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The use of cellulose-based compounds in coating and aqueous phase corrosion prevention is becoming more popular because they provide excellent protection and satisfy the requirements of green chemistry and sustainable development. Cellulose derivatives, primarily carboxymethyl cellulose (CMC) and hydroxyethyl cellulose (HEC), are widely employed in corrosion prevention. They function as efficient inhibitors by adhering to the metal's surface and creating a corrosion-inhibitive barrier by binding using their -OH groups. Their inhibition efficiency (%IE) depends upon various factors, including their concentration, temperature, chemical composition, the nature of the metal/electrolyte and availability of synergists (X-, Zn2+, surfactants and polymers). Cellulose derivatives also possess potential applications in anticorrosive coatings as they prevent corrosive species from penetrating and encourage adhesion and cohesion, guaranteeing the metal substrate underneath long-term protection. The current review article outlines the developments made in the past and present to prevent corrosion in both the coating phase and solution by using cellulose derivatives. Together with examining the difficulties of the present and the prospects for the future, the corrosion inhibition mechanism of cellulose derivatives in the solution and coating phases has also been investigated.
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Owing to their improved catalytic stability and ability to undergo repeated cycles, solid-supported catalysts show great potential for various catalytic reactions. In this study, we synthesized a catalyst comprising a palladium-2,2-bipyridine complex supported on TiO2 nanoparticles (TiO2@BDP-PdCl2) fully characterised and investigated its efficacy in Suzuki-Miyaura cross coupling reactions involving phenyl boronic acid with various aryl halides under mild reaction conditions. The 2,2'- bipyridine (bp) has shown excellent complexation properties for Pd (II) and it could be easily anchored onto functionalized TiO2 support by the bridging carboxylate ions. The composition and structure of the as-prepared catalyst was characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Transmission Electron Microscope (TEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis spectroscopy. The catalyst easily demonstrated separability, enhancing its practicality in catalytic processes. Subsequent utilization showed a consistent activity level, suggesting the stabilization of the aggregated catalyst species. This research sheds light on the importance of catalyst stability and maintenance during consecutive reaction cycles.
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The primary requirements for interfacial adsorption and corrosion inhibition are solubility and the existence of polar functional groups, particularly charges. Traditional organic inhibitors have a solubility issue due to the hydrophobic moieties they incorporate. Most documented organic inhibitors have aromatic rings, hydrocarbon chains, and a few functional groups. The excellent solubility and high efficacy of zwitterions and betaines make them the perfect replacements for insoluble corrosion inhibitors. Zwitterions and betaines are more easily soluble because of interactions between their positive and negative charges (-COO-, -PO3-, -NH3, -NHR2, -NH2R, -SO3- etc.) and the polar solvents. The positive and negative charges also aid these molecules' physical and chemical adsorption at the metal-electrolyte interfaces. They develop a corrosion-inhibiting layer through their adsorption. After becoming adsorbed at the metal-electrolyte interface, they act as mixed-type inhibitors, slowing both cathodic and anodic processes. They usually adsorb according to the Langmuir adsorption isotherm. In this article, the corrosion inhibition potential of zwitterions and betaines in the aqueous phase, as well as their mode of action, are reviewed. This article details the advantages and disadvantages of utilizing zwitterions and betaines for sustainable corrosion protection.
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Surfactants are well known for their colloidal and corrosion inhibition potential (CIP) due to their strong propensity to interact with metallic surfaces. However, because of their small molecular size and the fact that they are only effective at relatively high concentrations, their application in aqueous phase corrosion inhibition is often restricted. Polymeric surfactants, a unique class of corrosion inhibitors, hold the potential to eradicate the challenges associated with using surfactants in corrosion inhibition. They strongly bond with the metallic surface and offer superior CIP because of their macromolecular polymeric structure and abundance of polar functional groups. In contrast to conventional polymeric corrosion inhibitors, the inclusion of polar functional groups also aids in their solubilization in the majority of popular industry-based electrolytes. Some of the major functional groups present in polymeric surfactants used in corrosion mitigation include O (ether), glycidyl (cyclic ether), -CONH2 (amide), -COOR (ester), -SO3H (sulfonic acid), -COOH (carboxyl), -NH2 (amino), - + NR3/- + NHR2/- + NH2R/- + NH3 (quaternary ammonium), -OH (hydroxyl), -CH2OH (hydroxymethyl), etc. The current viewpoint offers state-of-the-art information on polymer surfactants as newly developing ideal alternatives for conventional corrosion inhibitors. The industrial scale-up, colloidal, coordination, adsorption properties, and structural requirements of polymer surfactants have also been established based on the knowledge obtained from the literature. Finally, the challenges, drawbacks, and potential benefits of using polymer surfactants have also been discussed.
