Different Degrees Of Crystallinity Research Articles

Insights into the Crystallinity-Dependent Photochemical Productions of Reactive Oxygen Species from Iron Minerals.

Iron minerals are widespread in earth's surface water and soil. Recent studies have revealed that under sunlight irradiation, iron minerals are photoactive on producing reactive oxygen species (ROS), a group of key species in regulating elemental cycling, microbe inactivation, and pollutant degradation. In nature, iron minerals exhibit varying crystallinity under different hydrogeological conditions. While crystallinity is a known key parameter determining the overall activity of iron minerals, the impact of iron mineral crystallinity on photochemical ROS production remains unknown. Here, we assessed the photochemical ROS production from ferrihydrites with different degrees of crystallinity. All examined ferrihydrites demonstrated photoactivity under irradiation, resulting in the generation of hydrogen peroxide (H2O2) and hydroxyl radical (•OH). The photochemical ROS production from ferrihydrites increased with decreasing ferrihydrite crystallinity. The crystallinity-dependent photochemical •OH production was primarily attributed to conduction band reduction reactions, with the reduction of O2 by conduction band electrons being the rate-limiting key process. Conversely, the crystallinity of iron minerals had a negligible influence on photon-to-electron conversion efficiency or surface Fenton-like activity. The difference in ROS productions led to a discrepant degradation efficiency of organic pollutants on iron mineral surfaces. Our study provides valuable insights into the crystallinity-dependent ROS productions from iron minerals in natural systems, emphasizing the significance of iron mineral photochemistry in natural sites with abundant lower-crystallinity iron minerals such as wetland water and surface soils.

Oxidation of cellulose fibers using LPMOs with varying allomorphic substrate preferences, oxidative regioselectivities, and domain structures

Lytic polysaccharide monooxygenases (LPMOs) are excellent candidates for enzymatic functionalization of natural polysaccharides, such as cellulose or chitin, and are gaining relevance in the search for renewable biomaterials. Here, we assessed the cellulose fiber modification potential and catalytic performance of eleven cellulose-active fungal AA9-type LPMOs, including C1-, C4-, and C1/C4-oxidizing LPMOs with and without CBM1 carbohydrate-binding modules, on cellulosic substrates with different degrees of crystallinity and polymer chain arrangement, namely, Cellulose I, Cellulose II, and amorphous cellulose. The potential of LPMOs for cellulose fiber modification varied among the LPMOs and depended primarily on operational stability and substrate binding, and, to some extent, also on regioselectivity and domain structure. While all tested LPMOs were active on natural Cellulose I-type fibers, activity on the Cellulose II allomorph was almost exclusively detected for LPMOs containing a CBM1 and LPMOs with activity on soluble hemicelluloses and cello-oligosaccharides, for example NcAA9C from Neurospora crassa. The single-domain variant of NcAA9C oxidized the cellulose fibers to a higher extent than its CBM-containing natural variant and released less soluble products, indicating a more dispersed oxidation pattern without a CBM. Our findings reveal great functional variation among cellulose-active LPMOs, laying the groundwork for further LPMO-based cellulose engineering.

Design of an UV-C shielded biopolymer based on a poly(lactic acid)/quercetin/magnesium composite

The use of biopolymers like poly(lactic acid) (PLA) doped with natural and harmless active agents in industrial, medical and food packaging applications is of great interest due to the multitude of property enhancements included. External factors, such as UV exposure, can accelerate the degradation process of these biomaterials and cause changes in structural and mechanical properties of medical or industrial devices. In this research, PLA-based composites with different degrees of crystallinity are fabricated using magnesium (Mg) particles and quercetin (Qr) as doping agents, providing new biomaterials with different responses against an UV-C radiation source. Physical surface changes are studied by atomic force microscopy (AFM), goniometry and scanning electron microscopy (SEM). Chemical modifications are evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Thermal response is studied by differential scanning calorimetry (DSC). PLA crystallinity is crucial in the polymer response to UV radiation. Under irradiation Mg particles cause a catalytic effect that enhances the degradation by hydrolysis of PLA chains. However, when Qr is present this effect is inhibited, making the Qr/Mg combination an ideal enrichment to protect the polymer from chemical photooxidation, while improving the surface mechanical properties of the new biocomposite.

