Anion Ordering Research Articles

Defect Properties, Anion Ordering, and Photochromic Mechanism in Yttrium Oxyhydride

Defect Properties, Anion Ordering, and Photochromic Mechanism in Yttrium Oxyhydride

Hierarchical ion interactions in the direct air capture of CO2 at air/aqueous interfaces.

The direct air capture (DAC) of CO2 using aqueous solvents is plagued by slow kinetics and interfacial barriers that limit effectiveness in combating climate change. Functionalizing air/aqueous surfaces with charged amphiphiles shows promise in accelerating DAC; however, insight into these interfaces and how they evolve in time remains poorly understood. Specifically, competitive ion interactions between DAC reagents and reaction products feedback onto the interfacial structure, thereby modulating interfacial chemical composition and overall function. In this work, we probe the role of glycine amino acid anions (Gly-), an effective CO2 capture reagent, that promotes the organization of cationic oligomers at air/aqueous interfaces. These surfaces are probed with vibrational sum frequency generation spectroscopy and molecular dynamics simulations. Our findings demonstrate that the competition for surface sites between Gly- and captured carbonaceous anions (HCO3-, CO32-, carbamates) drives changes in surface hydration, which in turn tunes oligomer ordering. This phenomenon is related to a hierarchical ordering of anions at the surface that are electrostatically attracted to the surface and their ability to compete for interfacial water. These results point to new ways to tune interfaces for DAC via stratification of ions based on relative surface propensities and specific ion effects.

Experimental study on freezing temperature and its influencing factors of loess contaminated by heavy metals

This paper attempts to reveal the freezing temperature and its influencing factors of heavy metal-contaminated loess by adopting two cooling methods: fast and slow grading. As a result, Lanzhou loess was used as an experimental material to make polluted soil with varying heavy metal concentrations and initial water content. The pollutant elements included Zn, Ni, Cu, Cr, Cd, and Pb. The findings demonstrate that: 1) The slow cooling rate causes supercooling, jumping, and a progressive decrease in the temperature of the polluted soil. Different cooling methods have no obvious effect on freezing temperature. Furthermore, the freezing temperature of contaminated soil varies depending on its water content. The impact of increasing water content on freezing temperature is not evident; 2) The freezing temperature of loess decreases with the increase of heavy metal ion content. The freezing temperature of loess polluted by Zn, Ni and Cd ions decreased linearly with the increase of ion content. The influence of cations on the freezing temperature of loess is as follows: Zn2+> Ni2+> Cd2+> Cr3+> Pb2+> Cu2+. The influence order of anions is Cl− > SO42−; 3) The freezing temperature of loess containing heavy metal ions is about equal to the freezing temperature of the corresponding heavy metal solution plus the freezing temperature of loess itself. The freezing temperature of heavy metal-polluted loess follows the temperature superposition principle.

Layered NaBa2M3Q3(Q2) (M = Cu or Ag; Q = S or Se) Chalcogenides and Local Ordering in Their Mixed-Anion Compositions.

Three new NaBa2M3Q3(Q2) (M = Ag or Cu; Q = S or Se) chalcogenides were prepared by using solid-state methods and structurally characterized by using single-crystal X-ray diffraction. NaBa2Ag3Se3(Se2) and NaBa2Cu3Se3(Se2) crystallize in monoclinic space group C2/m and have a two-dimensional structure composed of edge-sharing MSe4/4 tetrahedra separated by Na+ and Ba2+ cations, along with (Se2)2- dimers at the center of the spacings between [M3Se3]3- slabs. NaBa2Ag3S3(S2) adopts a related structure with space group C2/m but has additional, crystallographically distinct Ag atoms in the [Ag3S3]3- layer that are linearly coordinated. NaBa2Ag3Se3(Se2) and NaBa2Ag3S3(S2) have indirect band gaps measured to be 1.2 and 1.9 eV, respectively, which is supported by band structures calculated using density functional theory. Mixed-anion NaBa2Cu3Se5-xSx compositions were prepared to probe the presence of anion ordering and heteronuclear (S-Se)2- dimers. Structural analyses of the sulfoselenides indicate that selenium preferentially occupies the Q-Q dimer sites, while Raman spectroscopy reveals a mixture of (S2), (Se2), and heteronuclear (S-Se) units in the sulfur-rich products. The local ordering of the chalcogens is rationalized using simple bonding concepts and adds to a growing framework for understanding ordering phenomena in mixed-anion systems.

