothesis that PVA-ZnO-Li can be an efficient and affordable separator for MFC.

Solid-State Synthesis of Cobalt/NCS Electrocatalyst for Oxygen Reduction Reaction in Dual Chamber Microbial Fuel Cells.

Due to the high cost of presently utilized Pt/C catalysts, a quick and sustainable synthesis of electrocatalysts made of cost-effective and earth-abundant metals is urgently needed. In this work, we demonstrated a mechanochemically synthesized cobalt nanoparticles supported on N and S doped carbons derived from a solid-state-reaction between zinc acetate and 2-amino thiazole as metal, organic ligand in presence of cobalt (Co) metal ions ZnxCox(C3H4N2S). Pyrolysis of the ZnxCox(C3H4N2S) produced, Co/NSC catalyst in which Co nanoparticles are evenly distributed on the nitrogen and sulfur doped carbon support. The Co/NSC catalyst have been characterized with various physical and electrochemical characterization techniques. The Co content in the ZnxCox(C3H4N2S) is carefully adjusted by varying the Co content and the optimized Co/NSC-3 catalyst is subjected to the oxygen reduction reaction in 0.1 M HClO4 electrolyte. The optimized Co/NSC-3 catalyst reveals acceptable ORR activity with the half-wave potential of ~0.63 V vs. RHE in acidic electrolytes. In addition, the Co/NSC-3 catalyst showed excellent stability with no loss in the ORR activity after 10,000 potential cycles. When applied as cathode catalysts in dual chamber microbial fuel cells, the Co/NCS catalyst delivered satisfactory volumetric power density in comparison with Pt/C.

A Novel Nanocomposite Based on Triazine Based Covalent Organic Polymer Blended with Porous g-C3N4 for Photo Catalytic Dye Degradation of Rose Bengal and Fast Green.

Metal free visible light active photocatalysts of covalent organic polymers (COPs) and polymeric graphitic carbon nitride (g-C3N4) are interesting porous catalysts that have enormous potential for application in organic pollutant degradation. Imine condensation for COPs, and thermal condensation for g-C3N4 were used to produce the catalysts. FT-IR, Raman, NMR, UV-Vis Spectroscopy, X-ray diffraction, and scanning electron microscopy studies were used to investigate the structural, optical, and morphological features of the metal free catalysts. We have constructed COPs with a π-electron deficient (Lewis acidic) triazine core and π -electron rich (Lewis basic) naphthalene and anthraquinone rings coupled by -O and -N donors in this study. Furthermore, the prepared Bulk-g-C3N4 (B-GCN) was converted to porous g-C3N4 (P-GCN) using a chemical oxidation process, and the generated P-GCN was efficiently mixed with the COP to create a novel nanocomposite for photocatalytic application. Using the anthraquinone-based COP and P-GCN (1:1 ratio, PA-GCN) catalyst, the highest photodegradation efficiencies for the polymeric graphitic carbon nitride of 88.2% and 82.3% were achieved using the Fast green (FG) and Rose bengal (RB) dyes, respectively. The rate constant values of 0.032 and 0.024/min were determined for FG and RB degradation, respectively. Higher activity may be related to the incorporation of COP and PA-GCN, which act significantly well in higher visible light absorption, have superior reactive oxygen generation (ROS), and demonstrate an excellent pollutant-catalyst interaction.

2D MXene Nanomaterials as Electrocatalysts for Hydrogen Evolution Reaction (HER): A Review.

MXenes, a novel family of 2D transition metal carbide, nitride and carbonitride materials, have been gaining tremendous interest in recent days as potential electrocatalysts for various electrochemical reactions, including hydrogen evolution reaction (HER). MXenes are characterized by their etchable metal layers, excellent structural stability, versatility for heteroatoms doping, excellent electronic conductivity, unique surface functional groups and admirable surface area, suitable for the role of electrocatalyst/support in electrochemical reactions, such as HER. In this review article, we summarized recent developments in MXene-based electrocatalysts synthesis and HER performance in terms of the theoretical and experimental point of view. We systematically evaluated the superiority of the MXene-based catalysts over traditional Pt/C catalysts in terms of HER kinetics, Tafel slope, overpotential and stability, both in acidic and alkaline electrolytic environments. We also pointed out the motives behind the electro catalytic enhancements, the effect of synthesis conditions, heteroatom doping, the effect of surface terminations on the electrocatalytic active sites of various MXenes families. At the end, various possible approaches were recommended for a deeper understanding of the active sites and catalytic improvement of MXenes catalysts for HER.

