Alkaline metal tungstate anchored on functionalized-MWCNT: A co-active electrocatalyst for the detection of levofloxacin.

The widespread usage of levofloxacin (LVF) intake is executed for several urinary and respiratory systems infections in human. But, its over intake leads to severe damage to humans and the environment by its exposure. Hence the detection of LVF is concerned and we herein developed an electrocatalyst, strontium tungsten oxide nanospheres and later decorated onto the functionalized multiwall carbon nanotubes (SrWO4/f-MWCNT) to perform effective electrochemical recognition of LVF in aquatic and biological samples. Binary metal oxide with carbon composite SrWO4/f-MWCNT was developed due to its specific features as nanostructures. Various methods of investigation have been examined to identify the physiochemical characteristics like X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and morphological characteristics including field emission scanning electron microscopy, and transmission electron microscopy. The synthesized SrWO4/f-MWCNT sample crystalline size was around 32.9 nm. The SrWO4/f-MWCNT modified glassy carbon electrode (GCE) has been subjected to electrochemical investigation with a wide linear range of 0.049 µM-574.73 µM with good sensitivity 2.86 µA µM-1 cm2, the limit of detection at 14.9 nM for LVF sensing. Furthermore, the designed LVF detection exhibited excellent anti-interference, stability, reproducibility, and repeatability. The as-developed sensor's electrochemical outcomes indicate the superior performance inherent in the developed composite.

A Well-Defined Magnesium Complex of C70 6.

Controlling and understanding charge state and metal coordination in carbon nanomaterials is crucial to harnessing their unique properties. Here we describe the synthesis of the well-defined fulleride complex [{(Mesnacnac)Mg}6C70], 2, (Mesnacnac)=HC(MeCNMes)2, Mes=2,4,6-Me3C6H2, from the reaction of the ß-diketiminate magnesium(I) complex [{(Mesnacnac)Mg}2] with C70 in aromatic solvents. The molecular structure of complex 2 was determined, providing the first high-quality structural study of a complex with the C70 6- ion. In combination with solution state NMR spectroscopic and DFT computational studies, the changes in geometry and charge distribution in the various atom and bond types of the fulleride unit were investigated. Additionally, the influence of the (Mesnacnac)Mg+ cations on the global and local fulleride coordination environment was examined.

Metals on the Menu-Analyzing the Presence, Importance, and Consequences.

Metals are integral components of the natural environment, and their presence in the food supply is inevitable and complex. While essential metals such as sodium, potassium, magnesium, calcium, iron, zinc, and copper are crucial for various physiological functions and must be consumed through the diet, others, like lead, mercury, and cadmium, are toxic even at low concentrations and pose serious health risks. This study comprehensively analyzes the presence, importance, and consequences of metals in the food chain. We explore the pathways through which metals enter the food supply, their distribution across different food types, and the associated health implications. By examining current regulatory standards for maximum allowable levels of various metals, we highlight the importance of ensuring food safety and protecting public health. Furthermore, this research underscores the need for continuous monitoring and management of metal content in food, especially as global agricultural and food production practices evolve. Our findings aim to inform dietary recommendations, food fortification strategies, and regulatory policies, ultimately contributing to safer and more nutritionally balanced diets.

Square-planar Tetranuclear Cluster-based Alkaline Earth Metal-organic Frameworks with Enhanced Proton Conductivity.

Alkaline earth (AE) metal complexes have garnered significant interest in various functional fields due to their nontoxicity, low density, and low cost. However, there is a lack of systematic investigation into the structural characteristics and physical properties of AE-metal-organic frameworks (MOFs). In this research, we synthesized isostructural MOFs consisting of AE4(µ4-Cl) clusters bridged by benzo-(1,2;3,4;5,6)-tris(thiophene-2'-carboxylic acid) (BTTC3-) ligands. The resulting structure forms a truncated octahedral cage denoted as [AE4(m4-Cl)]6(BTTC)8, which further linked to a porous three-dimensional framework. Among the investigated AE ions (Ca, Sr, and Ba), the Ca4-MOF demonstrated good chemical stability in water compared to Sr4-MOF and Ba4-MOF. The N2 adsorption and solid-state UV-vis-NIR absorption behaviors were evaluated for all AE4-MOFs, showing similar trends among the different metal ions. Additionally, the proton conduction study revealed that the Ca4-MOF exhibited ultra-high proton conductivity, reaching 3.52×10-2 S cm-1 at 343 K and 98 % RH. Notably, the introduction of LiCl via guest exchange resulted in an improved proton conduction of up to 6.36×10-2 S cm-1 under similar conditions in the modified LiCl@Ca4-MOF. The findings shed light on the regulation of physical properties and proton conductivity of AE-MOFs, providing valuable insights for their potential applications in various fields.

