Metal Species Research Articles

Unveiling the influence of poisonous metals on NH3-SCR performance over NbOPO4 supported Cu-Ce catalyst

In this study, the underlying influence mechanism of different metal species, including K, Ca and Cd, on NbOPO4 supported Cu-Ce catalysts had been disclosed. Experimental results indicated that various metal species exhibited deactivating effect on SCR activities, where the deactivation effect decreased in the order of K > Ca ≈ Cd. Inherently, the pronounced decrease in SCR performances should be derived from the greatly deteriorated physicochemical properties, where various metal species deposited on CCP catalyst significantly suppressed redox ability and surface acidity and decreased surface area. However, compared with traditional V-W-Ti catalyst, NbOPO4 supported Cu-Ce catalyst still possessed superior resistance to different metal species.

Spesiasi dan Bioavailabilitas Merkuri dalam Sedimen Teluk Palu Pasca Gempa dan Tsunami dengan Metode Diffusive Gradient in Thin Film (DGT)

Speciation and bioavailability of mercury in the sediments of Palu Bay after the earthquake and tsunami were conducted using fractionation and Diffusion Gradient in Thin Films (DGT). This method has been conducted using sediment samples from the estuary of the Pondo River, Palu. Heavy metal speciation of mercury ions was conducted by looking at the distribution of mercury ions in various species by sequential extraction and heavy metal bioavailability of mercury ions. This method was conducted by looking at the migration of mercury ions from sediments into the seawaters using a Diffusive Gradient in Thin Films (DGT). The speciation of mercury ions concentration with sequential extraction as EFLE (easily, freely, leachable, exchangeable) fraction is about < 0.0005 ppm, the oxidizable fraction is about < 0.0005 ppm and the resistant fraction is between < 0.0005 ppm to 0.0063 ppm. The results of DGT experiments to study the migration of mercury ions from sediments into the seawaters during 3 days of immersion is between 0.01003 ppm and 0.01748 ppm. The availability of mercury ions concentration in the sediments allows for the migration of mercury ions into water.

Strong Metal‐Support Interaction Triggered by Molten Salts

Strong metal‐support interaction (SMSI) plays a vital role in tuning the geometric and electronic structures of metal species. Generally, a high‐temperature treatment (>500 °C) in reducing atmosphere is required for constructing SMSI, which may induce the sintering of metal species. Herein, we use molten salts as the reaction media to trigger the formation of high‐intensity SMSI at reduced temperatures. The strong ionic polarization of the molten salt promotes the breakage of Ti‐O bonds in the TiO2 support, and hence decreases the energy barrier for the formation of interfacial bonds. Consequently, a high‐intensity SMSI state is achieved in TiO2 supported Ir nanoclusters, evidenced by a large number of Ir‐Ti bonds at the interface, at a low temperature of 350 °C. Moreover, this method is applicable for triggering SMSI in various supported metal catalysts with different oxide supports including CeO2 and SnO2. This newly developed SMSI construction methodology opens a new avenue and holds significant potential for engineering advanced supported metal catalysts toward a broad range of applications.

Strong Metal-Support Interaction Triggered by Molten Salts.

Strong metal-support interaction (SMSI) plays a vital role in tuning the geometric and electronic structures of metal species. Generally, a high-temperature treatment (>500 °C) in reducing atmosphere is required for constructing SMSI, which may induce the sintering of metal species. Herein, we use molten salts as the reaction media to trigger the formation of high-intensity SMSI at reduced temperatures. The strong ionic polarization of the molten salt promotes the breakage of Ti-O bonds in the TiO2 support, and hence decreases the energy barrier for the formation of interfacial bonds. Consequently, a high-intensity SMSI state is achieved in TiO2 supported Ir nanoclusters, evidenced by a large number of Ir-Ti bonds at the interface, at a low temperature of 350 °C. Moreover, this method is applicable for triggering SMSI in various supported metal catalysts with different oxide supports including CeO2 and SnO2. This newly developed SMSI construction methodology opens a new avenue and holds significant potential for engineering advanced supported metal catalysts toward a broad range of applications.

