Shape-Preserved CoFeNi-MOF/NF Exhibiting Superior Performance for Overall Water Splitting across Alkaline and Neutral Conditions.

This study reported a multi-functional Co0.45Fe0.45Ni0.9-MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape-preserving two-step hydrothermal method. The resulting bowknot flake structure on NF enhanced the exposure of active sites, fostering a superior electrocatalytic surface, and the synergistic effect between Co, Fe, and Ni enhanced the catalytic activity of the active site. In an alkaline environment, the catalyst exhibited impressive overpotentials of 244 mV and 287 mV at current densities of 50 mA cm-2 and 100 mA cm-2, respectively. Transitioning to a neutral environment, an overpotential of 505 mV at a current density of 10 mA cm-2 was achieved with the same catalyst, showing a superior property compared to similar catalysts. Furthermore, it was demonstrated that Co0.45Fe0.45Ni0.9-MOF/NF shows versatility as a bifunctional catalyst, excelling in both OER and HER, as well as overall water splitting. The innovative shape-preserving synthesis method presented in this study offers a facile method to develop an efficient electrocatalyst for OER under both alkaline and neutral conditions, which makes it a promising catalyst for hydrogen production by water splitting.

Selective formation of high-valent iron in Fenton-like system for emerging contaminants degradation under near-neutral and high-salt conditions.

In view of the near-neutral and high-salt conditions, the Fenton technology with hydroxyl radicals (HO•) as the main reactive species is difficult to satisfy the removal of trace emerging contaminants (ECs) in pharmaceutical sewage. Here, a layered double hydroxide FeZn-LDH was prepared, and the selective formation of ≡Fe(IV)=O in Fenton-like system was accomplished by the chemical environment regulation of the iron sites and the pH control of the microregion. The introduced zinc can increase the length of Fe-O bond in the FeZn-LDH shell layer by 0.22 Å compared to that in Fe2O3, which was conducive to the oxygen transfer process between ≡Fe(III) and H2O2, resulting in the ≡Fe(IV)=O formation. Besides, the amphoteric hydroxide Zn(OH)2 can regulate the pH of the FeZn-LDH surface microregion, maintaining reaction pH at around 6.5-7.5, which could avoid the quenching of ≡Fe(IV)=O by H+. On the other hand, owing to the anti-interference of ≡Fe(IV)=O and the near-zero Zeta potential on the FeZn-LDH surface, the trace ECs can also be effectively degraded under high-salt conditions. Consequently, the process of ≡Fe(IV)=O generation in FeZn-LDH system can satisfy the efficient removal of ECs under near-neutral and high-salt conditions.

Degradation of polyvinyl alcohol (PVA) in neutral conditions based on copper-manganese bimetallic catalyst.

There have been many studies on the degradation of polyvinyl alcohol (PVA) by the Fenton-like method, but the narrow acid-base (pH) range, poor degradation effect, and time-consuming of the Fenton-like method limit its development. Therefore, to improve the shortcomings of the Fenton-like method, the study aimed to synthesize copper-manganese bimetal oxide loaded catalysts (MnCuO@γ-Al2O3) through the impregnation calcination method, and its potential to activate hydrogen peroxide (H2O2) for the degradation of PVA was evaluated. The X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer Emmett Teller (BET), energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) characterizations revealed the chemical composition, structure and morphology of the prepared MnCuO@γ-Al2O3, furthermore the synergistic mechanism was proposed. Results indicated that copper and manganese could successfully attach to γ-Al2O3 and reduce the specific surface area of γ-Al2O3, promoting the transformation of multivalent metals and the generation of oxygen vacancies. In addition, comparative experiments demonstrated that the PVA removal efficiency was significantly improved at the catalyst calcination temperature of 500 °C, reaction temperature of 70 °C, H2O2 dosage of 125 [Formula: see text], and catalyst dosage of 625 [Formula: see text] and more than 96% of PVA was removed within 20 min in neutral conditions. Lastly, four catalyst cycle degradation experiments of PVA were carried out, and the degradation effect could reach more than 96% in a certain time.