A database overview of metal-coordination distances in metalloproteins.

Metalloproteins are ubiquitous in all living organisms and take part in a very wide range of biological processes. For this reason, their experimental characterization is crucial to obtain improved knowledge of their structure and biological functions. The three-dimensional structure represents highly relevant information since it provides insight into the interaction between the metal ion(s) and the protein fold. Such interactions determine the chemical reactivity of the bound metal. The available PDB structures can contain errors due to experimental factors such as poor resolution and radiation damage. A lack of use of distance restraints during the refinement and validation process also impacts the structure quality. Here, the aim was to obtain a thorough overview of the distribution of the distances between metal ions and their donor atoms through the statistical analysis of a data set based on more than 115 000 metal-binding sites in proteins. This analysis not only produced reference data that can be used by experimentalists to support the structure-determination process, for example as refinement restraints, but also resulted in an improved insight into how protein coordination occurs for different metals and the nature of their binding interactions. In particular, the features of carboxylate coordination were inspected, which is the only type of interaction that is commonly present for nearly all metals.

Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals.

Birch reduction and similar dissolved metal-type transformations hold significant importance in the organic synthesis toolbox. Historically, the field has been dominated by alkali metal reductants. In this study, we report that largely neglected, low-reactive alkaline earth metals can become powerful and affordable reductants when used in a ball mill under essentially solvent-free conditions, in the presence of ethylenediamine and THF as liquid additives. Calcium can reduce both electron-deficient and electron-rich arenes, with yields of products similar to those obtained with lithium metal. Magnesium reveals enhanced reducing power, enabling the reduction of benzoic acids while keeping electron-rich aromatic moieties intact and allows for chemoselective transformations. The developed mechanochemical approach uses readily available and safer-to-handle metals, operates under air and ambient temperature conditions, and can be used for gram-scale preparations. Finally, we demonstrate that the developed conditions can be used for other dissolved metal-type reductive transformations, including reductive amination, deoxygenation, dehalogenation, alkene and alkyne reductions.

Enhanced hydrogen storage of alkaline earth metal-decorated Bn (n = 3-14) nanoclusters: a DFT study.

CONTEXT: Boron-based nanostructures hold significant promise for revolutionizing hydrogen storage technologies due to their exceptional properties and potential in efficiently accommodating and interacting with hydrogen molecules. In this paper, boron-based Bn (n = 3-14) nanoclusters decorated with alkaline earth metals (AEM = Ca and Be) were investigated for hydrogen storage applications based on density function theory (DFT) calculations. To evaluate H2 adsorption capability, the adsorption energies, frontier molecular orbitals (FMOs), natural bond orbital (NBO), and quantum theory of atoms in molecule (QTAIM) analysis are performed. The primary aim of this research work is to achieve targeted value of 5.5 wt% set by the US Department of Energy (DOE) for the year 2025. The results revealed that B5Ca2, B6Ca2, and B10Ca2 structures have the ability to hold up to 12H2 molecules with gravimetric capacities of 15.20, 14.21, and 8.60 wt%, respectively, when compared to other boron structures decorated with calcium. Similarly, for Be-decorated structure, B3Be2 structure can accommodate 3H2 molecules with gravimetric capacity of 10.59 wt%. The result of this study indicates that AEM-decorated Bn nanoclusters hold great promise as potential materials for hydrogen storage. METHODS: Density functional theory (DFT) approach at ωB97XD/6-311++G(d,p) level of theory is employed to investigate the possibility of storing H2 molecules on alkaline earth metal (AEM = Ca and Be)-decorated Bn (n = 3-14) nanoclusters. All DFT computations were performed using Gaussian 09 software. To calculate frontier molecular orbitals (FMOs) and quantum theory of atoms in molecule (QTAIM) analysis, we have used GaussView and Multiwfn software, respectively.