Hydrochemical and Formation Mechanism Studies of Groundwater in Quaternary Aquifer in a Northern Plain of China: An Example of Beijing Plain

Beijing Plain is a very active part of Beijing city regarding the socio-economic and human activities of the region. Over the past four decades, Beijing’s economic development and the continuous drought for nearly 10 years in the 2000s have negatively impacted the groundwater quantity and quality. Therefore, it is necessary to investigate the present situation of groundwater chemistry in this region to develop a comprehensive database and orientation for future research on groundwater quality evaluation. Mathematical statistics, Piper’s trilinear diagram, Gibbs plots, the ion ratio method and PHREEQC software 3.7.3 were used to analyze the groundwater hydrogeochemical characteristics and formation mechanisms of the quaternary aquifers of the Beijing Plain area. Hydrogeochemical results indicated that the groundwater is slightly alkaline, with pH values ranging from 6.76 to 8.65 and an average value of 7.92. The order of major cations in groundwater was Ca2+ > Na+ > Mg2+ > K+ with average values of 66.54 mg/L, 50.58 mg/L, 23.78 mg/L, and 1.81 mg/L, respectively, while the order of major anions was HCO3− > SO42− > Cl− with average values of 284.89 mg/L, 52.1 mg/L and 35.5 mg/L, respectively. The groundwater chemical types are Mg-Ca-Cl-HCO3, Na-Ca-HCO3, Mg-Ca-HCO3 and Mg-Na-HCO3. Research on the main influencing factors and PHREEQC hydrogeochemical inverse simulations results along the four pathways selected confirmed that rock weathering with sulfate, silicate and carbonate rock mineral dissolution and Na+, Mg2+ and Ca2+ ion reaction exchange influenced groundwater hydrogeochemical characteristics of the quaternary aquifers of the Beijing Plain area. Understanding the formation mechanisms of hydrogeochemistry in quaternary plains provides guidance for future studies and, through suggestions and case studies, facilitates decision-making by policy-makers on the sustainable management of groundwater resources.

Supramolecular methods: utilising ChemFETs to evaluate aqueous anion affinity of hydrophobic receptors

ABSTRACT The host–guest interaction and affinity of hydrophobic receptors towards aqueous anions can be evaluated by incorporating a receptor into a polymeric membrane and applying these membranes to FET-based sensing devices. A series of anions screened using these ChemFET (chemically sensitive field effect transistor) sensors based on different receptors can also provide a Hofmeister-like ordering of anions based on their respective detection limits. Although the general trends of selectivity coefficients often follow the Hofmeister Series, the specific anion affinity profiles are generally unique to each receptor and provide insight into receptor selectivity. In this methodspaper, we provide a detailed example of how our lab uses ChemFETs to evaluate host–guest interactions of hydrophobic host receptors with aqueous anions, and a detailed procedure for fabricating ChemFET sensor devices is presented along with selected case studies for readers interested in applying related ion recognition strategies in sensors of this type.

Peierls-like distortion drives anion ordering in rutile TiOF

Peierls-like distortion drives anion ordering in rutile TiOF

The Interplay of Electronic Configuration and Anion Ordering on the Magnetic Behavior of Hydroxyfluoride Diaspores.

