Oxide Research Articles

The green approach of chitosan/Fe2O3/ZnO-nanocomposite synthesis with an evaluation of its biological activities

AbstractBiopolymers embedded with nanoparticles of metal oxides (MOs) demonstrate a wide range of bio-functions. Chitosan-incorporated MOs are an interesting class of support matrices for enhancing the biological function, compared to other support matrices. Therefore, the importance of this study lies in exploiting chitosan as a carrier not of one metal as in previous studies, but of two metals in the form of a nanocomposite to carry out several biological functions. The coprecipitation approach was employed to synthesize chitosan/Fe2O3/ZnO-nanocomposite in the present research. The characterization of chitosan/Fe2O3/ZnO-nanocomposite was performed to find out the morphology and dispersion properties of chitosan/Fe2O3/ZnO-nanocomposite. The X-ray diffraction (XRD) investigation revealed that these were crystalline. Fourier transforms infrared (FTIR) spectrum bands were viewed at 400/cm and 900/cm, due to the stretching vibration of Fe and Zn oxygen bond. TEM showed that chitosan/Fe2O3/ZnO-nanocomposite was of 20–95 nm in size. chitosan/Fe2O3/ZnO-nanocomposite exhibited inhibitory potential against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Candida albicans with inhibition zones of 25 ± 0.1, 28 ± 0.2, 27 ± 0.1, and 27 ± 0.2 mm, respectively while didn’t inhibited Aspergillus niger. MIC value of nanocomposite was 15.62 ± 0.33 µg/mL for C. albicans, B. subtilis and E. coli, while it was 62.50 ± 0.66 µg/mL for Pseudomonas aeruginosa. Ranged values of nanocomposite MBC (15.62 ± 0.33 to 125 ± 1 µg/mL) were attributed to all tested bacteria. Different concentrations of chitosan/Fe2O3/ZnO-nanocomposite MBC (25, 50, and 75%) reflected anti-biofilm activity against E. coli (85.0, 93.2, and 96.0%), B. subtilis (84.88, 92.21, and 96.99%), S. aureus 81.64, 90.52, and 94.64%) and P. aurogenosa (90.11, 94.43, and 98.24%), respectively. The differences in the levels of antimicrobial activities may depend on the type of examined microbes. Antioxidant activity of chitosan/Fe2O3/ZnO-nanocomposite was recorded with excellent IC50 values of 16.06 and 32.6 µg/mL using DPPH and ABTS scavenging, respectively. Wound heal by chitosan/Fe2O3/ZnO-nanocomposite was achieved with 100% compared to the untreated cells (76.75% of wound closer). The cytotoxicity outcomes showed that the IC50 of the chitosan/Fe2O3/ZnO-nanocomposite was 564.32 ± 1.46 µg/mL normal WI-38 cells. Based on the achieved findings, the chitosan/Fe2O3/ZnO-nanocomposite is a very promising agent for perform pharmacological activities.

Electronic and magnetic phase diagram of Sr2FeO4 at high pressure: A synchrotron Mössbauer study

Transition metal (TM) oxides with high oxidation state TM ions exhibit a variety of unconventional electronic and magnetic states owing to electron correlations effects combined with highly covalent TM–O bonding. Here, we have studied the pressure dependence of electronic state and magnetism of the K2NiF4-type iron(IV) oxide Sr2FeO4 up to 89 GPa by temperature and magnetic field dependent energy-domain synchrotron Mössbauer spectroscopy and derived a (P,T) magnetic phase diagram. Considering also previous resistance studies [Rozenberg , ] several magnetic and electronic regimes with increasing pressure can be identified. Near 7 GPa, the insulating cycloidal antiferromagnetic low-P state is transformed into a semiconducting ferromagnetic state and the magnetic ordering temperature Tm increases from 55 K at ambient pressure to about 100 K at 13 GPa. Between 18 and about 50 GPa the system is ferromagnetic and metallic (FMM) with a strong rise of Tm to above room temperature (RT). Contrary to a recent theoretical study [Kazemi-Moridani , ], the FMM state is attributed to a high-spin t2g3eg1 electronic state with itinerant eg coupled to more localized t2g electrons. Between 50 and 89 GPa a doublet with large quadrupole splitting in the RT Mössbauer spectra indicates a partial high-spin to low-spin (t2g4) transition leading to a decrease in Tm again. The general features of the (P,T) phase diagram of Sr2FeO4 are comparable to those of other simple and A-site ordered iron(IV) perovskite-related oxides with the peculiarity that Sr2FeO4 adopts an insulating state without charge disproportionation of Fe4+ in the low-P region. The high-pressure behavior of Sr2FeO4 and other iron(IV) oxides may be relevant for exploring the role of Hund's physics in multiorbital systems and contributing to the understanding of the electronic situation in unconventional superconductors such as La3Ni2O7 and Sr2RuO4. Published by the American Physical Society 2024