An Alternative Concept in Making Hybrid Flow Batteries into Dendrite-Free Full-Flow Batteries

: In this study, the author proposes an alternative concept of using electrostatic force of cation-exchange resin to attract metal ions and nanoscale conductors onto the polymer matrix to conduct the electrons for the plating/stripping of the metal species. Due to the even distribution of the positively-charged functional groups inside the cation-exchange resin, metal formation can also be well distributed and safety issue caused by metal dendrite can be eliminated. By applying this transformative concept, various hybrid flow batteries could be “upgraded” to dendrite-free full-flow batteries. Interestingly, this new concept could also be generalized for all metal-based aqueous and nonaqueous hybrid systems to upgrade them into next-generation full-flow battery systems. This work offers an alternative concept to deliver unprecedented battery systems and the proof-of-concept would be more easily implemented than anticipated.

Distinct In Vitro Differentiation Protocols Differentially Affect Cytotoxicity Induced by Heavy Metals in Human Neuroblastoma SH-SY5Y Cells.

The SH-SY5Y cell line is widely used in neurotoxicity studies. However, the effects of inducing cell differentiation on the cytotoxic effects of heavy metals are unclear. Therefore, we investigated the effects of mercuric chloride (HgCl2), cadmium chloride (CdCl2), arsenic trioxide (As2O3), and methylmercury (MeHg) on SH-SY5Y cells differentiated in the presence of insulin-like growth factor-I (IGF-I) or all-trans retinoic acid (ATRA). Neurite outgrowth with distinct changes in neuronal marker expression, phenotype, and cell cycle was induced in SH-SY5Y cells by IGF-I treatment for 1day or ATRA treatment for up to 7days. The cytotoxic effects of HgCl2 decreased at lower concentrations and increased at higher concentrations in both IGF-I- and ATRA-differentiated cells compared with those in undifferentiated cells. Differentiation with IGF-I, but not with ATRA, increased the cytotoxic effects of CdCl2. Decreased cytotoxic effects of As2O3 and MeHg were observed at lower concentrations in IGF-I-differentiated cells, whereas increased cytotoxic effects of As2O3 and MeHg were observed at higher concentrations in ATRA-differentiated cells. Changes in the cytotoxic effects of heavy metals were observed even after 1day of ATRA exposure in SH-SY5Y cells. Our results demonstrate that the differentiation of SH-SY5Y cells by IGF-I and ATRA induces different cellular characteristics, resulting in diverse changes in sensitivity to heavy metals, which depend not only on the differentiation agents and treatment time but also on the heavy metal species and concentration.

In-situ encapsulation synthesis of Fe-SAPO-34 for efficient removal of tetracycline via peroxydisulfate activation: Highly dispersed active sites and ultra-low iron leaching

The agglomeration and leaching of metal species are critical issues for iron-based catalysts to remove tetracycline (TC) through peroxydisulfate (PDS) activation. In this work, iron-oxide species confined in cha cage of silicon aluminum phosphate zeolite (Fe-SAPO-34) was successfully synthesized by in-situ encapsulation method to address the above challenges. In Fe-SAPO-34/PDS system, approximately 92.6% TC was removed within 150 min at experimental conditions: [pH] = 3, [TC] = 20 mg/L, [Catalyst] = 0.10 g/L, [PDS] = 1 mM. Meanwhile, the biggest degradation rate constant is 0.03689 min−1, which surpasses the counterpart systems. This result originates from the well dispersion of Fe-oxide species in Fe-SAPO-34, providing more active sites for TC degradation. As expected, the Fe-oxide species leaching concentration is ultra-low (0.018 mg/L) in Fe-SAPO-34/PDS system, which is attributed that SAPO-34 has a confinement effect of cha cage and eight-ring pore openings to limit its leaching. The radical quenching tests and electron paramagnetic resonance (EPR) technology verify singlet oxygen (1O2) is the primary reactive oxygen species (ROS) in Fe-SAPO-34/PDS system. Furthermore, two possible pathways for TC degradation are proposed in line with the intermediate identified by liquid chromatography-mass spectrometry (LC-MS).