We report a new nickel hydroxyfluoride diaspore Ni(OH)F prepared using hydrothermal synthesis from NiCl2·6H2O and NaF. Magnetic characterization reveals that, contrary to other reported transition-metal hydroxyfluoride diaspores, Ni(OH)F displays weak ferromagnetism below the magnetic ordering temperature. To understand this difference, neutron diffraction is used to determine the long-range magnetic structure. The magnetic structure is found to be distinct from those reported for other hydroxyfluoride diaspores and shows an antiferromagnetic spin ordering in which ferromagnetic canting is allowed by symmetry. Furthermore, neutron powder diffraction on a deuterated sample, Ni(OD)F, reveals partial anion ordering that is distinctive to what has previously been reported for Co(OH)F and Fe(OH)F. Density functional theory calculations show that OH/F ordering can have a directing influence on the lowest energy magnetic ground state. Our results point toward a subtle interplay between the sign of magnetic exchange interactions, the electronic configuration, and anion disordering.

Anionic and Magnetic Ordering in Rare Earth Tantalum Oxynitrides with an n = 1 Ruddlesden-Popper Structure.

The new compounds R2TaO4-xNx with R = La, Ce, Nd, and Eu and 1.20 ≤ x ≤ 2.81 have been obtained by a solid-state reaction between metal nitrides and oxides or oxynitrides under N2 gas at temperatures between 1200 and 1700 °C. They are the first examples of rare earth transition metal oxynitrides with an n = 1 Ruddlesden-Popper structure and show different anion stoichiometries, crystal structures, and magnetic properties. Synchrotron X-ray powder diffraction and electron diffraction indicate that the lanthanum, cerium, and neodymium compounds crystallize in the orthorhombic space group Pccn, with cell parameters a = 5.72949(2), b = 5.73055(5), and c = 12.77917(6) Å for La2TaO1.31N2.69, a = 5.70500(5), b = 5.71182(4), and c = 12.61280(7) Å for Ce2TaO1.19N2.81, and a = 5.70466(3), b = 5.70476(5), and c = 12.32365(5) Å for Nd2TaO1.46N2.54. In contrast, Eu2TaO2.80N1.20 shows a tetragonal I41/acd superstructure doubling the c axis, with parameters a = 5.71867(2) and c = 25.00092(19) Å. Refinement of neutron powder diffraction data of Ce2TaO1.19N2.81 indicated the nitrogen order in the two equatorial positions of the tantalum octahedron, with refined N/O occupancies of 0.930(7)/0.070 and 0.876(13)/0.124, and the axial position is occupied by 50% of each anion. This anion ordering agrees with the distribution predicted by Pauling's second crystal rule. Magnetization measurements show that the cerium and europium compounds are ordered magnetically at low temperatures, while the neodymium compound remains paramagnetic down to 2 K, as a consequence of suppression of the effective magnetic moment of the latter when reducing the temperature.

Integrated Approach to Hydrogeochemical Assessment of Groundwater Quality in Major Industrial Zone of Punjab, Pakistan.

Groundwater contamination with arsenic (As) is a significant concern in Pakistan's Punjab Province. This study analyzed 69 groundwater samples from Faisalabad, Gujranwala, Lahore, and Multan to understand hydrogeochemistry, health impacts, contamination sources, and drinking suitability. Results revealed varying as concentrations across districts, with distinctive cation and anion orders. Faisalabad exhibited Na+ > Mg2+ > Ca2+ > K+ > Fe2+ for cations and SO42- > Cl- > HCO3- > NO3- > F- for anions. Gujranwala showed Na+ > Ca2+ > Mg2+ > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. In Lahore, demonstrated: Na+ > Ca2+ > Mg2+ > Fe > K+ for cations and HCO3- > SO42- > Cl- > NO3- > F- for anions. Multan indicated K+ > Ca2+ > Mg2+ > Na+ > Fe for cations and HCO3- > SO42- > Cl- > F- > NO3- ) for anions. Hydrochemical facies were identified as CaHCO3 and CaMgCl types. Principal Component Analysis (PCA), highlighted the influence of natural processes and human activities on groundwater pollution. Water Quality Index (WQI) result reveal that most samples met water quality standards. The carcinogenic risk values for children exceeded permissible limits in all districts, emphasizing a significant cancer risk. The study highlights the need for rigorous monitoring to mitigate (As) contamination and protect public health from associated hazards.