Engineered hybrid iron‐cobalt metal oxide nanoparticles for effective adsorption of malachite green dye

AbstractBACKGROUNDHybrid iron and cobalt metal oxide nanoparticles are well known; however, are not optimized in terms of size and stability. We engineered these hybrid nanoparticles using the co‐precipitation method and characterized them by various techniques, which are then used for the effective adsorption and removal of malachite green (MG) dye.RESULTSThe ideal conditions for synthesis are determined to be 50:50 ratio of Fe2O3 and CoO, pH of 11, temperature range of 40 °C–60 °C, and reactant addition time of 20 min. These hybrid nanoadsorbents effectively eliminated MG dye from aqueous solutions. Factors such as initial MG dye concentration, pH of the medium, contact time, temperature, and nanoadsorbent dose were optimized for the MG removal to achieve a maximum removal efficiency of 96.9%. Non‐linear fitting of data indicates that both Langmuir and Freundlich models provided the best fit, suggesting the presence of both monolayer and multilayer adsorption of MG on hybrid nanoparticles. The kinetics of MG dye removal are better controlled by the intraparticle diffusion (IPD) phenomenon. The adsorption of MG onto the hybrid nanoparticles was confirmed to be endothermic, with negative ΔG and positive ΔH values. The optimized synthetic conditions also positively impacted the hybrid nanoparticles which enhanced the adsorption and exhibited ferromagnetic behavior as compared to the superparamagnetic behavior reported in the literature, making them significantly important for dye removal applications.CONCLUSIONThese findings demonstrate the potential of optimized hybrid nanoparticles as effective nanoadsorbents for dye removal applications, with implications for further applications in photocatalysis and sensing. © 2024 Society of Chemical Industry (SCI).

Microstructure, Mechanical, and Tribological Properties of Nb-Doped TiAl Alloys Fabricated via Laser Metal Deposition

TiAl alloys possess excellent properties, such as low density, high specific strength, high elastic modulus, and high-temperature creep resistance, which allows their use to replace Ni-based superalloys in some high-temperature applications. In this work, the traditional TiAl alloy Ti-48Al-2Nb-2Cr (Ti4822) was alloyed with additional Nb and fabricated using laser metal deposition (LMD), and the impacts of this additional Nb on the microstructure and mechanical and tribological properties of the as-fabricated alloys were investigated. The resulting alloys mainly consisted of the γ phase, trace β0 and α2 phases. Nb was well distributed throughout the alloys, while Cr segregation resulted in the residual β0 phase. Increasing the amount of Nb content increased the amount of the γ phase and reduced the amount of the β0 phase. The alloy Ti4822-2Nb exhibited a room-temperature (RT) fracture strength under a tensile of 568 ± 7.8 MPa, which was nearly 100 MPa higher than that of the Ti4822-1Nb alloy. A further increase in Nb to an additional 4 at.% Nb had little effect on the fracture strength. Both the friction coefficient and the wear rate increased with the increasing Nb content. The wear mechanisms for all samples were abrasive wear with local plastic deformation and oxidative wear, resulting in the formation of metal oxide particles.

Selective discrimination and accurate quantification of five target vapors among multiple vapors using 2D CuO and Co3O4 sensors