Effect of Electrolyte Anions on the Activity of Iridium Oxide Catalysts for Water Electrolysis

Developing environmentally friendly and renewable energy sources is essential due to the environmental and energy security issues caused by traditional combustion of fossil fuel-based energy sources. Therefore, as a clean and sustainable energy carrier, hydrogen has attracted great attention in recent years. In this regard, water electrolysis utilizing renewable energy sources to produce hydrogen is considered one of the most promising technologies. It is believed elucidation of the reaction mechanism of highly active iridium oxides is promising for the further development of cost-efficient PEM water electrolysis catalysts. The properties of the MEA could be affected by many parameters such as the catalysts, operating temperature, and pressure1,2. Another important factor is the cation impurities that can be found in the circulating water, which could severely degrade the MEA performance during the operation of a PEM water electrolyze. However, there are less reports on anion impurities such as SO4 2- and PO4 3-. Therefore, in this study, the relationship between electrolyte anions and OER activity was investigated for IrOx catalysts with different crystal structure. By using operando X-ray absorption spectroscopy (XAS), we investigated the electronic state of Ir and O under operation potential.IrOx with different degree of crystallinity (SA3.5 and SA58) were provided by Tanaka Kikinzoku Kogyo K.K., Chemical & Refining Company and named after their BET surface areas. These two samples were then tested for electrochemical properties in different concentrations of phosphoric acid and perchloric acid, respectively. The electrochemical measurements were performed using a standard three-electrode cell connected to an MPG-205-NUC system (Bio-Logic). The cyclic voltammograms (CV) were scanned from 0.1 V to 1.2 V vs. RHE at 50 mV s-1. The electrochemical activities of the catalysts were subsequently investigated using linear sweep voltammetry (LSV) in the range of 1.1 to 1.7 V vs RHE at 10 mV s−1. operando XAS were collected using a home-made flow-type cell, where Pt wire and RHE worked as counter and reference electrodes, respectively. The catalyst ink was coated onto an Nafion membrane to prepare both the X-ray window and working electrode. The electrolyte was circulated at the flow rate of 100 mL min-1.The catalytic performance of IrOx was investigated at different types and content of electrolyte under H3PO4 and HClO4. Figure 1 shows the CVs of SA3.5 and SA58 under different types and content of electrolyte. In the presence of phosphate anions, SA3.5 showed a tendency to decrease Ir redox between 0.6 and 1.1 V with increasing electrolyte concentration. On the other hand, there were no obvious changes in SA58. It was found that IrOx catalysts have an great effect of specific adsorption of anions and low symmetry of monoclinic phase catalysts (SA 3.5) are more susceptible to anion poisoning. Figure 2 shows the result of examining the poisoning mechanism using soft X-ray XAS. O K-edge results present the formation of µ2-O (O-O) bond at around 528.7 eV, which was previously observed by Nong, H. N. et. al. through operando O-K edge measurements during OER process3. The peak intensity at 528.7 eV of the amorphous samples was in the same order as the OER activities. According to potential dependence change of the pre-edge peak, under the presence of phosphate anions, the hole formation to Ir-O hybrid orbitals was suppressed in SA3.5. This result indicates that the anion adsorbs to the active site, poisoning the catalyst surface and inhibiting the reaction. Acknowledgements This work is based on results obtained from a project (JPNP14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) of Japan. References Zhang, Y.; Zhu, X.; Zhang, G.; Shi, P.; Wang, A.-L.; et al. J. Mater. Chem. A: 2021, 9, 5890-5914.Chen, Z.; Duan, X.; Wei, W.; Wang, S.; Ni, B.-J.; et al. Nano Energy: 2020, 78, 105270.Nong, H. N.; Falling, L. J.; Bergmann, A.; et al. Nature 2020, 587 (7834), 408-413. Figure 1