Internal Electric Field Built on Heterointerface of H2TiO3/H4Ti5O12 Hybrid Enabling Promoted Li Extraction Performance.

With potentially high lithium (Li) exchange capacity and long cycle ability, Ti-based oxides of H2TiO3 and H4Ti5O12 are considered to be promising Li-ion sieve (LIS) materials applied for Li resource extraction in the liquid phase. However, the LISs usually demonstrate unsatisfactory Li exchange performance under the approximately neutral condition without the strong impetus derived from the rapid combination between OH- in the surrounding solution and H+ ionized from LIS. Herein, a hybrid of H2TiO3/H4Ti5O12 with rich phase boundaries is constructed via a facile one-step solid-state method. Owing to the different Fermi energy levels of the two phases, the electrons are transferred at the phase interface between H2TiO3 and H4Ti5O12, developing an internal electric field (IEF). The built IEF provides an extra driving force to boost the solid-phase Li+ transport, hence enhancing the Li extraction kinetics. Threrfore, the H2TiO3/H4Ti5O12 hybrid exhibits outstanding Li exchange performance of 42.43 and 20.50 mg g-1 under alkaline and neutral conditions, corresponding to the hightest Li extraction rate of 5.30 and 2.05 mg g-1 h-1 reported so far. Our work offers an innovative strategy to promote the Li exchange performance of LIS especially under neutral conditions.

Selective Removal of Emerging Organic Contaminants from Water Using Electrogenerated Fe(IV) and Fe(V) under Near-Neutral Conditions.

Fe(IV) and Fe(V) are promising oxidants for the selective removal of emerging organic contaminants (EOCs) from water under near-neutral conditions. The Fe(III)-assisted electrochemical oxidation system with a BDD anode (Fe(III)-EOS-BDD system) has been employed to generate Fe(VI), while the generation and contributions of Fe(IV) and Fe(V) have been largely ignored. Thus, we examined the feasibility and involved mechanisms of the selective degradation of EOCs in the Fe(III)-EOS-BDD system under near-neutral conditions. It was found that Fe(III) application selectively accelerated the electro-oxidation of phenolic and sulfonamide organics and made the oxidation system be resistant to interference from Cl-, HCO3-, and humic acid. Several lines of evidence indicated that EOCs were decomposed via direct electron-transfer process on the BDD anode and by Fe(IV) and Fe(V) but not Fe(VI), besides HO•. Fe(VI) was not generated until the exhaustion of EOCs. Furthermore, the overall contributions of Fe(IV) and Fe(V) to the oxidation of phenolic and sulfonamide organics were over 45%. Our results also revealed that Fe(III) was oxidized primarily by HO• to Fe(IV) and Fe(V) in the Fe(III)-EOS-BDD system. This study advances the understanding of the roles of Fe(IV) and Fe(V) in the Fe(III)-EOS-BDD system and provides an alternative for utilizing Fe(IV) and Fe(V) under near-neutral conditions.

Selective detection of glutathione by flower-like NiV2O6 with only peroxidase-like activity at neutral pH.

In view of the broad application prospect of peroxidase-like nanozymes in biomedical analysis, it is of great significance to eliminate the interference of their oxidase-like activity and enable them to work under neutral conditions. Herein, flower-like NiV2O6 was synthesized and their enzyme-mimicking activity was investigated. Through the regulation of pH, NiV2O6 nanozyme showed only peroxidase-like activity but not oxidase-like activity under neutral conditions, which could catalyze the oxidation of colorless 3,3',5,5'-tetramethylbenzidine into its blue product in the presence of H2O2. Furthermore, based on the competitive effect of glutathione (GSH) on the catalytic activity of nanozymes, a semi-quantitative/quantitative colorimetric assay was established for GSH detection by using peroxidase-like NiV2O6. The assay exhibited a good linear relationship in GSH concentration ranging from 3-100 µmol L-1, with a detection limit of 0.89 µmol L-1. Moreover, in the presence of formaldehyde as masking agent, this method showed satisfactory specificity for GSH under the interference of a variety of interfering substances and even biothiols. Concerning the practical application, the system was applied to monitor GSH level in fetal bovine serum, human serum and SiHa cells. Satisfyingly, the obtained results were consistent well with those of Ultra performance liquid chromatography (UPLC) and assay kit, indicating the constructed assay has great potential in clinical application.