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A typical ferrite/martensitic heat-resistant steel (T91) is widely used in reheaters, superheaters and power stations. Cr3C2-NiCr-based composite coatings are known for wear-resistant coatings at elevated temperature applications. The current work compares the microstructural studies of 75 wt% Cr3C2- 25 wt% NiCr-based composite clads developed through laser and microwave energy on a T91 steel substrate. The developed clads of both processes were characterized through a field emission scanning electron microscope (FE-SEM) attached with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and assessment of Vickers microhardness. The Cr3C2-NiCr based clads of both processes revealed better metallurgical bonding with the chosen substrate. The microstructure of the developed laser clad shows a distinctive dense solidified structure, with a rich Ni phase occupying interdendritic spaces. In the case of microwave clad, the hard chromium carbide particles consistently dispersed within the soft nickel matrix. EDS study evidenced that the cell boundaries are lined with chromium where Fe and Ni were found inside the cells. The X-ray phase analysis of both the processes evidenced the common presence of phases like chromium carbides (Cr7C3, Cr3C2, Cr23C6), Iron Nickel (FeNi3) and chromium-nickel (Cr3Ni2, CrNi), despite these phases iron carbides (Fe7C3) are observed in the developed microwave clads. The homogeneous distributions of such carbides in the developed clad structure of both processes indicated higher hardness. The typical microhardness of the laser-clad (1142 ± 65HV) was about 22% higher than the microwave clad (940 ± 42 HV). Using a ball-on-plate test, the study analyzed microwave and laser-clad samples' wear behavior. Laser-cladding samples showed superior wear resistance due to hard carbide elements. At the same time, microwave-clad samples experienced more surface damage and material loss due to micro-cutting, loosening, and fatigue-induced fracture.
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Commercially available QPPO/PVA based anion exchange membrane (AEM) BIII was to inquire the percentage discharge of anionic dye Eosin-B (EB) at terrain temperature from wastewater. The impact of EB initial concentration, membrane dosage, ionic strength, contact time and temperature on EB percentage removal was contemplated. The EB percentage removal was increased from 22 to 99.56% and 38.15-99.56% with contact time and membrane dosage respectively while decreased from 99.56 to 29%, 99.56 to 54.61% and 99.56 to 92.22% with enhancing initial concentration of EB, ionic strength and temperature respectively. Nonlinear isotherm models were utilized to demonstrate EB adsorption onto AEM BIII. Attained results exhibited that nonliner Freundlich isotherm model best fitted to EB adsorption onto AEM BIII. For EB adsorption onto AEM BIII, adsorption kinetics were inquired in detail by using several kinetic models but EB adsorption nicely fitted to pseudo-second-order kinetics. Similarly thermodynamic analysis was performed and results pointed to an exothermic adsorption of EB onto AEM BIII. The membrane could be reused for four concecutive cycles with loosing its efficiency.
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Águas Residuárias , Poluentes Químicos da Água , Corantes , Amarelo de Eosina-(YS) , Concentração de Íons de Hidrogênio , Termodinâmica , Adsorção , Cinética , ÂnionsRESUMO
MXenes are an innovative class of 2D nanostructured materials gaining popularity for various uses in medicine, chemistry, and the environment. A larger outer layer area, exceptional stability and conductivity of heat, high porosity, and environmental friendliness are all characteristics of MXenes and their composites. As a result, MXenes have been used to produce Li-ion batteries, semiconductors, water desalination membranes, and hydrogen storage. MXenes have recently been used in many environmental remediations, frequently surpassing conventional materials, to treat groundwater contamination, surface waters, industrial and municipal wastewaters, and desalination. Due to their outstanding structural characteristics and the enormous specific surface area, they are widely utilized as adsorbents or membrane materials for the desalination of seawater. When used for electrochemical applications, MXene-composites can deionize via Faradaic capacitive deionization (CDI) and adsorb various organic and inorganic pollutants to treat the water. In general, as compared to other 2D nanomaterials, MXene has superb characteristics; because of their magnificent characteristics and they exhibit strong desalination capability. The current review paper discusses the desalination capability of MXenes and their composites. Focusing on the desalination capacity of MXene-based nanomaterials, this study discusses the characteristics and synthesis techniques of MXenes their composites along with their ion-rejection capability and pervaporation desalination of water via MXene-based membranes, capacitive deionization capability, solar desalination capability. Furthermore, the challenges and prospects of MXenes and their composites are highlighted.