Selective and sensitive detection of volatile organic compounds (VOCs) are critically needed for various applications like environmental sustainability, industrial safety, healthcare, etc Metal oxides are one of the most explored chemiresistive sensing materials because of their high sensitivity, but they lack selectivity. This work reports synthesis of two metal oxides - CuO and Co3O4 using surfactant assisted hydrothermal method. The 2D morphologies of both the metal oxides were ensured through fielded emission scanning electron microscope. The polycrystalline nature of the materials was studied using X-ray diffractometer and bandgaps were found to be 1.72 eV (CuO) and 1.9 and 2.89 eV (Co3O4) through the Kubelka Munk plot. The two metal oxides were employed to detect four different concentrations (6–50 ppm) of five targeted VOCs (lung cancer biomarkers) - acetone, acetonitrile, isopropanol, methanol, and toluene. In addition, response of the sensors for 6–50 ppm of ethyl acetate, hexanal, ammonia, and NO2 were also recorded as these VOCs are naturally produced in the body as a result of metabolic processes. The responses were recorded for 10 min for all the gases with CuO and Co3O4. Despite the intrinsic metal oxides lacking selectivity towards a specific VOC, careful feature selection achieved a classification accuracy of 95% using random forest (RF) algorithm. Subsequent application of RF model on validation dataset yielded a 91% accuracy in identifying target VOCs. Multilinear regression (MLR) algorithm was then employed to quantify the concentrations of the VOCs and low mean absolute error (MAE) values were obtained.

Recent progress on Cobalt‐based Heterogeneous Catalysts for Hydrogen Production from Ammonia Borane

Ammonia borane (NH3BH3, AB) is a quintessential exemplar of chemical hydrogen storage materials and has been widely used in hydrogen evolution. Although expensive metal catalysts (such as Rh, Ru, Pt, Ag, etc.) exhibit high activity in the hydrolysis of ammonia borane, inexpensive metals are more economical. Cobalt (Co), in particular, is not only relatively inexpensive and readily available, but also possesses high activity and selectivity. Compared to other catalysts, cobalt‐based catalysts have better durability and can maintain catalytic activity for a longer period of time, making them favored by researchers. These catalysts demonstrate excellent stability, hydrogen evolution rate, and turn over frequency. This article summarized previous progress in low price metal cobalt‐based catalysts for hydrogen precipitation from ammonia borane, focusing on cobalt‐based catalysts supported on various supports, especially those supported on carbon materials, metal oxides, MOFs, and nickel foams. The characteristics of high‐performance catalytic systems are analyzed in detail. The development prospects of Co catalysts for hydrogen production from ammonia borane were also discussed.

Facile construction of binary metal oxide heterojunction with hexagonal boron nitride nanohybrid electrocatalyst for the detection of flutamide

BackgroundFlutamide (FU) is a potential anti-androgen drug significantly prescribed to all human beings. The high solubility and poor degradability of its metabolites can adversely affect the balance of the ecosystem. Therefore, developing an efficient and reliable technique to detect this pollutant is essential. Consequently, electrochemical sensors have been widely used for the monitoring of various real-world samples. MethodsHence, nickel-zinc oxide (NZO) with hexagonal boron nitride (h-BN) nanocomposite was prepared as a proficient electrocatalyst in FU detection. Several spectroscopic measurements were carried out to characterize the prepared materials. Our NZO/h-BN nanocomposite was utilized to modify the glassy carbon electrode (GCE) and its relative catalytic activity was scrutinized with impedance and various voltammetric techniques. Significant findingsBased on the results, our NZO/h-BN/GCE sensor exhibited high conductance, appreciable linear ranges, low detection limit (0.002 μM), optimal sensitivity (2.149 µA µM−1 cm−2), and high selectivity with good repeatability, and reproducibility results. Furthermore, the practical utility of the sensor was studied by monitoring FU in human and environmental samples. Based on the outcomes, our NZO/h-BN/GCE is a promising electrochemical platform for the detection of FU.

Ultra‐Thin Metal Oxide Superstructure of Pd(001) as Passivation Interlayer at Organic/Metal Interface

AbstractAt organic molecule/metal interfaces for electronic applications, it is required of the metal surface to be passivated in view of preserving the molecular properties of the ordered organic layer. This can be achieved by screening the metal with a single atomic layer of O, namely, ultra‐thin metal oxide (UTMO) layers. Cobalt tetraphenylporphyrins (CoTPP) on oxygen passivated Fe(001), with 1 ML O coverage, have revealed a molecule/substrate decoupling effect due to the formation of an ultra‐thin Fe oxide layer at the interface. However, the threshold concentration of surface O required to observe the decoupling effect has not been assessed yet. In this work, the possibility of stabilizing different ultra‐thin Pd oxide superstructures, characterized by a different number of O atoms per unit cell, is exploited to investigate the O decoupling effect on CoTPP films. Two Pd oxide superstructures are considered: Pd(001)‐p(2 × 2)O and Pd(001)‐p(√5 × √5)R27°O, with 0.25 and 0.80 ML O coverages, respectively, which are characterized by low‐energy electron diffraction (LEED), X‐ray and ultra‐violet photoelectron spectroscopies (XPS/UPS) and inverse photoemission spectroscopy (IPES). The results suggest a lower limit of 0.80 ML O coverage as a passivation interlayer to obtain an ordered and decoupled CoTPP monolayer on Pd(001).