Predominance of the alkaline earth(II) triscarbonatoactinyl(VI) complexes in different geochemical contexts: Review of existing data and estimation of potentially unidentified species.

From the available thermodynamic data in the literature, a review of the impact of the formation of complexes between triscarbonatoactinyl(VI) and alkaline earth(II) (Ae) is estimated under varying conditions. First, after analyzing the literature data and using the ascertained thermodynamic data available from the commissioned reviews from the Nuclear Energy Agency (Organization for the Economic Cooperation and Development) Thermochemical DataBank Project on actinides (An) U, Np, and Pu, and from recently determined AenUO2(CO3)3(4-2n)- thermodynamic functions, the formation of AenAnO2(CO3)3(4-2n)- complexes for Pu(VI) and Np(VI) are estimated using linear free energy relationships (LFERs). The data are in good agreement with the sole determination of AePuO2(CO3)32- from Jo et al. (Dalton Trans. 49, 11605), which gives a relative confidence in the LFERs, and allows the application to actual situations. From existing uranium data, first, the impact of the origin of the data on the calculated predominance is addressed under 0.1 M NaCl and atmospheric CO2(g); second, the influence of ionic strength and salinity on predominance is estimated; and finally, the influence of temperature up to 50 °C on the solubility of uraninite in a deep geological radioactive waste storage or disposal site is calculated. For neptunium and plutonium, the impact of the potential log10ß°(AenAnO2(CO3)3(4-2n)-) on Pourbaix diagrams of Pu and Np in Mg-Ca-CO3 media are estimated from Jo et al. (Dalton Trans. 49, 11605) and LFERs. Finally, the application to the speciation of Pu and Np in seawater is proposed.

Ca(II) and Yb(II) complexes featuring M(C≡C)4 structural motif: enforced proximity or genuine η2 -bonding?

Bis(carbazolide) complexes M[3,6-tBu2 -1,8-(RC≡C)2 Carb]2 (THF)n (R=SiMe3 , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe3 )2 ]2 (THF)2 with two molar equivalents of carbazoles. The complexes feature M(η2 -C≡C)4 structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η2 -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution. According to QTAIM analysis there are 4 bond critical points (3;-1) between the metal atom and each of the triple bonds, which are connected by a strongly curved, almost T-shaped bond pathway.

Pyrolysis and steam gasification properties of mangroves.

The rising atmospheric CO2 emissions from the burning of fossil fuels remains a global concern. Mangrove forests, which are important for global biodiversity, are known for their high carbon fixation capacity. However, the characteristics of the pyrolysis and gasification of mangroves remain unclear. Thus, this study focused on mangroves' basic pyrolysis and steam gasification properties for use as a gasification fuel. Three mangrove species: Rhizophora mucronata, Bruguiera cylindrica, and Avicennia marina, were used as experimental samples. In addition, three species of land wood were used for comparison: Eucalyptus, Japanese cedar, and Japanese cypress. In addition to the raw sample, a demineralized sample was used for each sample to account for the influence of the alkali and alkaline earth metals (AAEMs) on pyrolysis and steam gasification. Thermogravimetric analysis was performed to obtain thermogravimetric curves of mangroves and land wood. A laboratory-scale instrument for pyrolysis and gasification using a batch-type horizontal electric furnace was also used at 800 °C in an inert and steam atmosphere. The char yield of raw mangroves was high and independent of the Klason lignin content, suggesting that AAEMs influence char formation during the initial pyrolysis of the mangroves. The results of pyrolysis and gasification under steam atmosphere showed that the H2 production ratio (Steam/Inert) from mangroves was 2.52-5.33, compared to 1.76-2.35 for land woods, the addition of steam significantly enhanced the steam gasification of mangroves. Mangroves contain relatively large amounts of AAEMs, which indicates their potential as a gasification feedstock.

First Principles Study of the Photoelectric Properties of Alkaline Earth Metal (Be/Mg/Ca/Sr/Ba)-Doped Monolayers of MoS2.