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Água do Mar , Água , Contaminação de Medicamentos , Condutividade ElétricaRESUMO
Surfactants enjoy an augmented share of hydrophilicity and hydrophobicity and are well-known for their anticorrosive potential. The use of non-toxic surfactants is gaining growing interest because of the scaling demands of green chemistry. Green surfactants have successfully replaced traditional toxic surfactant-based corrosion inhibitors. Recently, many reports described the corrosion inhibition potential of green surfactants. The present article aims to describe the recent advancements in using green surfactants in corrosion mitigation. They create a charge transfer barrier through their adsorption at the interface of the metal and the environment. Their adsorption is well explained by the Langmuir adsorption isotherm. In the adsorbed layer, their hydrophilic polar heads orient toward the metal side and their hydrophobic tails orient toward the solution side. They block the active sites and retard the anodic and cathodic and act as mixed-type inhibitors. Their adsorption and bonding nature are fruitfully supported by surface analyses. They can form mono- or multilayers depending upon the nature of the metal, electrolyte and experimental conditions. The challenges and opportunities of using green surfactants as corrosion inhibitors have also been described.
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Surfactantes Pulmonares , Tensoativos , Tensoativos/química , Corrosão , Interações Hidrofóbicas e Hidrofílicas , AdsorçãoRESUMO
Multiple ecological contaminants in gaseous, liquid, and solid forms are vented into ecosystems due to the huge growth of industrialization, which is today at the forefront of worldwide attention. High-efficiency removal of these environmental pollutants is a must because of the potential harm to public health and biodiversity. The alarming concern has led to the synthesis of improved nanomaterials for removing pollutants. A path to innovative methods for identifying and preventing several obnoxious, hazardous contaminants from entering the environment is grabbing attention. Various applications in diverse industries are seen as a potential directions for researchers. MXene is a new, excellent, and advanced material that has received greater importance related to the environmental application. Due to its unique physicochemical and mechanical properties, high specific surface area, physiological compatibility, strong electrodynamics, and raised specific surface area wettability, its applications are growing. This review paper examines the most recent methods and trends for environmental pollutant removal using advanced 2D Mxene materials. In addition, the history and the development of MXene synthesis were elaborated. Furthermore, an extreme summary of various environmental pollutants removal has been discussed, and the future challenges along with their future perspectives have been illustrated.
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Poluentes Ambientais , Recuperação e Remediação Ambiental , Ecossistema , BiodiversidadeRESUMO
This study investigates the corrosion kinetics and crack propagation in buried transmission pipelines made of high-strength low alloy steel API X100. Despite its cost-effectiveness and ability to withstand high operating conditions without increasing pipe wall thickness, the corrosion kinetics in near-neutral pH environments for this steel grade is not fully understood. To address this gap, two numerical models were developed. The first model, using COMSOL Multiphysics v5.6, showed higher electrolyte potential at the corrosion defect center due to stress-induced defect growth, increasing corrosion susceptibility. The second model, employing the XFEM approach, evaluated crack initiation, propagation, and von Mises stress distribution along the crack path. This research contributes to a better understanding of corrosion and crack behavior in corroded pipelines, aiding in their performance improvement in near-neutral pH soil environments.