Cerium oxide for L-band Q-switched pulse laser generation

Cerium oxide (CeO2), a rare earth metal oxide belonging to the lanthanide group is a mature engineered nanoparticle that has been developed for various industry applications. The nanoparticle features defects in its lattice structure, which is highly advantageous for bandgap tuning, and is acclaimed for its least cytotoxicity among other metal oxides. In this work, CeO2 is employed as a saturable absorber (CeO2-SA) in the generation of an L-band Q-switched erbium-doped fiber laser. Q-switching was attained at 33.33 mW pump power threshold with a central wavelength of 1600.512 nm. Within 33.33 mW to 153.20 mW pump power range, the Q-switched laser obtained pulse repetition rates between 11.00 to 34.48 kHz, and pulse widths between 39.0 to 12.0 µs, with a high maximum pulse energy of 410 nJ. The Q-switched fiber laser remained stable over a 45-minute observation time at 153.20 mW pump power. The room temperature and direct mechanical deposition fabrication technique of the CeO2-SA in this work demonstrates the extreme simplicity and low cost of the device, which would reduce the overall cost and facilitate a wider technology adoption of pulse laser systems.

Synergistic degradation of p-nitrophenol using peroxymonosulfate activated with a bimetallic Mn3O4–Cu2O catalyst: Investigation of strong interactions between metal oxides

The use of efficient, eco-friendly catalysts is essential for activating peroxymonosulfate (PMS) to degrade organic contaminants in aqueous media. In this study, we developed a novel approach to fabricating bimetallic MnCu catalysts (Mn:Cu molar ratios: 10:1, 5:1, 3:1, and 2:1) comprising tetragonal Mn3O4 and cubic Cu2O. MnCu-5:1 exhibited superior catalytic activity for the degradation of p-nitrophenol (PNP) using PMS because of the synergistic interplay between Mn and Cu. Experimental and density functional theory (DFT) calculation data revealed that the mixed valence states and strong interactions between Mn and Cu in the MnCu-5:1 system increased the electron transfer efficiency and promoted electron transfer to PMS. The results of quenching experiments elucidated a primary radical mechanism and minor nonradical pathway for the PNP degradation over the MnCu-5:1/PMS system. DFT calculations confirmed a relatively high adsorption energy of the Mn3O4–Cu2O (MnCu) composite, indicating enhanced catalytic performance. The superior reactivity of the composite was verified by analyzing its density of states and electrostatic difference potential. Our findings offer fresh perspectives for harnessing the synergistic potential of less toxic mixed metal oxides for controlling catalytic properties and help achieve a better understanding of the activation mechanism for contaminant degradation over MnCu catalysts.

Transition metal atom on the two-dimensional Dirac structure RhB4/OsB4: A novel multifunctional electrocatalyst

The design of low-cost multifunctional electrocatalysts with high carrier mobility, high surface free energy and base surface activity facilitates hydrogen evolution reactions (HER) and oxygen reduction reactions (ORR), which are essential for the development of clean energy. Recent studies have shown significant progress in developing HER/ORR bifunctional catalysts, such as transition metal alloys, oxides, sulfides, and carbon-based composites. These materials are highly efficient in catalysis and help reduce costs. In this work, density functional theory is used to predict the performance of single atom catalysis (SACs) embedded with transition metal (TM) using two-dimensional (2D) Dirac node-ring semi-metal RhB4/OsB4 monolayer as substrate. Systematic calculations show that the TM@RhB4/OsB4 structure with thermodynamic and kinetic stability presents multiple active sites on the basal surface. Notably, Fe@RhB4 is an excellent hydrogen evolution reaction HER catalyst because Dirac cones occur near the Fermi level of this structure, providing high carrier densities and accelerating charge transfer between the catalyst and reaction intermediates. When the substrate RhB4/OsB4 is modified by Sc and Cu atoms, the band gap of the structure becomes small, which increases the conductivity of the original structure. The ΔGH* values of Sc@RhB4 and Cu@OsB4 were 0.118, and 9.38 meV, respectively, outperforming the ideal catalyst Pt. In addition, it is found that Fe@RhB4, and Mn@OsB4 exhibit outstanding catalytic properties for the oxygen reduction reaction (ORR), with overpotentials of 0.41V, and 0.40V, respectively, surpassing the performance of the reference catalyst Pt. It is exciting that the Fe@RhB4 exhibits ideal HER/ORR bifunctional electrocatalytic properties. This study will provide a theoretical basis for the development of multifunctional electrocatalysts in the field of Dirac nodal ring semi-metal materials by single atom doping technology.