Investigating the Reaction Mechanism of Iridium Oxides for PEM Water Electrolysis by Operando Soft X-Ray Absorption Spectroscopy

With the increase in fossil energy consumption and the attendant pronounced climate changes, the call for sustainable energy forms has become urgent and has attracted more and more attention.1 Hydrogen (H2), generated by the electricity-derived water electrolysis, is now considered the promising energy carrier for conversion between electricity and chemical energy.2 The most developed water electrolysis technology up to date is the proton-exchange membrane (PEM) water electrolysis, where commercial Pt/C works as the cathodic catalyst for hydrogen evolution reaction (HER) and noble metal-based materials serve as the anodic catalyst for oxygen evolution reaction (OER).3 Considering the sluggish four-electron reaction kinetics of OER and the harsh acidic environment of PEM water electrolysis, the selectivity of high-efficient OER catalysts is narrowed down to Ir-based catalysts because of their superior activity, long-term stability and corrosion resistance against acidic environment.4 However, the scarcity of Ir on earth has impeded the wide application of PEM water electrolysis and has driven the research of cost-efficient OER catalysts. In this study, we thoroughly investigated several amorphous IrOx catalysts with different degree of crystallinity (SA103, SA58, SA14.6 and SA58) and revealed the relation between their structures and OER activities. Besides, BET surface areas, X-ray diffraction (XRD), Transmission electron microscopy (TEM), scanning TEM (STEM), PDF, and XAS were measured to thoroughly understand the catalytic properties.XRD patterns in Figure 1(a) showed that compared with the well-crystallized IrO2, SA58 sample showed slightly broad peak, while the diffraction peaks were much broad of other samples, indicating their amorphous structures. The amorphous structure of IrOx was characterized through atomic pair distribution function (PDF) analyses as shown in Figure 1(b). Different from the typical tetragonal symmetry of crystal IrO2, the combination of orthorhombic symmetry and monoclinic symmetry was found in the amorphous IrOx. Further, OER activities of all samples were investigated in 0.1 M HClO4 and the current density was calculated against the BET surface areas to examine the intrinsic catalytic activity (Figure 1(c)). The crystallized SA58 sample showed the lowest activity, while SA3.5 sample outperformed all other amorphous oxides. From PDF, it was found that the highest OER active SA3.5 sample exhibited the highest monoclinic phase ratio content. The catalytic structure properties were further evidenced by the XAS results. EXAFS results showed different electronic environment of monoclinic phase samples and further fitting results were in good agreement with the PDF analyses. Moreover, O K-edge results showed the formation of µ2-O (O-O) bond at around 528.7 eV, which was previously observed by Nong, H. N. et. al. through operando O-K edge measurements during OER process.5 It was concluded that that the low symmetry of monoclinic phase in amorphous samples resulted in the structure defection, and thus lead to large amount of active electrophilic OI - species, which boosting the OER activity. This finding provided fundamental understanding of the amorphous iridium oxides and could promisingly shed light on the future OER catalyst design. Acknowledgements This work is based on results obtained from a project (JPNP14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) of Japan. References Götz, M.; Lefebvre, J.; Mörs, F.; McDaniel Koch, A.; Graf, F.; Bajohr, S.; Reimert, R.; Kolb, T., Renewable Power-to-Gas: A technological and economic review. Renew. Energy 2016, 85, 1371-1390.Dincer, I.; Acar, C., Review and evaluation of hydrogen production methods for better sustainability. Int. J. Hydrogen Energy 2015, 40 (34), 11094-11111.Carmo, M.; Fritz, D. L.; Merge, J.; Stolten, D., A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 2013, 38 (12), 4901-4934.An, L.; Wei, C.; Lu, M.; Liu, H.; Chen, Y.; Scherer, G. G.; Fisher, A. C.; Xi, P.; Xu, Z. J.; Yan, C.-H., Recent Development of Oxygen Evolution Electrocatalysts in Acidic Environment. Adv. Mater. 2021, 33 (20), 2006328.Nong, H. N.; Falling, L. J.; Bergmann, A.; Klingenhof, M.; Tran, H. P.; Spöri, C.; Mom, R.; Timoshenko, J.; Zichittella, G.; Knop-Gericke, A.; Piccinin, S.; Pérez-Ramírez, J.; Cuenya, B. R.; Schlögl, R.; Strasser, P.; Teschner, D.; Jones, T. E., Key role of chemistry versus bias in electrocatalytic oxygen evolution. Nature 2020, 587 (7834), 408-413. Figure 1

Can Multifunctionality of Bioresorbable BMGs be Tuned by Controlling Crystallinity?