Long-term agricultural reuse of treated wastewater and sewage sludge: developing a Time to Critical Content Index for metal species

This study evaluates the sustainability of spreading wastewater or sewage sludge on agricultural land, balancing benefits with contamination risks. Conventional ecological risk indices often fail to address the long-term accumulation of metals in soils. We investigate the feasibility of spreading based on current knowledge of potentially contaminating metals and their behavior in soil. We analyzed the speciation of metals (Ag, Cd, Co, Cr, Cu, Ni, Pb, Ti, Zn) through sequential extraction in sludge, treated wastewater, and soils after 14 years of application of sewage sludge and treated wastewater issued from an Algerian wastewater treatment plant. We introduce a Time to Critical Content Index (TCCI) that calculates the time required to reach critical levels of potentially mobile metals, considering total metal content and speciation. The TCCI takes into account product knowledge, soil characteristics, metal behavior, ecological/toxicological thresholds, and regulations. Applied to our case study, the TCCI indicates that spreading sewage sludge can continue despite metal contents exceeding regulatory ceiling values. The index serves as a precautionary measure, adaptable to evolving knowledge, providing a comprehensive framework for sustainable agricultural practices.Graphical

Evaluation of heavy metal speciation in waters of Hirakud reservoir: a Ramsar site in India.

The growing concern of aquatic heavy metal (HM) pollution is dependent on the toxic nature of its bio-available form. Thus, bio-availability is guided by the HM fractionation in water. This study was therefore conducted to evaluate the spatial impact on physicochemical fractionation of HM (Zn, Mn, Cu, and Fe) in the waters of the Hirakud reservoir in India. Speciation along different pores using a filtration technique was adopted to fractionate the HMs in water samples. The result suggests that the water of the study area is polluted with Cu (0.22-0.35mg/L), Mn (0.15-0.23mg/L), and Fe (1.90-3.10mg/L) that have crossed their permissible limits while Zn (0.17-0.97mg/L) was within the permissible standard. When studied for physical partitioning, the right dyke was comparatively more polluted than the left dyke. While the water samples were dominated by the dissolved fraction of heavy metals, it was construed that a large proportion of the HMs are in bio-available form. Further, a distinct impact of spatial variation on metal fractionation was also evident in the study with PCA revealing site-specific behaviour. Therefore, it can be concluded that multiple anthropogenic activities lead to the distribution and fractionation of HMs in water.

Ligand-Coordinated Pt Single-Atom catalyst facilitates Support-Assisted Water-Gas shift reaction

The water–gas shift (WGS) reaction (CO+H2O→CO2+H2,ΔH=-41.1kJ/mol) is an essential process in the production of hydrogen and has grown significantly in usage over time. In this study, we further explore a novel strategy that can create single-atom catalysts (SACs) from metal-ligand single-sites on high surface area oxide supports for catalyzing the WGS reaction. The metal–ligand approach results in high metal loading, exhibits an ultimate dispersion of metal species and maximizes atom efficiency. 1,10-phenanthroline-5,6-dione (PDO) was chosen as the ligand for its oxidative potential for stabilizing Pt metal cations via two different binding pockets. The single-atom nature of the Pt-ligand is characterized with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and transmission electron microscopy (TEM) techniques. The catalytic activity is evaluated for the WGS reaction, revealing that Pt-ligand SACs supported on defective TiO2 show higher inherent catalytic activity than Pt NPs and a significantly lower activation energy. This characteristic is generally desirable for the redox mechanism. Density functional theory (DFT) calculations reveal that metal–ligand SACs allow CO interaction with oxygen atoms from the TiO2 surface. The redox mechanism of the WGS reaction demonstrates a lower effective activation barrier than the associative mechanism for Pt-ligand SAC. Moreover, the metal–ligand strategy, according to DFT results, facilitates the reaction redox mechanism by reducing the CO binding energy and promoting CO2 and H2 formation process.