Al–O–Al defect complexes as possible candidates for channel electron mobility reducing trapping centers in 4H-SiC metal–oxide–semiconductor field-effect transistors

The deep-level drain current transient spectroscopy (Id-DLTS) measurements of Al-doped SiC metal–oxide–semiconductor field-effect transistors (MOSFETs) strongly suggest that the reduction in the channel mobility at low temperatures is related to a shallow trap detectable at 70 K. Using the Shockley–Reed–Hall (SRH) theory, the level of this trap has been extracted to be around 0.15 eV below the conduction band minimum of SiC. Density functional theory (DFT) calculations of AlSiNCAlSi and AlSiOCAlSi defect complexes have found one configuration of the AlSiOCAlSi complex, which has a charge transition level within the SRH extracted trap level range. Therefore, we suggest that these AlSiOCAlSi defects are likely candidates for traps responsible for the channel mobility reduction.

NiO nanoparticles-based gas sensors: A novel pulse-driven approach for enhanced and efficient hydrogen detection

In recent decades, enhancing response in metal oxide semiconductor-based gas sensors has emerged as a crucial parameter for practical applications. In this study, we present an innovative approach aimed at augmenting sensor response through pulsed heating, deviating from conventional strategies focused on sensitive nanomaterials design. By extending the trade-off between surface charge exchange and physisorption of analyte molecules, we significantly amplify the electrical responses from 12.8 (under isothermal conditions) to 32.1 when exposed to 1000 ppm H2 using a generic NiO sensor. This approach introduces a novel avenue for enhancing the electrical response of resistive-type sensors, offering potential advancements in portable devices for advanced health and environmental monitoring.

Self-template synthesis of pitch-based hierarchical porous carbon for high performance supercapacitor in aqueous and ionic liquid electrolytes

Pitch-based hierarchical porous carbons (PHPCs) have been fabricated by means of self-templated method that is adopting metal oxides and metallic salts impurities originate from coal tar pitch (CTP) precursor serve as in-situ hard template along with KOH activation. The porosity properties of PHPCs are significantly influenced by the mass ratio of KOH to pitch. The micro-morphology, hierarchical porosity constituted of co-existing micro-/meso-/macropores, specific surface area, surface elementary composition and electrochemical properties have been comprehensively investigated. It is shown that the high specific surface area (2479 m2 g-1), lay-stacked microstructure, hierarchical porosity characteristic and considerable oxygen-containing functional groups (4.51 a.t %) that synergistically facilitate the electrochemical performance of PHPCs. The electrochemical measurements results exhibit that the gravimetric capacitance for the optimal sample PHPCs-4 is as high as 317 F g-1 at a current density of 0.2 A g-1, with retention of 213 F g-1 even at 10 A g-1 in a three-electrode configuration. In a two-electrode device, the PHPCs-4 based symmetric supercapacitor cell exhibits a specific capacitance of 245 F g-1 at 0.1 A g-1, along with a good rate capability of 75.5% (185 F g-1 at 10 A g-1) and a considerable energy density of 8.51Wh kg-1 at a power density of 50 W kg-1. When tested in EMIMBF4 ionic liquid electrolyte at a cell voltage of 3.5 V, the assembled symmetric supercapacitor cell demonstrates a high energy density of 77 Wh kg-1 at a power density of 175 W kg-1, maintaining 65.3 Wh kg-1 at a current density of 1 A g-1, and 32.1 Wh kg-1 at a high power density of 17500 W kg-1. Furthermore, the specific capacitance of the PHPCs-4 based symmetric supercapacitor retains nearly 100% of its initial value over 5000 cycles in 6M KOH aqueous electrolyte and 91.4 % after 2500 cycles in EMIMBF4 ionic liquid electrolyte. This strategy exploits a novel approach to synthesizing hierarchical porous carbons from coal tar pitch using a self-templating method, offering potential benefits for various applications.