Hydrogeochemistry and Quality Assessment using Water Quality Indices of Surface and Groundwater of Konar Reservoir Region, Hazaribag District, Jharkhand, India

ABSTRACT In the present paper, the water quality of the Konar reservoir area in the Hazaribag district of Jharkhand, India, has been investigated and with this view, the different physico-chemical variables, including pH, Dissolved Oxygen, Electrical Conductivity, TDS, Temperature, cations (Ca2+, Mg2+, Na+, K+), anions (CO32−, HCO3−, Cl−, F−, SO42−, NO3−) have been analyzed. According to Schoeller diagram, the order of major cations and anions for groundwater are Ca2+ > Na+ > Mg2+ > K+ and HCO3− > SO42− > Cl− > NO3− and for surface water are Na+ > Ca2+ > Mg2+ > K+ and Cl− > HCO3− > NO3− > SO42− respectively. The calculated water quality index shows that 100% of the samples of surface water are of excellent water quality, while 17% of the samples of groundwater are of excellent and 83% fall under the good category. The Gibbs Plot indicates that the rock-water interaction mechanism is dominant, Giggenbach triangle indicates that the waters have not yet reached equilibrium and are still in an immature state, although the Piper plot demonstrates that most of the surface water samples (78%) are mixed facies of Ca2+-Mg2+-Cl− and 22% are of Na+–Cl− type. All groundwater samples are mixed facies of Ca2+– HCO3− type. According to the Durov plot, 100% of surface water samples exhibit simple dissolution or mixing and majority of the ions in all groundwater samples are calcium and bicarbonate, showing the influence of limestone deposits. Almost all of the water samples from the Konar reservoir area were found to be appropriate for irrigation, according to the Residual Sodium Carbonate, Residual Sodium Bicarbonate, Sodium Percentage, Permeability Index, Kelley’s Ratio, Sodium Adsorption Ratio, United States Salinity Laboratory (USSL) and Wilcox diagrams.

Geospatial analysis of toxic metal contamination in groundwater and associated health risks in the lower Himalayan industrial region

Once known for its clean and natural environment, the lower Himalayan region is now no exception to human-induced disturbances. Rapid industrial growth in Baddi-Barotiwala (BB) industrial region has led to degradation of groundwater resources in the area. Groundwater samples were collected from 37 locations to study the groundwater chemistry, geospatial variation of 15 toxic metals in groundwater, source apportionment, metals of concern and associated health risks in the region. The results showed rock dominated hydrogeology with decreasing order of anion and cation abundance as HCO3− > Cl− > SO42− > NO3− > Br− > F− and Ca+ > Na+ > Mg2+ > K+ > Li+ respectively. Concentrations of Iron (BDL-3.6 mg/l), Nickel (BDL-0.023 mg/l), Barium (0.22–0.89 mg/l), Lead (0.0001–0.085 mg/l) and Zinc (0.006–21.4 mg/l) were found above the permissible limits at few locations. Principal component analysis (PCA) and coefficient of variance (CV) showed both geogenic and anthropogenic origin of metals in groundwater of the BB industrial region. A consistent concentration of Uranium was detected at all the sampling locations with an average value of 0.0039 mg/l and poor spatial variation indicating its natural presence. Overall, non-carcinogenic (N-CR) risk in the study area via oral pathway was high for adults and children (Hazard Index > 1) with geogenic Uranium as the major contributor (Hazard Quotient > 1) followed by Zinc, Lead and Cobalt. Carcinogenic (CR) risk in the region was high for adults having mean value above the threshold (1E-04) with Nickel and Chromium as the metals of major concern. Spatial variation of health risks was overlayed on village boundaries of the region to identify the potential industrial sources of the metals of major concern. The results highlight the need for immediate remediation of groundwater resources in order to achieve a harmonious coexistence between industrialization and human well-being.

Ruddlesden-Popper Oxyfluorides La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1): Impact of the Ni/Cu Ratio on the Structure.