Evaluation of individual metal contribution on active sites tailoring in multimetallic oxygen evolution catalytic system

Synergistic effects among different metals have positioned multimetallic electrocatalysts as promising facilitators for enhancing the oxygen evolution reaction (OER), though understanding their precise mechanisms has remained elusive. Delving into the unique contributions of individual metals is crucial for comprehending the complex synergy within multimetallic systems. In this study, we employed quinary (Co, Ce, Fe, Cu, and Mn) molybdates as a model to systematically investigate the role of each metal species in tailoring active sites. Our systematic analyses unveiled the presence of crucial oxygen vacancies, which can be considered as the active sites in OER. Comparative analyses of the top-performing quinary molybdates and their quaternary counterparts highlighted distinct electronic interactions and varying densities of oxygen vacancies, indicative of the diverse electron and vacancy engineering capabilities inherent to different metals. Mott-schottky plots demonstrated the predominant contribution of Mn to specific catalytic activity, followed by Ce, Fe, Cu, and Co. Leveraging an in-situ methanol probing method, it was found that the introduction of Cu, Ce, Fe, and Mn weakened intermediate adsorption, with Mn and Ce having the most significant effects, whereas Co strengthened adsorption. This work can advance our comprehension of the role played by individual metals within multimetallic catalysts, thereby promoting a more profound understanding of synergistic effects.

Metal Bionanohybrids against Microbiologically Influenced Corrosion (MIC) Consortia.

In search of new materials that would help to prevent microbiologically influenced corrosion (MIC), we have designed and synthetized six different copper and copper-silver nanoparticle-enzyme hybrids using a mild-conditions method carried out in water and r.t. Characterization analyses exhibited the presence of small crystalline nanoparticles with diameters from 2 to 20 nm. X-ray diffraction determined that the Cu hybrids were composed of different copper species, depending on the synthetic protocol used, while the Cu-Ag hybrids were mainly composed of copper and silver phosphate metallic species. Then, the bacterial viability of three MIC-relevant enrichments, sulfate-reducing bacteria (SRB), slime-forming bacteria (SFB), and acid-producing bacteria (APB), was studied in the presence of the bionanohybrids. The results demonstrated a notable effect of all bionanohybrids against SRB, one of the most prominent bacteria associated with MIC. In particular, Cu-2 and Cu-Ag-2 showed a reduction in bacterial cells of 94% and 98% after 48 h, respectively, at a concentration of 100 ppm. They also exhibited high efficiencies against SFB, with Cu-Ag-1 and Cu-Ag-2 hybrids being the best, with bacterial reduction percentages of 98% after 45 h of exposition at a concentration of 100 ppm. However, in the case of APB, the effect of the hybrids was lost due to the low pH level generated during the experiment. Finally, the capacity of Cu-2 and Cu-Ag-2 to inhibit the adhesion of SRB to the surface of carbon steel coupons was evaluated. Fluorescence imaging of the surface of the coupons at 24 h demonstrated that the presence of the hybrids inhibited the growth of SRB, obtaining a maximum reduction of 98% with Cu-2. Overall, the results of this study demonstrate that these novel nanomaterials have a wide-range antibacterial effect and may have a promising future in the prevention and treatment of MIC.

A new insight on surface chemistry and redox species of transition metal (Fe, Mn) doped CeO2-SnO2/Al2O3 nanocomposites for automobile emission control

The ceria-tin/alumina mixed metal oxides (Ce/Sn =1) with different proportions of Fe & Mn dopants were synthesized and investigated in detailed approach for diesel emission reduction. The dopants created structural defects enhancing the oxygen ion mobility for exhaust treatment. The existence of surface-active oxygen sites and oxygen ion vacancy sites generated for charge compensation due to reduction of Ce4+, Sn4+ and dopants incorporation evidenced from XPS analysis. The Mn doped sample holds better physicochemical properties than Fe doped sample. The Mn doped sample with higher surface area of about 101.32 m2 g−1 exhibits greater active sites for better catalytic activity. The redox couples in the Mn-doped sample Ce4+/Ce3+, Sn4+/Sn2+, and Mn3+/Mn2+ helps in oxygen regeneration to contribute to exhaust treatment by oxygen ion conduction from bulk to the surface. This sample exhibited the 92 % of NOx reduction and proved to be a dynamic candidate for diesel emission reduction.