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Green and renewable energy is the key to overcoming energy-related challenges such as fossil-fuel depletion and the worsening of environmental habituation. Among the different clean energy sources, hydrogen is considered the most impactful energy carrier and is touted as an alternate fuel for clean energy needs. Even though noble metal catalysts such as Pt, Pd, and Au exhibit excellent hydrogen evolution reaction (HER) activity in acid media, their earth abundance and capital costs are highly debatable. Hence, developing cost-effective, earth-abundant, and conductive electrocatalysts is crucial. In particular, various two-dimensional (2D) transition metal carbides and their compounds are gradually emerging as potential alternatives to noble metal-based catalysts. Owing to their improved hydrophilicity, good conductivity, and large surface areas, these 2D materials show superior stability and excellent catalytic performances during the HER process. This review article is a compilation of the different synthetic protocols, their impact, effects of doping on molybdenum and tungsten carbides and their derivatives, and their application in the HER process. The paper is more focused on the detailed strategies for improving the HER activity, highlights the limits of molybdenum and tungsten carbide-based electrocatalysts in electro-catalytic process, and elaborates on the future advancements expected in this field.
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Antibiotics are essential medications for human and animal health, as they are used to battle urinary infections and bacterial diseases. Therefore, the rapid determination of antibiotic drugs in biological samples is necessary to address the current clinical challenge. Here, we developed a heterojunction ternary composite of BiOCl/BiVO4 nanosheets enriched with graphene oxide (BiOCl/BiVO4@GO) for accurate and minimal-level detection of an antihistamine (promethazine hydrochloride, PMZ) in urine samples. The BiOCl/BiVO4 nanosheets were prepared by a wet chemical approach using a deep eutectic green solvent. The spectroscopic and analytical methods verified the formation and interaction of the BiOCl/BiVO4@GO composite. Our results showed that the thoroughly exfoliated BiOCl/BiVO4@GO composite retained good electrical conductivity and fast charge transfer toward the electrode-electrolyte interface in neutral aqueous media. In addition, the experimental conditions were accurately optimized, and the BiOCl/BiVO4@GO composite showed excellent electrocatalytic activity toward the oxidation of PMZ. Indeed, the BiOCl/BiVO4@GO composite demonstrated a good linear response range (0.01-124.7 µM) and a detection level of 3.3 nM with a sensitivity of 1.586 µA µM-1 cm-2. In addition, the BiOCl/BiVO4@GO composite had excellent storage stability, good reproducibility, and reliable selectivity. Finally, the BiOCl/BiVO4@GO displayed a desirable recovery level of PMZ in urine samples for real-time monitoring.
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Grafite , Antibacterianos , Eletrodos , Grafite/química , Antagonistas dos Receptores Histamínicos , Reprodutibilidade dos TestesRESUMO
Metal organic frameworks (MOFs), which constitute a new class of porous organic-inorganic hybrid materials, have gained considerable attention in the fields of electrochemical energy storage and conversion devices owing to their open topological structures, large surface areas, tunable morphologies, and extreme redox activity. A synthesis protocol that comprises coprecipitation followed by controlled calcination processes to design a battery-type electrode is used. This electrode consists of three-dimensional (3D), ant cave-like polyhedrons of nickel-cobalt alloy on graphitic carbon (GC; NiCo@GC) nanostructures; trimesic acid is used as a potential MOF-linker. The developed NiCo@GC sample exhibits mesoporous characteristics with the maximum surface area of 94.08 m2 g-1 at 77 K. In addition, the redox activity at different sweep rates reveals the battery-type charge storage behavior of the NiCo@GC electrode; its three-electrode assembly provides 444 C g-1 specific capacity at 2 A g-1 with long-term capacity retention. The constructed supercapattery (SC) devices (i.e., AC//NiCo@GC) achieved capacity, specific energy, and specific power are 74.3 mAh g-1 , 39.5 Wh kg-1 , and 665 W kg-1 , respectively. Owing to its reasonable electrochemical characteristics, the prepared NiCo@GC material is a promising candidate for supercapattery electrodes for portable electronic devices.