The energy band structure, density of states, and optical properties of monolayers of MoS2 doped with alkaline earth metals (Be/Mg/Ca/Sr/Ba) are systematically studied based on first principles. The results indicate that all the doped systems have a great potential to be formed and structurally stable. In comparison to monolayer MoS2, doping alkaline earth metals results in lattice distortions in the doped system. Therefore, the recombination of photogenerated hole-electron pairs is suppressed effectively. Simultaneously, the introduction of dopants reduces the band gap of the systems while creating impurity levels. Hence, the likelihood of electron transfer from the valence to the conduction band is enhanced, which means a reduction in the energy required for such a transfer. Moreover, doping monolayer MoS2 with alkaline earth metals increases the static dielectric constant and enhances its polarizability. Notably, the Sr-MoS2 system exhibits the highest value of static permittivity, demonstrating the strongest polarization capability. The doped systems exhibit a red-shifted absorption spectrum in the low-energy region. Consequently, the Be/Mg/Ca-MoS2 systems demonstrate superior visible absorption properties and a favorable band gap, indicating their potential as photo-catalysts for water splitting.

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model.

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution - Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. The model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg2+. With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5-11), solute/solid ratio (1.37 × 10-5- 8.33 × 10-4 mol-solute/g-solid), ionic strengths (0.01 M - 0.7 M), and background electrolytes (Na+, Cs+, Rb+, Cl-, and NO3-) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg2+ to reduce Cd2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

Effect of cooking temperature on metal concentrations and speciation in fish muscle and seal liver.

Fish and marine mammals constitute a significant part of the country food diet of many Indigenous communities in Canada. These animals sometimes accumulate essential elements as well as elevated levels of toxic metals. We experimentally assessed how changes in cooking temperature (23-99 °C by boiling) modified elemental concentrations in whitefish muscle and grey seal liver (two organs commonly consumed in some northern communities). Wet and dry elemental concentrations changed linearly as a function of temperature, and two patterns were observed: methylmercury, selenium, and rare earth elements tended to remain associated with the food during cooking, whereas alkali, alkaline-earth metals, and arsenic were significantly transferred to cooking juices. Mass balances indicated that speciation of mercury was stable during cooking. Because elements generally behaved similarly as those of their periodic table group or their ecotoxicological classes (A, B, intermediate), we propose that elemental behavior during cooking is partly a function of chemical affinity, and this relationship can be used to predict the behavior of data-poor elements of emerging concern, such as technology-critical elements. Furthermore, the marked increases and decreases in elemental concentrations during cooking (e.g., -14% As and +39% Se in whitefish; -22% Cd and +55% Hg in seal liver, on a wet weight basis) should be considered when assessing risk because current exposure models usually only consider elemental concentrations in raw food.

Preparation of multilayer strontium-doped TiO2/CDs with enhanced photocatalytic efficiency for enrofloxacin removal.

Multilayer strontium-doped TiO2/carbon dots (CDs) materials (TC) were produced via sol-gel-layered carbonization method. A thorough analysis of the fabricated composites via XRD, SEM, and XPS revealed that strontium ions, TiO2 and CDs, were combined with each other to form layered structures. According to the UV-Vis diffuse reflectance spectrograms and (αhv)1/2 vs. hv plots, the electron-donor property of strontium ions caused a more positive TC conduction band position than that in the pure TiO2, thereby increasing the visible-light absorption range of TC. Based on the photocatalytic degradation data, the degradation rate of enrofloxacin was 84.7% at the dosage of 0.05 g·L-1 and the concentration of 10 mg·L-1. The capture experiments and ESR results showed that ·O2- and e- played a major role in the degradation process of TC. The possible degradation mechanism of enrofloxacin was explained in terms of decarboxylation and defluorination, as was detected via ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) analysis.

1H NMR and EPR Spectroscopies Investigation of Alginate Cross-Linking by Divalent Ions.

Alginate is a natural polymer widely applied in materials science, medicine, and biotechnology. Its ability to bind metal ions in order to form insoluble gels has been comprehensively used to create capsules for cell technology, drug delivery, biomedical materials, etc. To modify and predict the properties of cross-linked alginate, knowledge about the mechanism of alginate binding with metal ions and the properties of its gels is necessary. This article presents the results obtained by proton Nuclear Magnetic Resonance Spectroscopy for alginate containing calcium and strontium (alkaline earth metal diamagnetic) ions and by Electron Paramagnetic Resonance Spectroscopy for alginate with copper (Cu) and manganese (Mn) (transition metal paramagnetic) ions. It was found that in the case of calcium (Ca) and Mn ions, their concentration does not affect their distribution in the alginate structure and the cross-linking density. In the case of strontium (Sr) and Cu ions, their number affects the number of binding sites and, accordingly, the cross-linking density. Thus, the cross-linking of alginate depends mainly on the characteristics of specific cations, while the nature of the bond (ionic or coordination type) is less important.