Synthesis of NiZn-based paddle-wheel metal-organic framework and its use as a catalytic precursor for ethylene dimerization

A bimetallic pillared-layered MOF based on Ni and Zn with improved catalytic activity was synthesized and applied in the ethylene oligomerization reaction. According to the XANES spectra, the MOF possesses Ni in the 2+ oxidation state, a well-known active catalytic precursor in oligomerization systems. In addition, Ni and Zn oxide or metallic species were not identified, indicating the absence of impurity phases. µ-XRF and SEM-EDS techniques showed the homogeneous distribution of Ni and Zn species across the SBUs of the bimetallic MOF. Ni/Zn-MOF was applied in the ethylene oligomerization reaction using EASC as the co-catalyst, and the results were compared to its monometallic counterpart Ni-MOF. The bimetallic material Ni/Zn-MOF obtained a TOF corresponding to 135 ×103 h−1, which accounts for a 60 % increase in the catalytic activity achieved by Ni-MOF (85 ×103 h−1) under 15 bar of ethylene in a Parr reactor. Moreover, the results obtained in this work are remarkable compared to literature reports for Ni-based MOFs, demonstrating that the co-catalyst employed plays an important role in the catalytic activity. However, Ni/Zn-MOF showed a lower selectivity to α-C4 oligomers (36 %) against 58 % obtained by Ni-MOF. According to the reuse tests conducted, the bimetallic MOF can be reused for up to two reactions (under 5 bar ethylene in a glass reactor), although presenting a considerable loss in activity due to the formation of metallic Ni.

Copper-Catalyzed Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Assisted by TEMPOL in Liquid Sunlight Methanol.

2,5-Diformylfuran (DFF) is a significant biomass-derived compound with diverse applications in novel furan-based materials, fragrances, fuel additives, and drug synthesis. A pivotal challenge in DFF synthesis is developing a method to produce DFF under mild conditions using sustainable feedstocks. In this study, an affordable 4-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOL)- assisted Cu(OAc)2 catalytic system for aerobic oxidation reaction of HMF to DFF in liquid sunlight methanol solvent was developed. The effects of parameters such as metal species, catalyst amount, solvent species, ligand structure, and reaction temperature were systematically investigated. The evolution of product distribution in the reaction solution at various times was monitored and analyzed using 1H-NMR spectroscopy. FT-IR and ESI-MS characterizations were employed to integrate experimental findings and elucidate the reaction mechanism. The highest DFF yield of 96% and complete conversion of HMF were obtained. Furthermore, a total DFF yield of 68.6% was achieved from fructose using a two-steps method, demonstrating the potential for scalable production. The establishment of this catalytic system presents a novel approach for the selective preparation of DFF from sustainable feedstocks.

Testing combined effects of environmental trace metals/arsenic and marine trophic status on the bioaccumulation in Pacific oysters: Insights from 22-site field samplings

Pacific oysters were sampled from 22 human-impacted sites in northeastern Japan to measure Cr, Cu, Zn, Pb, Cd, and As. The hazard quotient was slightly >1 for Cu and/or As at two sites, but <1 for all metal species and As at the other sites, indicating low human health risks. Oysters' Cu, Zn, and Pb contents were positively related to their concentrations in the sediment, while Cr and As were not. Oysters' Cu and Zn were negatively related to the inorganic nitrogen in seawater, while oysters' Pb and As showed positive relationships with the particulate organic carbon. These findings suggest that marine trophic status affects oysters' metal uptake differently among the metal species. Furthermore, oysters' Cr, Cu, Zn, and Pb contents were negatively related to their eicosapentaenoic acid content and condition index. Therefore, the nutritional conditions of oysters may influence their elimination or accumulation of these metals.

Serum protein albumin and chromium: Mechanistic insights into the interaction between ions, nanoparticles, and protein

The interaction of human proteins and metal species, both ions and nanoparticles, is poorly understood despite their growing importance. These materials are the by-products of corrosion processes and are of relevance for food and drug manufacturing, nanomedicine, and biomedical implant corrosion. Here, we study the interaction of Cr(III) ions and chromium oxide nanoparticles with bovine serum albumin in physiological conditions. This study combined electrophoretic mobility measurements, spectroscopy, and time-of-flight secondary ion mass spectrometry with principal component analysis. It was determined that neither metal species resulted in global albumin unfolding. The Cr(III) ions interacted strongly with amino acids found in previously discovered metal binding sites, but also were most strongly implicated in the interaction with negatively charged acid residues, suggesting an electrostatic interaction. Bovine serum albumin (BSA) was found to bind to the Cr2O3 nanoparticles in a preferential orientation, due to electrostatic interactions between the positive amino acid residues and the negative chromium oxide nanoparticle surface. These findings ameliorate our understanding of the interaction between trivalent chromium ions and nanoparticles, and biological macromolecules.