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Estruturas Metalorgânicas , Eletroquímica , Eletrodos , Níquel , OxirreduçãoRESUMO
Water contamination by hazardous organic pollutants poses an extreme threat to the environment and globally endangers aquatic life and human health. Hence, the removal of toxic organic effluents from water sources is necessary to ensure a healthy green environment. To this end, a new class of emerging, visible-light-driven Zn- and Ni-based ternary metal-selenide (Zn1-xNixSe) nanophotocatalysts, with tunable nanostructures via regulation of the stoichiometric ratios of Zn and Ni, were synthesized for efficient water purification by a facile one-pot hydrothermal process. These catalysts exhibit outstanding porous properties, with large surface areas and average particle sizes of around 80 ± 10 nm. The as-prepared ternary Zn1-xNixSe catalysts enable improved optical properties, intrinsic conductivity, bandgap reductions, and large numbers of active sites compared with pristine materials, thereby exhibiting outstanding degradation properties against various dye molecules, including Congo red, methyl orange, and chrome-IV upon visible light irradiation. The improved photodegradation capabilities of the Zn1-xNixSe catalysts may be attributed to the synergistic combinations of Zn and Ni selenides, which in turn minimize the recombination rates of the photogenerated carriers compared to their individual constituents. These findings clearly demonstrate that the proposed ternary Zn1-xNixSe catalysts could be potentially used to remove toxic organic contaminants from industrial wastewater.
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Vermelho Congo , Nanoestruturas , Compostos Azo , Corantes , Humanos , Águas Residuárias , ZincoRESUMO
Chemically, chitosan is a linear polysaccharide constituted of arbitrarily distributed D-glucosamine and N-acetyl-D-glucosamine constituents combined together via ß-1,4-glycosidic linkage. Because of increasing ecological awareness and strict environmental regulations, species of natural and biological origin such as chitosan can be identified as ideal environmental sustainable alternative to replace traditional heterocyclic (toxic) corrosion inhibitors. Although, chitosan contains numerous electron rich sites however chitosan itself is not highly effective aqueous phase corrosion inhibitors. Aqueous phase application of chitosan is limited because of its limited solubility. However, chemically modified chitosan derivatives, such as chitosan based Schiff bases (CSBs) exhibit remarkable solubility in such electrolytes. Therefore, recently various reports dealing with the anticorrosion potential of CSBs have been reported. Present review article describes the collections on CSBs as aqueous phase corrosion inhibitors. Nature of CSBs adsorption through chelation (coordination) has also been discussed based on literature outcomes.
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Quitosana/química , Bases de Schiff/farmacologia , Corrosão , Desenho de Fármacos , Bases de Schiff/química , Solubilidade , Propriedades de SuperfícieRESUMO
In this study, we fabricated a nanoporous oxide layer by anodization to improve corrosion resistance of type 304 stainless steel (SS) gas tungsten arc weld (GTAW). Subsequent heat treatment was performed to eliminate any existing fluorine in the nanoporous oxide layer. Uniform structures and compositions were analyzed with field emission scanning electron microscope (FESEM) and X-ray diffractometer (XRD) measurements. The corrosion resistance of the treated SS was evaluated by applying a potentiodynamic polarization (PDP) technique and electrochemical impedance spectroscopy (EIS). Surface morphologies of welded SS with and without treatment were examined to compare their corrosion behaviors. All results indicate that corrosion resistance was enhanced, making the treatment process highly promising.
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In this investigation, a sequences of iron diselenide (FeSe2) nanomaterials as the competent and highly stable catalysts for the detoxification of aqueous organic dye pollutants such as Congo red (CR) and methylene blue (MB) through Electro-Fenton (EF) process using hydrogen peroxide as an initiator have been studied. The utilized selenium precursors include selenium metal, selenious acid (H2SeO3) and selenium dioxide (SeO2) which were employed for the synthesis of FeSe2 catalysts through a wet chemical strategy. It has been observed that based on the employed precursors, different morphologies ranges of the FeSe2 catalysts were obtained: microgranualr particles to nano-stick to nanoflakes. The crystalline nature and phase purity of the obtained FeSe2 catalysts were determined through XRD, Raman and HR-TEM analyses which confirmed their orthorhombic ferroselite structure. Among the prepared FeSe2 catalysts, FS-2 (using H2SeO3) displayed better porous properties as compared to other catalysts and achieved the highest surface area of 74.68 m2g-1. The narrow bandgap (0.88 eV) and fast conversion of Fe2+/Fe3+ cycle of FeSe2 led CR and MB degradation of 93.3% and 90.4%, respectively. The outcome of this study demonstrates improved catalytic properties of FeSe2 nanostructures for the efficient detoxification of hazardous and toxic effluents.
