RESUMO
Methane oxidation using molecular oxygen remains a grand challenge in which the obstacle is not only the activation of methane but also the reaction with oxygen, considering the mismatch of the ground spin states. Herein, we report TiO2-supported Pt nanocrystals (Pt/TiO2) with surface Pt-Ti alloyed layers that directly convert methane into oxygenates by using O2 as the oxidant with the assistance of CO. The oxygenate yield reached 749.8 mmol gPt-1 in a H2O aqueous solution over 0.1% Pt/TiO2 under 31 bar of mixed gas (20:5:6 CH4:CO:O2) at 150 °C for 3 h, while the CH3OH selectivity was 62.3%. On the basis of the control experiments and spectroscopic results, we identified the surface Pt-Ti alloy as the active sites. Moreover, CO promoted the dissociation of O2 on the surface of Pt-Ti alloyed layers and the subsequent activation of CH4 to form oxygenated products.
RESUMO
The vast bulk of polystyrene (PS), a major type of plastic polymers, ends up in landfills, which takes up to thousands of years to decompose in nature. Chemical recycling promises to enable lower-energy pathways and minimal environmental impacts compared with traditional incineration and mechanical recycling. Herein, we demonstrated that methanol as a hydrogen supplier assisted the depolymerization of PS (denoted as PS-MAD) into alkylbenzenes over a heterogeneous catalyst composed of Ru nanoparticles on SiO2. PS-MAD achieved a high yield of liquid products which accounted for 93.2â wt % of virgin PS at 280 °C for 6â h with the production rate of 118.1â mmolcarbon gcatal. -1 h-1. The major components were valuable alkylbenzenes (monocyclic aromatics and diphenyl alkanes), the sum of which occupied 84.3â wt % of liquid products. According to mechanistic studies, methanol decomposition dominates the hydrogen supply during PS-MAD, thereby restraining PS aromatization which generates by-products of fused polycyclic arenes and polyphenylenes.
RESUMO
As surrogates of polybrominated diphenyl ethers (PBDEs), new flame retardants (NFRs) include a series of chlorinated and brominated flame retardants. Though the NFRs are thought to induce similar thyroid hormone (TH) disrupting effects as PBDEs, few studies have focused on them. Given the increasing levels of NFRs in the environment, more in depth investigation of the potential TH disrupting effects of NFRs is warranted. This research involved a health survey to collect data and examine the associations between PBDEs, NFRs and TH. 174 school students lived near a petrochemical complex in South China participated in the survey, completing questionnaires and providing blood samples. Thirteen congeners of PBDEs, eight species of NFRs, TH and thyroid-stimulating hormone (TSH) were measured. The median levels of ΣPBDE (sum of thirteen congeners of PBDEs) and ΣNFR (sum of eight species of NFRs) for students were 140 and 240â¯ngâ¯g-1 lipid, respectively. Nonmonotonic relationships were observed between quartile levels of PBDEs, NFRs and corresponding TH. In contrast to ΣPBDE that was positively associated with triidothyrine (T3) level, ΣNFR was not statistically associated with TH. ΣPBDE + NFR (sum of thirteen congeners of PBDEs and eight species of NFRs) was significantly associated with T3 level.
Assuntos
Retardadores de Chama/análise , Éteres Difenil Halogenados/sangue , Hormônios Tireóideos/sangue , Criança , China , Retardadores de Chama/efeitos adversos , Humanos , Bifenil Polibromatos/sangue , Bifenilos Policlorados/sangue , Instituições Acadêmicas , Estudantes , Tireotropina/sangueRESUMO
A rapid and sensitive method for the determination of earthy-musty odorous compounds, 2-methylisoborneol, 2-isopropyl-3-methoxy pyrazine, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, and geosmin, in water samples has been developed. The method was based on coupling a new polyvinylidene fluoride (PVDF) hollow-fiber liquid-phase microextraction system with gas chromatography-mass spectrometry (GC-MS). The PVDF hollow fibers have high porosity and an enhanced solvent compatibility for extraction of the target analytes. Experimental conditions were optimized by investigating the type of extraction solvent, sample pH, sodium chloride concentration, stirring speed, extraction time, and GC-MS conditions. Under optimized conditions, the earthy-musty odorous compounds exhibited good linearity (R>0.995) in the concentration range of 6.2-250ng/L. The repeatability and reproducibility of the method were lower than 6.8% and 9.8%, respectively. The limit of detection and limit of quantification values were lower than 2.0 and 6.2ng/L, respectively. The analysis of different water samples such as tap, pond, rive and waste water indicated minimal matrix effects. Analyte recoveries for real samples spiked at different concentrations were between 84.4% and 117.5%.