Sedimentation and transformation of heavy metals during the transport from the Yellow River estuary to the sea: Evidence from surface sediments of the Yellow River subaqueous delta

Estuarine and coastal areas are one of the ultimate sinks for terrestrial heavy metals which play a vital role on the aquatic ecosystem. This study examined heavy metals contents and speciations in Yellow River subaqueous delta surface sediment, to characterize their sedimentation and transformation during transport from estuary to the sea. The results showed that higher concentrations were found in the seaward and the shear front affected areas. The surface sediments were generally not contaminated by heavy metals, except for Cd was highly enriched, while the post-standardization spatial distribution reflected the effect of estuarine processes as a “filter” that effectively intercepting heavy metals. The dominated phase was residual fraction for Cr, Cu, Zn, Cd, while reducible fraction for Ni and carbonate fraction for Pb. The transformation of heavy metal species was mainly influenced by the changes in the sediment components such as carbonate minerals, organic matter and FeMn oxides.

Distribution and geochemical speciation of metals in the sediments of marine aquaculture areas in Japan.

Metal contamination is a crucial environmental issue because of its persistence and toxicity, which can have deleterious effects on aquatic ecosystems. Coastal sediments serve as reservoirs for metals. Aquaculture is an important human activity in coastal areas; however, the actual status of metal distribution in these areas has not been well characterized. We investigated the distribution and geochemical speciation of metals in the sediments of the Japanese aquaculture areas of Shidugawa and Furue Bays. Total metals were generally in the order Zn > Cu > Ni > Cd > Pb and occurred at high levels at the sites in the inner parts and near the fish cages in the sampling areas. Pearson's correlations and principal component analysis results suggested that the metals in these aquaculture areas might originate from several sources, such as fish feces, fish feeds, corrosion of antifouling material residues, and local anthropogenic activities, including fertilizers and manures. Furthermore, metals were mainly in silts and fine sediments, associated with residual speciation, followed by organic fractions, oxides, and high fractions of exchangeable Cd. These results provide important insights into the accumulation of metals in sediments for better managing marine aquaculture in Japan.

Agrochemical inputs to managed oil palm plantations are a probable risk to ecosystems: Results from a screening level risk assessment

Palm oil is a high value crop widely grown in the tropics. The management of palm oil is characterised by widespread agrochemical use. Here we report the results of a screening level risk assessment conducted from the available literature on the environmental concentration of agrochemicals in surface waters and soils in palm oil growing areas. To date, only a small number of published studies have measured pollutant concentrations in and around palm oil plantations. To identify potential high-risk contaminants, a standard SSD based risk assessment, establishing risk quotients for detected contaminants, was conducted in relation to available species sensitivity distributions. A probabilistic SSD based risk assessment, calculating potential risk distributions, was also conducted for contaminants with the required number of data points available. Metals were the most commonly detected (and measured) substances and also presented the greatest risk, especially copper and zinc, but also nickel, lead and cadmium. For these metals, environmental concentrations overlapped levels found to cause effects in toxicity studies, indicating the potential for adverse outcomes from exposure. To fully understand the extent of this risk, more detailed studies are needed that assess metal speciation states and bioavailability under the prevailing soil and water chemistry conditions in palm oil plots. Limited studies have measured pesticide concentrations in palm oil systems. In these few cases, only a few active substances have been measured. From the limited information available, potential risks are indicated due to the presence of some insecticides. However, fungicides are also widely used for palm oil disease management, but little data studies are available to assess both exposure and potential effects. To further assess the potential chemical footprint of different palm oil management practices, studies are needed that systematically assess pollutant levels across a range of chemical groups to consider effects within a mixture context.