Interaction of Protein Isolate with Anthocyanin Extracted from Black Soybean and Its Effect on the Anthocyanin Stability.

The interactions between black soybean protein isolate (B-SPI) and cyanidin 3-O-glucoside (C3G), anthocyanin extracted from black soybean coat was investigated under neutral conditions. The fluorescence spectra showed that C3G had fluorescence quenching effects on B-SPI. Thermodynamic parameters showed that ∆G < 0, which demonstrated that the binding was a spontaneous reaction. Since ΔH > 0 and ΔS > 0, the interactions between C3G and B-SPI was mainly hydrophobic interactions. Fourier infrared spectroscopy results suggested that the contents of α-helix and ß-sheet structure showed an increasing trend, whereas the ß-angle content displayed a decreasing trend. The degradation of C3G followed first-order kinetics at 85 °C and 100 °C. After the interactions with B-SPI, the degradation rate constant was decreased and the half-life of C3G was prolonged from 70.25 ± 0.90 min to 175.64 ± 38.04 min at 85 °C, from 62.68 ± 1.1 min to 72.51 ± 2.5 min at 100 °C (p < 0.05). The results indicated that the interactions of B-SPI and C3G improved the thermal stability of C3G under heating conditions.

Laccase isoform diversity in basidiomycete Lentinus strigosus 1566: Potential for phenylpropanoid polymerization.

Three laccase isoforms with different physicochemical properties could be purified from culture liquid of basidiomycete Lentinus strigosus 1566 obtained during submerged cultivation. The purified laccases possessed individual selectivity in relation to different phenolic compounds. Laccases I, II, and III (59, 65, and 61 kDa respectively) were more active in acidic conditions at around 70 °C. However, in contrast to laccases I and II, laccase III retained its activity (8-30%) and stability during at least one week of incubation at neutral conditions that allows its biotechnological application carried out at neutral environment. The activation phenomena for some of the purified laccases from L. strigosus 1566 during incubation at high temperature, different pH, and sulfates is shown and discussed. According to MALDI-TOF analysis, laccases I and II are most closely related to the laccase of Panus rudis (AAR13230). Transformation of phenylpropanoids by the predominant laccases of L. strigosus 1566 to different polymers was demonstrated, indicating a great potential for producing novel pharmaceutical valuable analogues of lignans, stilbenes, flavonoids, and etc.. The studied laccases, which are products of the same strain, can become a convenient model for further studies of the structural mechanisms of the shift of T-/pH-optima, activation, and T-/pH-stability.

Correlation between pH and molar iron/ligand ratio during ciprofloxacin degradation by photo-Fenton process: Identification of the main transformation products.

Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe2+, Fe3+ and Fe3+-citrate and Fe3+-oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C17H19FN3O4, m/z 348; C17H21FN3O5, m/z 366; and C13H12FN2O3, m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C17H21FN3O5, m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions.

Anchoring CoO Domains on CoSe2 Nanobelts as Bifunctional Electrocatalysts for Overall Water Splitting in Neutral Media.

A facile in situ partial surface-oxidation strategy to integrate CoO domains with CoSe2 nanobelts on Ti mesh (denoted as CoO/CoSe2) via direct calcination of CoSe2-diethylenetriamine precursors is reported. The resulted self-supported CoO/CoSe2 exhibits an outstanding activity and stability in neutral media toward both hydrogen evolution reaction and oxygen evolution reaction.

Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes.

Herein, we report an unprecedented regioselective and entirely atom-economic cobalt(III)-catalyzed method for the non-annulative, intermolecular carboamination of alkenes. The methodology enables the direct synthesis of unnatural amino acid derivatives and proceeds under redox-neutral conditions with a completely regioselective C-C bond and C-N bond formation. Furthermore, this reaction exemplifies the inherently different mechanistic behavior of the Cp*CoIII catalyst and its Cp*RhIII counterpart, especially towards ß-H-elimination.