Ca-Mg-Zn bulk metallic glasses (BMGs) are promising biomaterials for orthopaedic applications because when they get reabsorbed, a retrieval surgery is not needed. In this study, Ca-Mg-Zn metallic glasses with different compositions, Ca56.02Mg20.26Zn23.72 and Zn50.72Mg23.44Ca25.84, were fabricated by induction melting followed by copper mould casting. Their degree of crystallinity was modified by annealing, obtaining exemplar specimens of fully amorphous, partially amorphous (i.e., a BMG composite (BMGC)) and fully crystalline alloys. The microstructure, thermodynamic and corrosion performance of these alloys were evaluated as well as their electrochemical behaviour. The results of polarisation tests demonstrate that the corrosion resistance of the Zn-rich alloy is markedly better than the Ca-rich BMG. Corrosion rates of these Ca-and Zn-rich alloys with different degrees of crystallinity illustrate that the corrosion behaviours of alloys strongly depend on their microstructure, which shows a positive correlation between the corrosion current density and the crystallised volume fraction of the alloy. This study aims to shed light on the impact of the amorphicity-to-crystallinity ratio on the multifunctional properties of BMGs/BMGCs, and to assess how feasible it is to fine-tune those properties by controlling the percentage of crystallinity.

Effect of oxygen plasma-treatment on surface functional groups, wettability, and nanotopography features of medically relevant polymers with various crystallinities

The surface properties of polymeric biomaterials play a crucial role in their biocompatibility and performance. This study explores the application of cold oxygen plasma treatment as a versatile technique for surface modification of polymeric materials with different degrees of crystallinity: crystalline high-density polyethylene (HDPE), crystalline-amorphous poly(chloro‑paraxylylene) (parylene C), and amorphous aromatic polyether-based polyurethane (PU). The investigations focus on the generation of surface functional groups and hydrophilicity, as well as nanotopography. X-ray photoelectron spectroscopy (XPS) analysis confirmed the generation of oxygen-containing functional groups, resulting in controlled wettability (water contact angle), while atomic force microscopy (AFM) showed topography modifications in the nanoscale. At the same time, it was revealed that oxygen plasma treatment did not affect the bulk properties (confirmed by TG and XRD). The effects of the same plasma treatment conditions varied significantly among the different polymers studied, depending on their crystallinity. This was discussed in terms of the preferential etching of amorphous regions in the polymeric structures. The findings emphasize the advantages of oxygen plasma treatment for tailoring the surface properties of polymeric biomaterials, highlighting its significance for biomedical applications.

Analysis of the Degree of Crystallinity of Aluminosilicates of the Kaolinite Subgroup According to the IR Spectroscopy Data

The data of X-ray diffraction and IR spectroscopy of synthetic aluminosilicates of the kaolinite subgroup with different degrees of crystallinity are analyzed. The samples are obtained under hydrothermal conditions in alkaline and neutral media with different durations of synthesis. It is shown that as the synthesis time increases a gradual transition of the amorphous phase to the crystalline phase is observed, which is reflected in the IR spectra by the shift of the bands related to the oscillations of the groups in the octahedral and tetrahedral grids. The first band of stretching vibrations of hydroxyl groups at 3628 cm–1 appears after three days of hydrothermal treatment in a neutral medium, and under alkaline conditions with the same duration of treatment, two more bands are observed at 3687 and 3668 cm–1. The detected changes in the IR spectra correspond to the appearance of the characteristic X-ray reflections of halloysite according to the XRD data. Thus, IR spectroscopy can be considered as a method for a qualitative assessment of the degree of crystallinity.

