Search

The restriction of sulfur content in fuels has become increasingly stringent as a result of the growing environmental concerns. Although several MOF-derived materials like POM@MOF composites have shown the ability to catalyze oxidative desulfurization (ODS), their catalytic activities inevitably obstructed by the encapsulated catalytic sites like POM due to the blockage of cavities. Therefore, MOFs with intrinsic and accessible catalytic sites are highly desirable for their applications in ultradeep ODS. Herein, four representative Zr-based MOFs (Zr-MOFs), namely, UiO-66, UiO-67, NU-1000, and MOF-808, were assessed for catalytic ODS. These MOFs were confirmed that they have peroxidase-like activity and can catalyze ODS with H 2 O 2 as oxidant. Among them, MOF-808 showed the highest catalytic activity and it can fully desulfurize dibenzothiophene (DBT) in a model gasoline with a S concentration of 1000 ppm under 40 °C within 5 min. An extremely low apparent Arrhenius activation energy (22.0 KJ·mol -1 ) and an extraordinarily high TOF value (42.7 h -1 ) were obtained, ranking MOF-808 among the best catalysts for the catalytic DBT oxidation. Further studies confirmed that the excellent catalytic activity is mainly responsible for the high concentration of the accessible Zr-OH(H 2 O) catalytic sites decorated in MOF-808. The superoxide radicals ( • O 2 - ) and hydroxyl radicals ( • OH) were identified and were proved to involve in the DBT oxidation. Besides, the effects of Brönsted and lewis acidity to the catalytic efficiency were also discussed. Based on the experimental results, a plausible mechanism concerning on Zr-OH(H 2 O) groups promoting the H 2 O 2 decomposion in to both • O 2 - and • OH was first proposed. Moreover, MOF-808 can be facilely reused for at least eight runs without significant loss of its catalytic activity. By the integration of facile synthesis, high catalytic efficiency, and good stability, MOF-808 thus represents a new benchmark catalyst for catalytic oxidative desulfurization.

The composition, distribution, and degradation of chromophoric dissolved organic matter (CDOM) in the lower reach and estuary of the Minjiang River were analyzed using fluorescence excitation-emission matrices-parallel factor analysis (EEMs-PARAFAC) and microbial and photochemical degradation experiments. The results show that there are three types of fluorescence components in the study area:humic-like, tyrosine-like, and tryptophan-like. The humic-like components are the main components in the river zone, while the protein-like components become dominant with increasing salinity in the estuary. The change of the CDOM abundance shows a notable spatial distribution pattern. The absorption coefficient a (280) of CDOM is lower in the river, increases after entering the urban area, shows a decreasing trend in the suburbs, and rapidly declines in the estuary. A conservative estimate of the contribution of the Fuzhou urban area to the CDOM of the Minjiang River is 8%. The a (280) in the river is susceptible to microbial and photochemical degradation and the degradation percentages are (28±8)% and (44±7)%, respectively. The bioavailability and photochemical reactivity of a (280) are much higher in the river than in the estuary. The humic-like, tyrosine-like, and tryptophan-like components show a higher photochemical reactivity in the river, with degradation percentages of (75±0.5)%, (58±21)%, and (73±3)%, respectively. The fluorescent components are not labile with respect to microbial degradation and humic-like components are accumulated after 28 days of microbial culture.