Electrocoagulation treatment of raw palm oil mill effluent: Optimization process using high current application.

In the electrocoagulation wastewater treatment process, extremely polluted water treatment requires an effective technique, and using high current is one of those. This study aims to optimize electrocoagulation parameters such as operation time, electrodes gap and the initial pH by applying high current intensity to treat palm oil mill effluent (POME) via Box-Behnken design (BBD) method. Chemical oxygen demand (COD), biological oxygen demand (BOD), and suspended solids (SS) were used as the response variables in the quadratic polynomial model. Most of the selected models in the analysis of variance (ANOVA) have shown significant results. A high connection between the parameters and dependent variables was surprisingly discovered in this study which the obtained value of R2 for removal percentage of COD, BOD and SS were 0.9975, 0.9984 and 0.9979 respectively. Optimal removal was achieved at 19.07 A of current intensity (equivalent to 542 mA/cm2 of current density), 44.97 min of treatment time, 8.60 mm of inter-electrode distance and 4.37 of pH value, resulted in 97.21%, 99.26% and 99.00% of COD, BOD and SS removal respectively. This optimized scheme of operating parameters combination offers an alternate choice for enhancing the treatment efficiency of POME and also can be a benchmark for other researchers to treat highly polluted wastewater.

Recent progress in transition metal oxide/sulfide quantum dots-based nanocomposites for the removal of toxic organic pollutants.

Water is an essential solvent that is extremely necessary for the survival of life. Water pollution due to the increased utilization of water for various processes, including domestic and industrial activities, poses a special threat that contaminates both surface and ground water. In recent years, advanced oxidation processes (AOPs) have been applied to deal with wastewater problems, which is a green method used to oxidize organic contaminants with strong oxidative radical species. Among the AOPs, photocatalytic technology is one of the most promising strategies for wastewater cleaning, which fulfills the aims of environmentally friendly and sustainable development. Owing to their unique electronic, optical, and structural properties, nanoscale semiconductors have received substantial interest as materials for AOPs, particularly inspired by their superb quantum confinement effects and large surface-area-to-volume ratio, which are essential for catalytic reaction kinetics. Recent advancements have revealed that semiconductor nanocrystals, known as quantum dots (QDs), are newly emerging zero-dimensional (0-D) nanomaterials, which have garnered much attention owing to their special physiochemical characteristics such as high conductivity, thermo-chemical and opto-mechanical stability, high adsorption coefficients, and, most importantly, their admirable recyclability. In this review, we provide a clear understanding of the importance of semiconductor QD-based nanocomposites in the degradation of organic pollutants, in addition to the mechanism involved in the reaction process. Following this, the enhancement of different materials, such as metal oxides and metal sulfide QD-based nanocomposites, is discussed in the context of combating environmental pollution.

Theoretical Study on a Nitrogen-Doped Graphene Nanoribbon with Edge Defects as the Electrocatalyst for Oxygen Reduction Reaction.

Both theory and experiment show that sp2 carbon nanomaterials doped with N have great potential as high-efficiency catalysts for oxygen reduction reactions (ORR). At present, there are theoretical studies that believe that C-sites with positive charge or high-spin density values have higher adsorption capacity, but there are always some counter examples, such as the N-doped graphene nanoribbons with edge defects (ND-GNR) of this paper. In this study, the ORR mechanism of ND-GNR was studied by density functional theory (DFT) calculation, and then the carbon ring resonance energy was analyzed from the perspective of chemical graph theory to elucidate the cause and distribution of active sites in ND-GNR. Finally, it was found that the overpotential of the model can be adjusted by changing the width of the model or dopant atoms while still ensuring proper adsorption energy (between 0.5 and 2.0 eV). The minimum overpotential for these models is approximately 0.36 V. These findings could serve as guidelines for the construction of efficient ORR carbon nanomaterial catalysts.

Highly Active and Durable Core-Shell fct-PdFe@Pd Nanoparticles Encapsulated NG as an Efficient Catalyst for Oxygen Reduction Reaction.