Evaluating the role of magnesium aluminate nano spinel in phase composition, meso-porosity, compressive strength, and drying shrinkage of alkali-activated slag

The effect of nano magnesium aluminate (MA) spinel on the performance of blast-furnace slag with low NaOH content (3 wt%) was explored for the first time in the present work. Two different temperatures (500 and 800 °C) were applied to prepare nano spinel with different degrees of crystallinity. The impact of nano MA spinel crystallinity and content on phase composition, microstructure, compressive strength, meso-porosity, and drying shrinkage of alkali-activated slag (AAS) was evaluated. The results showed that nano spinel prepared at 500 °C (MA500) reduced the drying shrinkage and increased the compressive strength of AAS significantly, while MA800 showed a lower effect. The activated mixtures containing 0.5 wt% nano spinel demonstrated the highest performance regardless of nano spinel type. Adding nano spinel induced the formation of a hydrotalcite phase and enhanced the incorporation of Al inside calcium silicate hydrate, resulting in a substantial improvement in the performance of AAS. Nano spinel achieved the concept of “sustainability”, which strongly contributes to producing high-performance materials with low carbon footprint by utilizing low sodium hydroxide content.

Authigenic Mineral Formation in Aquifers near the Uranium Sludge Storage Facility of Chepetsky Mechanical Plant during the Formation of a Biogeochemical Barrier in a Laboratory and Field Experiment

In this work, authigenic microbial mineral formation in groundwater near the uranium sludge storage at SC Chepetsky Mechanical Plant (ChMP) (Glazov, Russia) was analysed in field and laboratory experiments using thermodynamic modelling when the microbial community was activated by a mixture of acetate, glucose and whey. It was found that the mineral basis of the barrier consisted of aggregated soil particles with freshly deposited phases of carbonate and sulphide minerals of different degrees of crystallinity. An important factor in the formation of calcium phases is microbial denitrification, which is accompanied by an increase in pH values of the medium. The main factors of uranium immobilisation in the biogeochemical barrier were revealed, including its reduction to insoluble forms of uranium dioxide, adsorption on ferrous and sulphide-ferrous minerals, as well as the formation of phosphate phases through the addition of phosphorus-containing whey and co-precipitation or co-crystallisation in calcite phases.

The Colíder Paleoproterozoic felsic volcanism: New insights into stratigraphy and petrogenesis in the southern Amazonian Craton

The eastern side of Alta Floresta Mineral Province (AFMP) (União do Norte region) comprises an effusive/subvolcanic phase, explosive phase, and epiclastic rocks. The effusive/subvolcanic phase comprises massive porphyritic rhyolite with different degrees of crystallinity, porphyritic rhyolite with flow structure, and microcrystalline rhyolite. The explosive phase is characterized by welded lapilli tuff, lapilli tuff with flow structure, stratified lapilli tuff, and tuff with accretionary lapilli. Sandstones and siltstones characterize epiclastic rocks. There are porphyritic rhyolite dikes that cut the volcanic sequence. The rocks of the Colíder Group are rhyolites (>70 % SiO2) with calcic-alkaline to alkaline-calcic affinity. A rhyolitic rock is predominantly ferroan and metaluminous, while a pyroclastic rock is predominantly magnesian to ferroan and meta- to peraluminous in composition. The rocks have a high LREE content, and slight fractionation of HREE suggests they have hybrid geochemical characteristics of high potassium calc-alkaline, shoshonitic, and suggestive affinities of A-type magmas, probably produced in a post-collisional orogenic environment. These rocks have a relatively high level of Ba and Rb and a negative anomaly for Sr, P, Nb, Ta, and Ti, suggesting an intra-plate mantle source with contributions from a metasomatized mantle edge. The rocks do not have adakitic characteristics nor fertility for Cu-Au (Sr/Y < 1.9 and LaN/YbN < 38.0) as in other regions of the AFMP. The welded lapilli tuff rocks show U-Pb age of 1838 ± 17 Ma and 1817 ± 2 Ma and are the older explosive phases. The effusive/subvolcanic phase has U-Pb ages of 1800 ± 3 Ma and 1792 ± 3 Ma obtained in the massive porphyritic rhyolite. The age interval of approximately 46 Ma (1838–1792 Ma) suggests the presence of two or more volcanic cycles or distinct volcanic events. Based on the interpretation of volcanic and epiclastic deposits and remote sensing products, the paleoenvironmental reconstruction includes subaerial with effusive/subvolcanic and explosive stages in a probable eroded volcanic caldera system with epiclastic rocks from a fluvial depositional system. This volcanic scenario provides more information about the Colíder–Teles Pires volcano-plutonic event, uniquely mapped in AFMP, and offers new insights into the tectonic frame of the Amazonian craton.