Possible metal oxide cathode materials for Al-ion batteries: A first principle study

This study investigates various Aluminum (Al) -ion oxide cathode materials, considering their structural properties/stability, cell voltage, band gap analysis, and electrical/ion-diffusion rate-capability. The studied materials are AlMn2O4, AlMoO3, AlTiO2, AlV2O5, AlLiCo2O4, and AlCo2O4. The calculations are conducted using Density Functional Theory (DFT) methods, specifically Generalized Gradient Approximation (GGA) and GGA + U. We employ various noble approaches and techniques to assess the properties of the materials. The findings reveal structural stability after deintercalation of Al ion for all the considered structures. AlMn2O4 exhibits the highest stability due to its strong structural framework, while TiO2 is suspected for this property. Voltage estimation suggests higher possible voltages for AlCo2O4 and AlLiCo2O4 materials, despite not being experimentally examined. Calculated intrinsic-like and extrinsic-like band gaps demonstrate the highest conduction for AlCo2O4. Evaluation of rate-capability recognizes the highest electrical/ion-diffusion rate-capability for AlCo2O4 and AlLiCo2O4. Finally, this study introduces two new superior electrode materials for Al-ion batteries (AIBs), i.e. AlLiCo2O4 and AlCo2O4, with promising properties for future AIBs.

The beginning of iron corrosion - high-resolution visualization with 3D electron tomography

Understanding the genesis and early-phase reactions of iron corrosion is essential for the early detection, mitigation and prevention of metal degradation. In this work, high-resolution 3D tomography of metallic iron oxidation was acquired using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In particular, dendritic capillaries (<0.5 nm) were observed during the initial oxidation of fresh nanoscale zero-valent iron due to the differential oxygen diffusion and iron atoms migration. This observation led to the proposal of a nanoscale “pothole” model for early-phase corrosion, wherein hollowing out of the metal nanoparticle and formation of nanovoids beneath the iron/oxide interface through Kirkendall effect. Coalescence of the nanocapillaries results in the ultimate collapse of metal structure and/or functional failure. Using nanoscale zero-valent iron as a research model, this work provides unprecedented insights into the nano- and atomic-scale mechanisms of iron oxidation, paving the way for advanced detection and prevention strategies for iron corrosion.

Selective Extraction of Valuable and Critical Metals in Cassiterite Concentrate by Dry Chlorination, Part I: Thermodynamic and Modelling Perspective

The chlorination of oxides of major concern in cassiterite concentrate with various chlorinating agents is investigated in light of their thermodynamic feasibilities to extract and recover their valuable metal components. Mechanisms responsible for the processes and their Gibbs free energy changes as a function of temperature to selectively separate and/or recover the metal(s) of interest and unwanted ones as their metallic chlorides are identified. Attention is given to gaseous (Cl2 and Cl2 + CO mixture) and solid (CaCl2 and MgCl2) chlorine sources, from which Cl2 + CO shows no reaction selectivity for any of the oxides but a feasible metal chloride formation for all. Chlorine gas (Cl2), on the other hand, could selectively form chlorides with metals of +2 oxidation state in their oxides, leaving those of high oxidation state unreacted. MgCl2, unlike CaCl2, is found capable of producing calcium, ferrous, and stannic chloride from their metallic oxides with enhanced reaction tendencies in the presence of silicon dioxide (SiO2). An overall study of the thermodynamic feasibility of all chlorine sources looked at alongside operational and environmental viabilities suitably suggests MgCl2 for a selective extraction of the valuable metal components in a cassiterite concentrate, in which case, moderate temperatures seem promising.

Unveiling the mechanistic synergy in Mn-doped NiO catalysts with atomic-burry structure: Enhanced CO oxidation via Ni-OH and Mn bifunctionality