Alkaline earth metals for osteogenic scaffolds: From mechanisms to applications.

Regeneration of bone defects is a significant challenge today. As alternative approaches to the autologous bone, scaffold materials have remarkable features in treating bone defects; however, the various properties of current scaffold materials still fall short of expectations. Due to the osteogenic capability of alkaline earth metals, their application in scaffold materials has become an effective approach to improving their properties. Furthermore, numerous studies have shown that combining alkaline earth metals leads to better osteogenic properties than applying them alone. In this review, the physicochemical and physiological characteristics of alkaline earth metals are introduced, mainly focusing on their mechanisms and applications in osteogenesis, especially magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Furthermore, this review highlights the possible cross-talk between pathways when alkaline earth metals are combined. Finally, some of the current drawbacks of scaffold materials are enumerated, such as the high corrosion rate of Mg scaffolds and defects in the mechanical properties of Ca scaffolds. Moreover, a brief perspective is also provided regarding future directions in this field. It is worth exploring that whether the levels of alkaline earth metals in newly regenerated bone differs from those in normal bone. The ideal ratio of each element in the bone tissue engineering scaffolds or the optimal concentration of each elemental ion in the created osteogenic environment still needs further exploration. The review not only summarizes the research developments in osteogenesis but also offers a direction for developing new scaffold materials.

Synthesis of Sterically Encumbered Alkaline-Earth Metal Amides Applying the In Situ Grignard Reagent Formation.

Magnesium and calcium are too inert to deprotonate amines directly. For the synthesis of bulky amides alternative strategies are required and in the past, N-bound trialkylsilyl groups have been used to ease metalation reactions. The in situ Grignard reagent formation in stirred suspensions of magnesium or calcium with hydryl halide and imine in THF allows the synthesis of a plethora of amides with bulky silyl-free substituents. Ball milling protocols partially favor competitive side reactions such as aza-pinacol coupling reactions. Calcium is the advantageous choice for the in situ Grignard reagent formation and subsequent addition onto the imines yielding bulky calcium bis(amides) whereas the stronger reducing heavier alkaline-earth metals strontium and barium are less selective and hence, the aza-pinacol coupling reaction becomes competitive. Exemplary, the solid-state molecular structures of [(Et2 O)Mg(N(Ph)(CHPh2 )2 ] and [(Et2 O)2 Ca(N(Ph)(CHPh2 )2 ] have been determined.

Sr(II) and Ba(II) Alkaline Earth Metal-Organic Frameworks (AE-MOFs) for Selective Gas Adsorption, Energy Storage, and Environmental Application.

Two new alkaline earth metal-organic frameworks (AE-MOFs) containing Sr(II) (UPJS-15) or Ba(II) (UPJS-16) cations and extended tetrahedral linker (MTA) were synthesized and characterized in detail (UPJS stands for University of Pavol Jozef Safarik). Single-crystal X-ray analysis (SC-XRD) revealed that the materials are isostructural and, in their frameworks, one-dimensional channels are present with the size of ~11 × 10 Å2. The activation process of the compounds was studied by the combination of in situ heating infrared spectroscopy (IR), thermal analysis (TA) and in situ high-energy powder X-ray diffraction (HE-PXRD), which confirmed the stability of compounds after desolvation. The prepared compounds were investigated as adsorbents of different gases (Ar, N2, CO2, and H2). Nitrogen and argon adsorption measurements showed that UPJS-15 has SBET area of 1321 m2 g-1 (Ar) / 1250 m2 g-1 (N2), and UPJS-16 does not adsorb mentioned gases. From the environmental application, the materials were studied as CO2 adsorbents, and both compounds adsorb CO2 with a maximum capacity of 22.4 wt.% @ 0 °C; 14.7 wt.% @ 20 °C and 101 kPa for UPJS-15 and 11.5 wt.% @ 0°C; 8.4 wt.% @ 20 °C and 101 kPa for UPJS-16. According to IAST calculations, UPJS-16 shows high selectivity (50 for CO2/N2 10:90 mixture and 455 for CO2/N2 50:50 mixture) and can be applied as CO2 adsorbent from the atmosphere even at low pressures. The increased affinity of materials for CO2 was also studied by DFT modelling, which revealed that the primary adsorption sites are coordinatively unsaturated sites on metal ions, azo bonds, and phenyl rings within the MTA linker. Regarding energy storage, the materials were studied as hydrogen adsorbents, but the materials showed low H2 adsorption properties: 0.19 wt.% for UPJS-15 and 0.04 wt.% for UPJS-16 @ -196 °C and 101 kPa. The enhanced CO2/H2 selectivity could be used to scavenge carbon dioxide from hydrogen in WGS and DSR reactions. The second method of applying samples in the area of energy storage was the use of UPJS-15 as an additive in a lithium-sulfur battery. Cyclic performance at a cycling rate of 0.2 C showed an initial discharge capacity of 337 mAh g-1, which decreased smoothly to 235 mAh g-1 after 100 charge/discharge cycles.