Correlation between microstructure, thermodynamic stability, and electric work of tin sulfide active anode materials for Li-ion batteries

The precipitation and hydrothermal synthesis methods were utilized to prepare phase pure SnS and SnS2 materials with different degrees of crystallinity, particle sizes, and morphology. The crystallite size, morphology, and phase composition of the as-synthesized materials were determined. The limiting molar enthalpies of solution of sulfur, the as-prepared materials, and that of a commercially available, macro-crystalline SnS2 in tin were established by drop calorimetry and subsequently, the enthalpies of formation were derived. The obtained enthalpies of formation of SnS range from − 48.8 to − 52.8 kJ mol−1 of atoms and for SnS2 from − 50.2–51.0 kJ mol−1 of atoms, which aligns well with existing literature results. For SnS, a trend towards less exothermic enthalpy of formation with decreasing crystallite size was observed. The obtained data of the as-prepared SnS2 materials did not clearly show such a trend and were further compared to that from commercially available, macro-crystalline SnS2. The obtained enthalpy of formation was even less exothermic compared to as-prepared SnS2 materials. After ball-milling of macro-crystalline SnS2 its formation enthalpy was the most exothermic of all SnS2 samples. An explanation of these unexpected results is given based on the energetics of crystallite size versus particle shape and size. Furthermore, the as synthesized and purchased materials were subjected to electrochemical discharge tests, and from the resulting voltage (as a function of x in LixSnS and LixSnS2) curves, the electrochemical work of the lithiation reactions was derived.

The use of plant-derived polymeric coating to modulate iron corrosion for bone scaffold applications

The present work reports, the use of plant-derived thermoset coating to control iron (Fe) corrosion in simulated body fluid for bone scaffolds applications by varying the curing temperature of the plant-derived polymers, namely poly[xylitol-(1,12-dodecanedioate)] (PXDD). The physicochemical characterizations of the scaffolds indicate that a different degree of crystallinity has been observed as P120Fe (PXDD cured at 120 °C and then coated on Fe) shows a more crystalline structure while P140Fe (PXDD cured at 140 °C) has a more amorphous nature. The amorphous form of P140Fe leads to expedited corrosion compared to P120Fe and pure Fe owing to the hydrophilic property and the higher hydrolysis effect in the former. The plant-derived PXDD could be a promising coating material to control the corrosion of Fe-based scaffolds for temporary bone implant applications.

Highly Strain-Stable Intrinsically Stretchable Olfactory Sensors for Imperceptible Health Monitoring.

Intrinsically stretchable gas sensors possess outstanding advantages in seamless conformability and high-comfort wearability for real-time detection toward skin/respiration gases, making them promising candidates for health monitoring and non-invasive disease diagnosis and therapy. However, the strain-induced deformation of the sensitive semiconductor layers possibly causes the sensing signal drift, resulting in failure in achievement of the reliable gas detection. Herein, a surprising result that the stretchable organic polymers present a universal strain-insensitive gas sensing property is shown. All the stretchable polymers with different degrees of crystallinity, including indacenodithiophene-benzothiadiazole (PIDTBT), diketo-pyrrolo-pyrrole bithiophene thienothiophene (DPPT-TT) and poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiad-iazolo [3,4-c] pyridine] (PCDTPT), show almost unchanged gas response signals in the different stretching states. This outstanding advantage enables the intrinsically stretchable devices to imperceptibly adhere on human skin and well conform to the versatile deformations such as bending, twisting, and stretching, with the highly strain-stable gas sensing property. The intrinsically stretchable PIDTBT sensor also demonstrates the excellent selectivity toward the skin-emitted trimethylamine (TMA) gas, with a theoretical limit of detection as low as 0.3ppb. The work provides new insights into the preparation of the reliable skin-like gas sensors and highlights the potential applications in the real-time detection of skin gas and respiration gas for non-invasive medical treatment and disease diagnosis.

