It is well documented that the traditional Fenton reagent (i.e., the combination of Fe(II) and HO) produces hydroxyl radical (OH) under acidic conditions, while at near-neutral pH the reactive intermediate converts to ferryl ion (Fe(IV)) that can oxidize sulfoxides to produce corresponding sulfones, markedly differing from their OH-induced products. However, it remains unclear whether Fe(IV) is generated in the Fe(II) activated peroxydisulfate (PDS) process, where sulfate radical (SO) is long recognized as the dominant intermediate in literature. Here we demonstrated that SO oxidized methyl phenyl sulfoxide (PMSO, a model sulfoxide) to produce biphenyl compounds rather than methyl phenyl sulfone (PMSO). Interestingly, the formation of PMSO was observed when PMSO was treated by the Fe(II)/PDS system over a wide pH range, and the yields of PMSO were quantified to be ∼100% at acidic pH 3-5. The identification of Fe(IV) in the Fe(II)/PDS system could also reasonably explain the literature results on alcohol scavenging effect and ESR spectra analysis. Further, a Fe(IV)-based kinetic model was shown to accurately simulate the experimental data. This work urges re-evaluation of the Fe(II)/PDS system for environmental decontamination, given that Fe(IV) would have different reactivity toward environmental contaminants compared with SO and/or OH.
The reactions between peroxymonosulfate (PMS) and quinones were investigated for the first time in this work, where benzoquinone (BQ) was selected as a model quinone. It was demonstrated that BQ could efficiently activate PMS for the degradation of sulfamethoxazole (SMX; a frequently detected antibiotic in the environments), and the degradation rate increased with solution pH from 7 to 10. Interestingly, quenching studies suggested that neither hydroxyl radical (•OH) nor sulfate radical (SO4•-) was produced therein. Instead, the generation of singlet oxygen (1O2) was proved by using two chemical probes (i.e., 2,2,6,6-tetramethyl-4-piperidinol and 9,10-diphenylanthracene) with the appearance of 1O2 indicative products detected by electron paramagnetic resonance spectrometry and liquid chromatography mass spectrometry, respectively. A catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PMS and BQ and the subsequent decomposition of this intermediate into 1O2. Accordingly, a kinetic model was developed, and it well described the experimental observation that the pH-dependent decomposition rate of PMS was first-order with respect to BQ. These findings have important implications for the development of novel nonradical oxidation processes based on PMS, because 1O2 as a moderately reactive electrophile may suffer less interference from background organic matters compared with nonselective •OH and SO4•-.
Urchinlike CuO modified by reduced graphene oxide (rGO) was synthesized by a one-pot microwave-assisted hydrothermal method. The as-prepared composites were characterized using various characterization methods. A humidity sensor based on the CuO/rGO composites was fabricated and tested. The results revealed that the sensor based on the composites showed much higher impedance than pure CuO. Compared with the sensors based on pristine rGO and CuO, the sensor fabricated with the composites exhibited relatively good humidity-sensing performance in terms of response time and response value. The humidity-sensing mechanism was also briefly introduced. The enlargement of the impedance and improvement of the humidity-sensing properties are briefly explained by the Schottky junction theory.
Wearable and stretchable electronics including various conductors and sensors are featured with their lightweight, high flexibility, and easy integration into functional devices or textiles. However, most flexible electronic materials are still unsatisfactory due to their poor recoverability under large strain. Herein, we fabricated a carbon nanotubes (CNTs) and polyurethane (PU) nanofibers composite helical yarn with electrical conductivity, ultrastretchability, and high stretch sensitivity. The synergy of elastic PU molecules and springlike microgeometry enable the helical yarn excellent stretchability, while CNTs are stably winding-locked into the yarn through a simple twisting strategy, making good conductivity. By virtue of the interlaced conductive network of CNTs in microlevel and the helical structure in macrolevel, the CNTs/PU helical yarn achieves good recoverability within 900% and maximum tensile elongation up to 1700%. With these features, it can be used as a superelastic and highly stable conductive wire. Moreover, it also can monitor the human motion as a rapid-response strain sensor by adjusting the content of the CNTs simply. This general and low-cost strategy is of great promise for ultrastretchable wearable electronics and multifunctional devices.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.