The development of non-noble metal catalysts for low-temperature CO oxidation is a pivotal subject in various disciplines. In this study, an optimized Mn-doped NiO catalyst (Mn-NiO-0.5), prepared via aerosol pyrolysis with an equal molar ratio of Ni to Mn, demonstrates remarkable performance. It achieves an 82 % CO conversion at -20 °C and a 100 % conversion between 10 °C and 800 °C. The catalyst’s turnover frequency (TOF) for CO oxidation significantly surpasses that of previously reported noble-metal-based catalysts, underscoring its superior efficiency. Dynamic analyses suggest that the enhanced catalytic activity is a result of the unique atom burr structure, which presents an extensive surface area replete with abundant active sites. This structural feature is instrumental in maximizing the catalyst’s interaction with CO molecules. Experimental findings, corroborated by density functional theory (DFT) calculations, elucidate the mechanism of CO oxidation on the Mn-NiO-0.5 catalyst. The process is facilitated by the synergistic action of bimetallic sites, where the Ni–OH site acts as the primary adsorption point for CO. Subsequently, the CO is oxidized to bicarbonate through the interaction with the oxygen (O or O2) at adjacent Mn sites. This pioneering study introduces a paradigm-shifting insight: the effectiveness of non-noble metal oxide catalysts can now compete with, and in some cases, outperform their noble metal counterparts. This breakthrough is set to transform the industry, presenting a compelling alternative to conventional noble metal catalysts and propelling the evolution of state-of-the-art environmental conservation technologies.

In situ bioaccumulation of metals by Prosopis juliflora and its detoxification potential at the metal contaminated sites

Heavy metals emanate from diverse anthropogenic activities and the top soil in the vicinity of these activities acts as an immediate sink and facilitates diffusion of heavy metals into the food chain. In the semi-arid plains of India, Prosopis juliflora is the most common and dominant weed along the motorways and barren lands including industrial environs. This investigation hypothesizes the adaptive nature of Prosopis juliflora in the metal enriched soils and attempts to understand its hyper-accumulating potential of metals besides bioconversion/detoxification capability. Prosopis juliflora samples (root, stem, leaves, and pods) from 100 sites in the environs of anthropogenic activities (vehicular emissions and industrial operations) were analyzed for heavy metal concentrations (Cu, Fe, Cr, Cd, Ni, Pb). Prosopis juliflora accumulate metals at the rate of 0.138 mg/kg/day DW for Copper (Cu), Fe: 0.142 mg/kg/day DW, Cr: 0.114 mg/kg/day DW, Ni: 0.048 mg/kg/day DW, Pb: 0.052 mg/kg/day DW, Cd: 0.009 mg/kg/day DW. Furthermore, X-ray Photoelectron Spectroscopy (XPS) metal oxidation state analysis revealed that in the pods of Prosopis juliflora heavy metals (Fe, Cr, Pb) largely existed in non-toxic form (toxic:non-toxic - 3:6), while in the under canopy soil, metals predominantly existed in toxic form (toxic:non-toxic - 7:2); conclusively XPS results ascertains the heavy metal bioconversion/detoxification potential of the plant. These findings suggest that presence of Prosopis juliflora coppice in the barren landscapes across the transportation corridors and metal based industrial zones may ideally favor phyto-remediation of heavy metals.

Biocompatible and capacitive PDA-Ov-Co3O4@CC anode augmented exoelectrogens enrichment and extracellular electron transfer in microbial fuel cells

Metal oxides rich in oxygen vacancies (Ov) possess excellent intrinsic conductivity, variable valence metal center and high capacitance, which were potential candidates as microbial fuel cells anode. However, their high bacterial toxicity greatly hindered the activity of biofilm. To solve this issue, in this work, polydopamine (PDA) covered capacitive Ov doped Co3O4 nanosheets were designed and successfully grown on carbon cloth (CC). The introduction of Ov significantly promoted the charge storage, the net charge and the accumulated charge were 217.1 and 2680.3 C/m2, respectively, surpassed Co3O4 anode without Ov. In addition, Ov also decreased the charge-transfer resistance (Rct), effectively accelerating EET. The Rct of PDA/Ov-Co3O4@CC was 29.51 Ω, lower than CC (382.10 Ω). The cover of PDA prevented the direct contact between metal ions and microorganisms, greatly enhanced the bacterial viability. The power density of MFCs with PDA/Ov-Co3O4@CC anode was 2.77 W/m2, 1.45 times higher than that of bare CC (1.90 W/m2). In addition, PDA/Ov-Co3O4@CC anode displayed excellent coulombic efficiency and daily COD removal amount (23.5 % and 147.6 mg/L/d), higher than the control groups. The community analysis showed the abundance of Geobacter on PDA/Ov-Co3O4@CC anode was 91 %, higher than other anodes. Present study developed a facile and effective PDA coating strategy to simultaneously enhance the biocompatibility and capacitance of Ov-rich metal oxides, which will be a promising method for the preparation of high performance MFCs anode.