Ruddlesden-Popper oxyfluorides La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1) were obtained by topochemical reaction of oxide precursors La2Ni1-xCuxO4, prepared by citrate-based soft chemistry synthesis, with polyvinylidene fluoride (PVDF) as the fluorine source. Systematic changes of the crystal structure in the oxide as well as the oxyfluoride substitution series were investigated. For 0.2 ≤ x ≤ 0.9, the oxyfluorides adopt the monoclinic (C2/c) structural distortion previously solved for the x = 0.8 compound based on neutron powder diffraction data, whereas the sample with a lower Cu content of x = 0.1 crystallizes in the orthorhombic (Cccm) structure variant of La2NiO3F2. The orthorhombic-to-monoclinic structural transition was found to be the result of an additional tilt component of the Jahn-Teller elongated CuO4F2 octahedra. The structural transitions were additionally studied by DFT calculations, confirming the monoclinic space group symmetry. The "channel-like" anionic ordering of the endmembers La2NiO3F2 and La2CuO3F2 was checked by 19F MAS NMR experiments and was found to persist throughout the entire substitution series.

Investigation of O/N Ordering in Perovskite-Type Oxynitrides La1−xYxTa(O,N)3 on Long Range and Short Scale

Oxynitrides such as LaTa(O,N)3 are attractive materials as photoelectrodes for photoelectrocatalytic solar water splitting. The potential anionic ordering in their perovskite-type structure has been shown to impact the materials’ properties. Given the importance attributed to it, the present study reports a detailed experimental analysis supported by simulations of the anionic ordering of La1−xYxTa(O,N)3. The influence of O/N and yttrium content on the anionic order was assessed. Neutron diffraction analysis was performed on four different nominal compositions—LaTaON2, LaTaO2N, La0.9Y0.1TaON2, and La0.9Y0.1TaO2N—at 10 K and 300 K to study potential long-range ordering. Neutron pair distribution function (PDF) analysis was performed on all samples at 10 K and on non-Y-substituted samples at 300 K to evaluate short-range ordering. There was no evidence of long-range O/N order in any of the compounds. In contrast, at a short range (1.5 Å ≤ r < 6 Å), a Pnma (a−b+a−) tilting pattern and local cis-ordering of the anions were seen. The latter faded rapidly, leaving the Pnma tilting pattern in a 6 Å ≤ r ≤ 11 Å range. At higher distances, the PDF analysis agreed with the Imma (a−b0a−) O/N disordered long-range structure. As the O/N content changed, not much difference in behavior was observed. Yttrium substitution introduced some disorder in the structure; nonetheless, it showed marginal influence on octahedral tilting and anionic ordering.

Interactions between the protein barnase and co-solutes studied by NMR

Protein solubility and stability depend on the co-solutes present. There is little theoretical basis for selection of suitable co-solutes. Some guidance is provided by the Hofmeister series, an empirical ordering of anions according to their effect on solubility and stability; and by osmolytes, which are small organic molecules produced by cells to allow them to function in stressful environments. Here, NMR titrations of the protein barnase with Hofmeister anions and osmolytes are used to measure and locate binding, and thus to separate binding and bulk solvent effects. We describe a rationalisation of Hofmeister (and inverse Hofmeister) effects, which is similar to the traditional chaotrope/kosmotrope idea but based on solvent fluctuation rather than water withdrawal, and characterise how co-solutes affect protein stability and solubility, based on solvent fluctuations. This provides a coherent explanation for solute effects, and points towards a more rational basis for choice of excipients.

Synthesis and symmetry of perovskite oxynitride CaW(O,N)3.

Perovskite oxynitrides, in addition to being promising electrocatalysts and photoabsorbers, present an interesting case study in crystal symmetry. Full or partial ordering of the O and N anions affects global symmetry and influences material performance and functionality; however, anion ordering is challenging to detect experimentally. In this work, we synthesize a novel perovskite oxynitride CaW(O,N)3 and characterize its crystal structure using both X-ray and neutron diffraction. Through co-refinement of the diffraction patterns with a range of literature and theory-derived model structures, we demonstrate that CaW(O,N)3 adopts an orthorhombic Pnma average structure and exhibits octahedral distortion with evidence for preferred anion site occupancy. However, through comparison with a large, low-symmetry unit cell, we identify the presence of disorder that is not fully accounted for by the high-symmetry model. We compare CaW(O,N)3 with SrW(O,N)3 to demonstrate the broader presence of such disorder and identify contrasting features in the electronic structures. This work signifies an updated perspective on the inherent crystal symmetry present in perovskite oxynitrides.