Cleaner production of iron-coated quartz sand composites for efficient phosphorus adsorption in sanitary wastewater: A design of experiments (DoE) approach

Phosphorus (P) adsorption and recovery from sanitary wastewater is a promising route to produce more sustainable fertilizers. Multivariate Design of Experiments (DoE) techniques were used to develop a cleaner process to produce Fe-coated quartz sand composites with applications in Phosphorus (P) adsorption from sanitary effluents. Nine different process parameters were investigated and correlations between process inputs and physicochemical characteristics of adsorbents were elucidated. It was found that Goethite and Magnetite phases with different degrees of crystallinity were obtained depending on the conditions applied during the synthesis by coprecipitation. Statistical models fitted to an experimental multivariate database were used to predict the best conditions for synthesizing an efficient P adsorbent. In addition, a zero-waste process for the production of the adsorbents is reported. The best adsorbent produced, an aqueous suspension containing particles of a SiO2@FeOOH composite, exhibited a P (KH2PO4) adsorption capacity of 12.4 mg P/g (C0 = 10 mg P/L, pH 6.0) and robust performance when applied in simulated sanitary effluent, reaching 97% of P removal efficiency (C0 = 5 mg P/L). Considering the value of the green star area index (GSAI), the optimized method (suspension) was 65% green, reaching the maximum score for four of the ten principles involved, denoting the greenness of the proposed method. The optimized adsorbent has appropriate characteristics to be applied in sanitary effluent treatment processes for capturing and recovering residual P, contributing to a more sustainable management of natural resources.

Influence of crystallization on the shape memory effect of poly (lactic acid)

The objective of this study is to investigate the influence of crystallization on the shape memory effect (SME) of poly (lactic acid) (PLA). Different thermal treatment times were applied to the PLA to obtain different degrees of crystallinity. Additionally, a PLA sample was cooled rapidly to obtain an amorphous PLA. The characterization techniques used in this study were Fourier transform infrared spectroscopy, x-ray diffraction, Dynamic Mechanical Analysis, the differential scanning calorimetry, optical microscopy, and the SME was evaluated by fold-deploy and torsion modes. Results show that crystallization positively affected the SME, both in shape fixity and shape recovery. Different crystallization times provided different degrees of crystallinity, and the SME gradually increased with increasing crystallinity. Additionally, it was found that the SME of PLA is higher in water. The study concludes that the crystallization process plays a crucial role in the SME of PLA, and this work contributes to the understanding of the relationship between crystallization and the SME of PLA, which can contribute to the development of new technologies and applications for shape memory polymers.

Fe(II)-Catalyzed Transformation of Ferrihydrite with Different Degrees of Crystallinity.

Natural occurring ferrihydrite (Fh) nanoparticles have varying degrees of crystallinity, but how Fh crystallinity affects its transformation behavior remains elusive. Here, we investigated the Fe(II)-catalyzed transformation of Fh with different degrees of crystallinity (i.e., Fh-2h, Fh-12h, and Fh-85C). X-ray diffraction patterns of Fh-2h, Fh-12h, and Fh-85C exhibited two, five, and six diffraction peaks, respectively, indicating the order of crystallinity: Fh-2h < Fh-12h < Fh-85C. Fh with the lower crystallinity has a higher redox potential, corresponding to the faster Fe(II)-Fh interfacial electron transfer and Fe(III)labile production. With the increase of initial Fe(II) concentration ([Fe(II)aq]int.) from 0.2 to 5.0 mM, the transformation pathways of Fh-2h and Fh-12h change from Fh → lepidocrocite (Lp) → goethite (Gt) to Fh → Gt, but that of Fh-85C switches from Fh → Gt to Fh → magnetite (Mt). The changes are rationalized using a computational model that quantitatively describes the relationship between the free energies of formation for starting Fh and nucleation barriers of competing product phases. Gt particles from the Fh-2h transformation exhibit a broader width distribution than those from Fh-12h and Fh-85C. Uncommon hexagonal Mt nanoplates are formed from the Fh-85C transformation at [Fe(II)aq]int.= 5.0 mM. The findings are crucial to comprehensively understand the environmental behavior of Fh and other associated elements.