Development of highly active and durable catalysts for oxygen reduction reaction (ORR) alternative to Pt-based catalyst is an essential topic of interest in the research community but a challenging task. Here, we have developed a new type of face-centered tetragonal (fct) PdFe-alloy nanoparticle-encapsulated Pd (fct-PdFe@Pd) anchored onto nitrogen-doped graphene (NG). This core-shell fct-PdFe@Pd@NG hybrid is fabricated by a facile and cost-effective technique. The effect of temperature on the transformation of face-centered cubic (fcc) to fct structure and their effect on ORR activity are systematically investigated. The core-shell fct-PdFe@Pd@NG hybrid exerts high synergistic interaction between fct-PdFe@Pd NPs and NG shell, beneficial to enhance the catalytic ORR activity and excellent durability. Impressively, core-shell fct-PdFe@Pd@NG hybrid exhibits an excellent catalytic activity for ORR with an onset potential of ∼0.97 V and a half-wave potential of ∼0.83 V versus relative hydrogen electrode, ultrahigh current density, and decent durability after 10 000 potential cycles, which is significantly higher than that of marketable Pt/C catalyst. Furthermore, the core-shell fct-PdFe@Pd@NG hybrid also shows excellent tolerance to methanol, unlike the commercial Pt/C catalyst. Thus, these findings open a new protocol for fabricating another core-shell hybrid by facile and cost-effective techniques, emphasizing great prospect in next-generation energy conversion and storage applications.

Sustainable Synthesis of Co@NC Core Shell Nanostructures from Metal Organic Frameworks via Mechanochemical Coordination Self-Assembly: An Efficient Electrocatalyst for Oxygen Reduction Reaction.

Herein, a new type of cobalt encapsulated nitrogen-doped carbon (Co@NC) nanostructure employing Znx Co1-x (C3 H4 N2 ) metal-organic framework (MOF) as precursor is developed, by a simple, ecofriendly, solvent-free approach that utilizes a mechanochemical coordination self-assembly strategy. Possible evolution of Znx Co1-x (C3 H4 N2 ) MOF structures and their conversion to Co@NC nanostructures is established from an X-ray diffraction technique and transmission electron microscopy analysis, which reveal that MOF-derived Co@NC core-shell nanostructures are well ordered and highly crystalline in nature. Co@NC-MOF core-shell nanostructures show excellent catalytic activity for the oxygen reduction reaction (ORR), with onset potential of 0.97 V and half-wave potential of 0.88 V versus relative hydrogen electrode in alkaline electrolyte, and excellent durability with zero degradation after 5000 potential cycles; whereas under similar experimental conditions, the commonly utilized Pt/C electrocatalyst degrades. The Co@NC-MOF electrocatalyst also shows excellent tolerance to methanol, unlike the Pt/C electrocatalyst. X-ray photoelectron spectroscopy (XPS) analysis shows the presence of ORR active pyridinic-N and graphitic-N species, along with CoNx Cy and CoNx ORR active (M-N-C) sites. Enhanced electron transfer kinetics from nitrogen-doped carbon shell to core Co nanoparticles, the existence of M-N-C active sites, and protective NC shells are responsible for high ORR activity and durability of the Co@NC-MOF electrocatalyst.

High-energy asymmetric supercapacitors based on free-standing hierarchical Co-Mo-S nanosheets with enhanced cycling stability.

Layered transition metal sulfides (TMS) are emerging as advanced materials for energy storage and conversion applications. In this work, we report a facile and cost-effective anion exchange technique to fabricate a layered, multifaceted, free standing, ultra-thin ternary cobalt molybdenum sulfide nanosheet (Co-Mo-S NS) architecture grown on a 3D porous Ni foam substrate. The unique Co-Mo layered double hydroxides are first synthesized as precursors and consequently transformed into ultra-thin Co-Mo-S NS. When employed as an electrode for supercapacitors, the Co-Mo-S NS delivered an ultra-high specific capacitance of 2343 F g-1 at a current density of 1 mA cm-2 with tremendous rate capability and extraordinary cycling performance (96.6% capacitance retention after 20 000 cycles). Furthermore, assembled Co-Mo-S/nitrogen doped graphene nanosheets (NGNS) in an asymmetric supercapacitor (ASC) device delivered an excellent energy density of 89.6 Wh kg-1, an amazing power density of 20.07 kW kg-1, and superior cycling performance (86.8% capacitance retention after 50 000 cycles). Such exceptional electrochemical performance of Co-Mo-S NS is ascribed to the good electrical contact with the 3D Ni foam, ultra-high contact area with the electrolyte, and enhanced architectural softening during the charging/discharging process. It is expected that the fabricated, unique, ultra-thin Co-Mo-S NS have great potential for future energy storage devices.