A DFT Study of Alkaline Earth Metal-Doped FAPbI3 (111) and (100) Surfaces.

Density functional theory calculations have been performed to study the effect of replacing lead by alkaline earth metals on the stability, electronic and optical properties of the formamidinium lead triiodide (FAPbI3) (111) and (100) surfaces with different terminations in the form of FAPb1-xAExI3 structures, where AE is Be, Mg or Ca. It is revealed that the (111) surface is more stable, indicating metallic characteristics. The (100) surfaces exhibit a suitable bandgap of around 1.309 and 1.623 eV for PbI5 and PbI6 terminations, respectively. Increases in the bandgaps as a result of Mg- and Ca-doping of the (100) surface were particularly noted in FAPb0.96Ca0.04I3 and FAPb0.8Ca0.2I3 with bandgaps of 1.459 and 1.468 eV, respectively. In the presence of Be, the band gap reduces critically by about 0.315 eV in the FAPb0.95Be0.05I3 structure, while increasing by 0.096 eV in FAPb0.96Be0.04I3. Optimal absorption, high extinction coefficient and light harvesting efficiency were achieved for plain and doped (100) surfaces in the visible and near UV regions. In order to improve the optical properties of the (111)-PbI3 surface in initial visible areas, we suggest calcium-doping in this surface to produce FAPb0.96Ca0.04I3, FAPb0.92Ca0.08I3, and FAPb0.88Ca0.12I3 structures.

Dissociation and removal of alkali and alkaline earth metals from sewage sludge flocs during separate and assisted thermal hydrolysis.

High levels of alkali and alkaline earth metals (AAEM, including K, Na, Ca, and Mg) in sludge needs to be removed in pretreatment process for alleviating adverse effects on subsequent disposal. Theoretically, the liquid environment provided by the pretreatment technology of thermal hydrolysis (TH) is the ideal condition for the dissolution of AAEM. Therefore, this work quantified AAEM removal efficiency of TH and carbonaceous skeleton (CSkel) assisted TH that we previously proposed for sludge dewatering. Then the mechanism of AAEM dissociating from sludge was explored through the new perspective of biological structure evolution and chemical species transformation. The results showed that all of the AAEM in raw sludge was trapped in extracellular polymer substances (EPS) and cells. Only the water-soluble K/Na in EPS could be released by TH to the supernatant, the residual K/Na in EPS was organically linked with humic matters that were generated through the degradation of proteins. Water/NH4Ac-soluble K/Na in cells still stayed inside with a more stable form of HCl-soluble after TH. Fortunately, with the assistance of CSkel, this part of K/Na could be leached out due to organic acids derived from hemicellulose decomposition. In such a case, the removal efficiency of K/Na was elevated to 55.5% and 72.5%, respectively. Unlike K/Na, nearly all the Ca/Mg in EPS were transferred to cell residuals during TH. They were combined with the bio-phosphorus in cell residuals as the form of HCl-soluble Ca/Mg-P precipitates, rather than carbonates, sulfates or other compounds. This precipitation reaction was also moderately suppressed in CSkel-assisted TH with low pH, then 7.7% and 34.1% of Ca/Mg were taken away by filtrate. This means that appropriately raising the reaction temperature and adding CSkel with high hemicellulose/cellulose contents can promote the removal of AAEM in sludge during TH process.