Theoretical study of the structural and energetic properties of Ce1-xZrxO2 nanoparticles via molecular dynamics simulations.

The combination of ceria (CeO2) with different metal oxides (MO2), e.g. Ce1-xMxO2, has been strategically used to enhance its intrinsic properties. Moreover, the controlled synthesis of mixed oxide nanoparticles (NPs) opens the opportunity to explore the size dependence and chemical composition of the physical-chemical properties. However, our atomic-level understanding of how the physical-chemical and thermodynamic characteristics change with particle size and composition remains far from satisfactory. Here, we used force-field molecular dynamics simulations to investigate the effects of composition (x) and size on the physical-chemical properties of Ce1-xZrxO2 NPs with diameter from 1 (32 cations) up to 3 nm (256 cations), where x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0. We found abrupt changes in potential energy versus temperature for NPs with more than 108 cations, indicating a structural phase transition from disordered to ordered structures, which was confirmed by the radial distribution function. We found a linear relationship between the phase transition temperature (Tpt) and the size and composition of the NPs: the increase in the molar fraction of Zr4+ and the reduction in particle size are related to lower Tpt temperature and less defined decays of potential energy versus temperature. NPs larger than 56 cations show a radial distribution function with several peaks, which is related to the order of cations and anions in these structures. These peaks gradually disappear as the size decreases and the fraction of Zr4+ increases. Similar trends were observed with X-ray diffraction analysis; for example, fluorite-like motifs occur even with 56 cations in the case of ceria, but only for NPs with 108 cations for zirconia. Common neighbor analysis confirmed that NPs with well-defined values of the temperature Tpt have face-centered cubic (fcc)-like domains in the core region. The number of ordered fcc cations increases with increasing NP size and decreasing Zr4+ concentration. Finally, we observed that ceria nucleate first during simulated annealing and occupy highly coordinated sites within the core, while Zr4+ prefers the lowest coordinated sites on the surface.

Disrupting the Hofmeister bias in salt liquid-liquid extraction with an arylethynyl bisurea anion receptor.

Host-mediated liquid-liquid extraction is a convenient method for the separation of inorganic salts. However, selective extraction of an anion, regardless of its hydrophilicity or lipophilicity as qualitatively described by its place in the Hofmeister series, remains challenging. Herein we report the complete disruption of the Hofmeister-based ordering of anions in host-mediated extraction by a rigidified tweezer-type receptor possessing remarkably strong anion-binding affinity under the conditions examined. Experiments introduce a convenient new method for determination of anion binding using phosphorus inductively coupled plasma mass spectrometry (ICP-MS) to measure extraction of tetra-n-butylphosphonium (TBP+) salts from water into nitrobenzene, specifically examining the disrupting effect of the added arylethynyl bisurea anion receptor. In the absence of the receptor, the salt partitioning follows the expected Hofmeister-type ordering favoring the larger, less hydrated anions; the analysis yields the value -24 kJ mol-1 for the standard Gibbs energy of partitioning of TBP+ cation from water into nitrobenzene at 25 °C. Selectivity is markedly changed by the addition of receptor to the nitrobenzene and is concentration dependent, giving rise to three selectivity regimes. We then used SXLSQI liquid-liquid equilibrium analysis software developed at Oak Ridge National Laboratory to fit host-mediated extraction equilibria for TBP+ salts of Cl-, Br-, I-, and NO3- to the distribution data. While the reverse-Hofmeister 1 : 1 binding of the anions by the receptor effectively cancels the Hofmeister selectivity of the TBPX partitioning into nitrobenzene, formation of unexpected 2 : 1 receptor : anion complexes favoring Cl- and Br- dominates the selectivity at elevated receptor concentrations, producing the unusual order Br- > Cl- > NO3- > I- in anion distribution wherein a middle member of the series is selected and the most lipophilic anion is disfavored. Density functional theory calculations confirmed the likelihood of forming 2 : 1 complexes, where Cl- and Br- are encapsulated by two receptors adopting energetically competitive single or double helix structures. The calculations explain the rare non-Hofmeister preference for Br-. This example shows that anion receptors can be used to control the selectivity and efficiency of salt extraction regardless of the position of the anion in the Hofmeister series.