Dissolution of aluminum hydroxide to provide Al and to neutralize acidity for the removal and recovery of fluoride through cryolite crystallization

Dissolution of aluminum hydroxide (Al(OH)3(s)) was investigated for providing Al and at the same time neutralizing the acidity generated in the recovery of fluoride through the crystallization of cryolite. The alkalinity provided by the dissolution of Al(OH)3(s) combined with Na2CO3 reduces the total treatment cost for fluoride recovery by 45%, compared to when other aluminum salts were used. In this study, two types of aluminum hydroxide having different degrees of crystallinity of 61.53% and 25.57%, denoted as crystalline Al(OH)3(s) (CAH) and amorphous Al(OH)3(s) (AAH), respectively, were investigated. The results showed that the dissolution of AAH was very efficient but an excess amount of AAH adsorbed the freshly formed AlFx3−x complexes, impairing the purity of cryolite. On the other hand, the dissolution of the CAH was mostly dependent on the time, the Al dosage, and the initial pH of the solution. Upon reaching equilibrium, the dissolved Al to the initial F molar ratio reached 2/6. With the mixed volume ratio of 1:1 between the raw HF solution and the HF solution being equilibrated with CAH initially, the removal of F reached 96% and the cryolite formation was positively confirmed based on the XRD analysis of the resulting solid.

Cobalt Phosphide Nanoparticles Synthesized by Solvothermal Phosphidization of Metal-Organic Frameworks for Electrocatalytic Oxygen Evolution

Active and stable electrocatalysts for oxygen evolution reaction (OER) are crucial in the widespread application of water electrolyzers. Cobalt phosphide nanoparticles (Co-P) with different degrees of crystallinity are synthesized via solvothermal phosphidization of Co metal-organic frameworks and P4 using different solvents. The Co-P can be converted to active OER electrocatalysts in 1 M KOH, with the most active reaching 10 mA cm-2 OER current densities at 270 mV overpotential. The OER intermediate adsorption energy is tuned by the electron interactions in the crystalline/amorphous heterostructured Co-P, which show the highest intrinsic OER activity. After the long-term OER in base, surface phosphides are converted to (oxy)hydroxides that are the active species towards OER.

Amorphous RuCoP Ultrafine Nanoparticles Supported on Carbon as Efficient Catalysts for Hydrogenation of Adipic Acid to 1,6-Hexanediol.

As an important raw material for organic synthesis, the 1,6-hexanediol (HDOL) is synthesized by the complicated two-step process traditionally. The hydrogenation of adipic acid (AA) is a potential way to prepare 1,6-hexanediol. At present, amorphous RuMP (M: Co, Ni, Fe, etc.)-based alloys with low Ru content were developed by co-precipitation as the efficient catalysts for converting AA to HDOL via hydrogenation. Among these RuMP catalysts, RuCoP alloys exhibited the highest selectivity and yield to HDOL owing to the electronic effect. The selectivity and yield of HDOL for the optimized RuCoP/C sample was achieved to 80% and 64%, respectively, at 65 bar and 220 °C. A series of RuCoP alloys with different degrees of crystallinity and particle sizes were prepared to investigate the effect of morphology and structure on its catalytic performance. The results indicated that the high catalytic activity of RuCoP/C resulted from its rich active sites due to its amorphous phase and small particle size.