Construction of three-dimensional reduced graphene oxide wrapped nZVI doped with Al2O3 as the ternary Fenton-like catalyst: Optimization, characterization and catalytic mechanism.

The rational design and synthesis of novel nanocomposites as effective heterogeneous catalysts is meaningful for the advances in Fenton-like technology. Herein, multiple variants of three-dimensional reduced graphene oxide wrapped nZVI doped with Al2O3 (3D-RGO@nZVI/Al2O3) were prepared by three different self-assembly methods. The composites were characterized by field emission scanning electron microscopy, nitrogen adsorption/desorption isotherms, Raman spectrum analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. A series of experiments on chloramphenicol degradation at different pH values were employed to evaluate the catalytic properties of the prepared catalysts. With the systematical investigation of their morphologies, chemical components and catalytic performance, the optimal 3D-RGO@nZVI/Al2O3 catalyst was synthesized, which was favorable for inducing the Fenton-like reaction by activation of dissolved oxygen (DO) within a wide pH range. The anchored nZVI particles were the main active sites for catalytic oxidation, and doped Al3+ played a major role in buffering the pH of CAP solution. Electron spin resonance spectroscopy revealed the existence of the superoxide radicals (·O2-) and singlet oxygen (1O2), which provides a new insight into the reaction mechanism of reactive oxygen species in the Fenton-like system. This work is an essential effort to explore the promoting effect of synthesis methods on the catalytic behavior of catalysts, and to further study the Fenton-like reaction triggered by DO activation.

Spectrum of PAH gene mutations and genotype-phenotype correlation in patients with phenylalanine hydroxylase deficiency from Shanxi province.

BACKGROUND: Phenylalanine hydroxylase deficiency (PAHD) is an autosomal recessive inborn error that affects phenylalanine (Phe) metabolism. It has a complex phenotype with many variants and genotypes among different populations. Shanxi province is a high-prevalence area of PAHD in China. METHODS: In this study, eighty-nine PAHD patients were subjected to genetic testing using Sanger sequencing, followed by multiplex ligation-dependent probe amplification analysis (MLPA). Allelic and genotypic phenotype values (APV and GPV, respectively) were used for genotype-based phenotypic prediction. RESULTS: Fifty-one types of variants, including three novel forms, were identified. The predominant variant was p.R243Q (22.09%), followed by p.R53H (10.47%), p.EX6-96A > G (9.30%), p.V399V (5.23%) and p.R413P (3.49%). Notably, mild hyperphenylalaninemia (MHP) has a high prevalence in this region (up to 45.76%), and the variant p.R53H was solely observed in patients of MHP. According to the genotype-phenotype prediction, the APV/GPV system was well correlated with the metabolic phenotype of most PAHD patients. CONCLUSION: We have systematically constructed the mutational and phenotypic spectrum of PAH in Shanxi province. Hence, this study will help to further understand the genotype-phenotype associations in PAHD patients, and it may offer more reliable genetic counseling and management.

Nanoscale Fe0/Cu0 bimetallic catalysts for Fenton-like oxidation of the mixture of nuclear-grade cationic and anionic exchange resins.

Spent resins generated from the nuclear industrial processes are still difficult to be treated and disposed. Fenton-like processes have great application potential in the treatment of spent resins, but the Fenton reaction mechanisms and resin degradation pathways remain challenging. In this study, nanoscale Fe0/Cu0 bimetallic catalysts were prepared and characterized for the Fenton-like degradation of the mixture of cationic and anionic resins. High catalytic property of Fe0/Cu0 bimetallic nanoparticles activated by H2O2 was evaluated, according to the effects of various nanoparticles, temperature, catalyst amount, H2O2 concentration and the mixing ratio of cationic and anionic resins. Combined the shape and color changes of mixed resins with the experimental and calculated characterization results, different degradation difficulty of cationic and anionic resins and their degradation mechanisms were studied. According to the density functional theory calculations of the optimized resin molecules with the Fe0/Cu0 catalyst, the mechanisms of Fenton-like reactions and the degradation of mixed resins through the synergistic effect of Fe and Cu species were proposed. The comprehensive Fenton-like reactions and degradation mechanisms provide new insights to advance the treatment of spent resins and organic polymers by Fenton-like processes.

Enhanced heterogeneous Fenton-like degradation of nuclear-grade cationic exchange resin by nanoscale zero-valent iron: experiments and DFT calculations.

Nanoscale zero-valent iron (nZVI) was prepared and used as a heterogeneous Fenton-like catalyst for the degradation of nuclear-grade cationic exchange resin. The properties of nZVI before and after reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface area analysis. The results showed that nZVI-H2O2 system exhibited the enhanced degradation of cationic resins, compared with Fe2+-H2O2, Cu0-H2O2, and Fe0/Cu0-H2O2 systems. The effects of initial temperature, nZVI dose, and H2O2 concentration were studied, and the higher temperature and nZVI dose with relatively low H2O2 concentration brought faster degradation rate. The degradation of cationic resins followed the pseudo-first-order kinetics with the apparent activation energy of 53.29 kJ/mol. According to the experimental and calculated infrared and UV-visible spectra, the carbon skeleton of cationic resins was broken with the detachment of benzene ring and the desulfonation of resin polymer by hydroxyl radicals (•OH), generating long-chain alkenes. These intermediates were further oxidized through the hydroxyl substitution, hydrogen abstraction, ring cleavage, or carbonylation reactions, finally forming carboxylic acids remained in solution.