A gate-opening controlled metal-organic framework for selective solid-phase microextraction of aldehydes from exhaled breath of lung cancer patients.

A stainless steel fiber was coated with a gate-opening controlled metal-organic framework ZIF-7 via a sol-gel method and applied to the solid-phase microextraction of aldehydes (hexanal, heptanal, octanal, nonanal, decanal) from exhaled breath by lung cancer patients. The effects of temperature and time on the sorption and desorption were optimized. Under optimum condition, the modified fiber displays enrichment factors (typically ranging from 300 to 10,000), low limits of detection (0.61-0.84 µg L-1), and wide linear ranges of hexanal, heptanal (5-500 µg L-1) and octanal, nonanal, decanal (10-1000 µg L-1). The high extraction capability for aldehydes is thought to result from (a) the combined effects of the large surface area and the unique porous structure of the ZIF-7, (b) the hydrophobicity and gate-opening effect of the sorbent, (c) the high selectivity of the window, and (d) the presence of unsaturated metal-coordination sites. The coated fiber is thermally stable and can be re-used >150 times. The relative standard deviation (RSD) for six replicate extractions using a single fiber ranged from 1.4-15.3% for intra-day and 2.4-16.1% for inter-day. The fiber-to-fiber reproducibility for three fibers prepared in parallel was in the range of 2.4-12.6% (RSD). The method was applied to the extraction of aldehydes from real samples and to the quantitation by gas chromatography. Recoveries from spiked samples ranged from 84 to 113%. Graphical abstract A metal-organic framework ZIF-7 coated stainless steel fiber was prepared via sol-gel method. The self-made fiber was applied in the solid phase microextraction of aldehydes from exhaled breath of lung cancer patients.

Rational design of CdS/BiOCl S-scheme heterojunction for effective boosting piezocatalytic H2 evolution and pollutants degradation performances.

Piezocatalysis as an emerging technology is broadly applied in hydrogen evolution and organic pollutants degradation aspects. However, the dissatisfactory piezocatalytic activity is a severe bottleneck for its practical applications. In this work, CdS/BiOCl S-scheme heterojunction piezocatalysts were constructed and explored the performances of piezocatalytic hydrogen (H2) evolution and organic pollutants degradation (methylene orange, rhodamine B and tetracycline hydrochloride) under strain by ultrasonic vibration. Interestingly, CdS/BiOCl presents a volcano-type relationship between catalytic activity and CdS contents, namely firstly increases and then decreases with the increase of CdS content. Optimal 20 % CdS/BiOCl endows superior piezocatalytic H2 generation rate of 1048.2 µmol g-1h-1 in methanol solution, which is 2.3 and 3.4 times higher than that of pure BiOCl and CdS, respectively. This value is also much higher than the recently reported Bi-based and most of other typical piezocatalysts. Meanwhile, 5 % CdS/BiOCl delivers the highest reaction kinetics rate constant and degradation rate toward various pollutants compared with other catalysts, which also exceeds that of the previously numerous results. Improved catalytic capacity of CdS/BiOCl is mainly ascribed to the construction of S-scheme heterojunction for enhancing the redox capacity as well as inducing more effective charge carriers separation and transfer. Moreover, S-scheme charge transfer mechanism is demonstrated via electron paramagnetic resonance and Quasi-In-situ X-ray photoelectron spectroscopy measurements. Eventually, a novel piezocatalytic mechanism of CdS/BiOCl S-scheme heterojunction has been proposed. This research develops a novel pathway for designing highly efficient piezocatalysts and provides a deeper understanding in construction of Bi-based S-scheme heterojunction catalysts for energy conservation and wastewater disposal applications.