Theoretical insights into the effect of surface structure and anion ordering on the properties of SrTaO2N for photocatalytic water splitting

AbstractAs one of the representative perovskite‐type oxynitride photocatalysts, SrTaO2N has the ability to split water in the visible‐light region. It was found that the surface modification and interfacial design of SrTaO2N‐based materials are closely related to the photocatalytic activity, but the microscopic mechanisms of these experimental phenomena are not well understood. In this work, we have utilized density functional theory (DFT) calculations to investigate the effect of anion ordering and exposed terminations on the electronic structures, optical absorption, water adsorption and the mechanisms of water oxidation and reduction reactions of SrTaO2N. Our results indicate that cis configurations are more stable than trans configurations. The anion ordering has an important effect on the band gap and optical absorption coefficient. The terminations with exposed Ta atoms are more stable and have bigger work functions than those with exposed Sr atoms possibly due to the bonding ionicity and surface dipoles. The dissociative adsorption of water is energetically more favorable than the molecular adsorption on most surfaces. The highly active sites of hydrogen evolution reaction (HER) are the exposed nonmetal atoms. Terminations with exposed Sr and N atoms have lower overpotentials (0.70–0.77 V) of oxygen evolution reaction (OER) than others. They are comparable to the calculated results of common photocatalysts, such as Co3O4 and TiO2. This study sheds light on the relationship between the termination structure with different anion orders and the photocatalysis‐related properties of SrTaO2N at a molecular level, which provides guidance for constructing highly active photocatalytic materials.

Assessment of some bottled natural mineral waters and spring waters in Algeria using multivariate statistical analysis, hydrogeochemical approaches and water quality index (WQI)

ABSTRACT In Algeria, the consumption of mineral waters has grown enormously, indicating that these waters have safe quality for drinking use. The objectives of the present study are to evaluate the physicochemical characteristics of 43 bottled mineral waters and to identify the main hydrogeochemical processes governing water chemistry using a combination of geochemical techniques and multivariate statistical approaches. The results revealed that the abundance order of cations and anions (mg/L) are Ca2+> Na+> Mg2+> K+, HCO3 −> SO4 2−> Cl−> NO3 −. In addition, the comparison between the obtained results and World Health Organization (WHO) standards showed that the analysed physicochemical parameters (pH, Na+, Cl−, SO4 2−, NO3 −) are within the acceptable limits of the World Health Organization (WHO) for drinking except TDS, Ca 2+, Mg2+, K+, HCO3 −, which exceed the WHO permissible limits in few water samples. Hydrogeochemical types in the study area were Ca2+-HCO3 −, Ca2+-Mg2+-HCO3 −, Ca-Mg2+-SO4 2—Cl-, Na+-HCO3 − and Na+-Cl−types, with a low mineral and intermediate mineral contents based on Van der Aa’s classification. The Gibbs plot specifies that almost all samples (93%) fall in water–rock interaction dominance. The major hydrogeochemical processes acting are dissolution of carbonate minerals, ion-exchange mechanisms and silicate weathering. Principal component analysis (PCA) was applied to hydrochemical data of mineral water samples. The results suggest that hydrochemistry in the region is affected not only by geogenic processes but also is impacted by anthropogenic activities. The comparative evaluation of the different water quality indices (WQI) shows that there is a difference between indices values for the same water sample, which may be attributed to the weighting methods, aggregation methods, and the limits of classes used in the calculation of each index. The results from this study can provide the basis for local decision-makers to develop suitable water management strategies and protection against any pollution risk.