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Nanoestruturas , Selênio , Catálise , Peróxido de Hidrogênio , FerroRESUMO
Three novel N-hydrospiro-chromeno-carbonitriles namely, 2-amino-7,7-dimethyl-1',3',5-trioxo-1',3',5,6,7,8-hexahydrospiro[chromene-4,2'-indene]-3-carbonitrile (INH-1), 3-amino-7,7-dimethyl-2',5-dioxo-5,6,7,8-tetrahydrospiro[chromene-4,3'-indoline]-2-carbonitrile (INH-2) and 3'-amino-7',7'-dimethyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-2'-carbonitrile (INH-3) were synthesized using the principles of green chemistry and applied as corrosion inhibitors for mild steel in acidic medium using computational simulations and experimental methods. Experimental and computational studies revealed that inhibition effectiveness of the INHs followed the sequence: INH-3 (95.32%) > INH-2 (93.02%) > INH-1 (89.16%). The investigated compounds exhibit mixed-type corrosion inhibition characteristics by blocking the active sites on the surface of mild steel. EIS study revealed that the INHs behave as interface-type corrosion inhibitors. EDX analyses supported the adsorption mechanism of corrosion inhibition. A DFT study carried out for gaseous and aqueous forms of inhibitor molecules indicated that interactions of INHs with the mild steel surface involve charge transfer phenomenon or donor-acceptor interactions. A Monte Carlo (MC) simulation study revealed that only a fractional segment of the molecule lies parallel to the steel surface, since the INH molecules are not completely planar. The results of computational studies and experimental analyses were in good agreement.
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High-performance, nonprecious metal bifunctional electrocatalysts for the oxygen reduction and evolution reactions (ORR and OER, respectively) are of great importance for rechargeable metal-air batteries and regenerative fuel cells. A comprehensive study based on statistical design of experiments is presented to investigate and optimize the surfactant-assisted structure and the resultant bifunctional ORR/OER activity of anodically deposited manganese oxide (MnOx) catalysts. Three classes of surfactants are studied: anionic (sodium dodecyl sulfate, SDS), non-ionic (t-octylphenoxypolyethoxyethanol, Triton X-100), and cationic (cetyltrimethylammonium bromide, CTAB). The adsorption of surfactants has two main effects: increased deposition current density due to higher Mn2+ and Mn3+ concentrations at the outer Helmholtz plane (Frumkin effect on the electrodeposition kinetics) and templating of the MnOx nanostructure. CTAB produces MnOx with nanoneedle (1D) morphology, whereas nanospherical- and nanopetal-like morphologies are obtained with SDS and Triton, respectively. The bifunctional performance is assessed based on three criteria: OER/ORR onset potential window (defined at 2 and -2 mA cm-2) and separately the ORR and OER mass activities. The best compromise among these three criteria is obtained either with Triton X-100 deposited catalyst composed of MnOOH and Mn3O4 or SDS deposited catalyst containing a combination of α- and ß-MnO2, MnOOH, and Mn3O4.The interaction effects among the deposition variables (surfactant type and concentration, anode potential, Mn2+ concentration, and temperature) reveal the optimal strategy for high-activity bifunctional MnOx catalyst synthesis. Mass activities for OER and ORR up to 49 A g-1 (at 1556 mVRHE) and -1.36 A g-1 (at 656 mVRHE) are obtained, respectively.
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The long-term weight loss, ion release, and surface composition of 316L, Co-28Cr-6Mo and Ti-6Al-4V alloys were investigated in a simulated body environment. The samples were immersed in phosphate-buffered saline (PBS) solutions with various human serum albumin (HSA) concentrations for 8, 14, and 22 weeks. The specimens initially lost weight up to 14 weeks and then slightly gained weight. The analysis of the released ions was performed by induced coupled plasma-optical emission spectrometer (ICP-OES). The results revealed that the precipitation of the dissolved Fe and Co could cause the weight gain of the 316L and Co-28Cr-6Mo alloys. The surface chemistry of the specimens was determined by X-ray photoelectron spectroscopy (XPS). The XPS analysis of Co-28Cr-6Mo alloy showed that the interaction of Mo with HSA is different from Mo with bovine serum albumin (BSA). This was also observed for Na adsorption into the oxide layer of Ti-6Al-4V alloy in the presence of HSA and BSA.