Stable Radicals with Protective Umbrellas Integrated on the Surface of 2D Layered Materials

Radicals are closely related to human life and health and have been widely used in biology, chemistry, functional materials, etc. However, the high reactivity, disorder, and short half-lives limit their wide applications. Therefore, it remains a great challenge to prepare stable and ordered radicals. Herein, radicals are prepared with protective umbrellas (diethylmethyleneamine, DEMA) that are integrated on the surface of 2D layered materials to isolate water and oxygen and enhance the stability of radicals. Taking 2D black phosphorus (BP) as an example: triethylamine reacts with dichloromethane to form quaternary ammonium salts with further Hoffmann elimination to produce DEMA radicals that could react with one electron of a lone pair electrons in P on the surface of BP to produce P radicals, which shows a prolonged half-life of 21 days at room temperature. First-principle calculations and electron paramagnetic resonance fitting confirm that the steric hindrance constructed by dense DEMA passivation layer acts as a protective umbrella and the 2D coupling of P radicals and other P atoms in 2D BP plane to enhance the stability and strong superexchange interaction of P radicals. Furthermore, it is a general strategy to produce stable radicals integrated on the 2D plane.     

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Lead-free sodium niobate nanowires with strong piezo-catalysis for dye wastewater degradation

In this work, the hydrothermally-synthesized sodium niobate nanowires were used to decompose Rhodamine B dye solution through the piezo-catalytic effect. With the sodium niobate catalyst, a high piezo-catalytic degradation ratio of ～80% was achieved under the excitation of vibration for the Rhodamine B dye solution (～5?mg/l). These active species in the catalytic process, hydroxyl radicals and superoxide radicals with the strong oxidation ability, were also observed, which confirmed the key role of piezoelectric effect for piezo-catalysis. The piezo-catalysis of sodium niobate nanowires provides a high-efficiency and reusable tool in application in depredating the dye wastewater.     

裂解态正癸烷点火延迟时间的理论研究（英）

在先进飞行器发动机中,吸热碳氢燃料在进入燃烧室之前会发生热裂解反应,生成未反应燃料和小分子裂解产物的混合物(称为裂解态燃料)。本工作研究了在1300~1800 K、0.1~3.0 MPa和当量比为1.0的条件下,不同的裂解转化率、裂解压力、点火压力和自由基对正癸烷裂解着火特性的影响。通过采用一种精确的组合机理,从理论上计算了流动反应器中3.0和5.0 MPa下正癸烷裂解组分,与文献中的实验结果吻合较好。结果表明,正癸烷在3 MPa和5 MPa下裂解的出口转化率分别为46.2%和58.8%,裂解产物分布一致,但乙烯的含量随着压力的升高明显的降低,而烷烃含量随着压力的增大而增加。尽管自由基总体含量很低,但在3 MPa条件下裂解产物中的自由基浓度依然高于5 MPa条件下。对于点火延迟时间的计算结果则表明,裂解态正癸烷的点火延迟时间随着转化率的增大而延长,且在5 MPa下随着转化率的变化更明显。相同转化率下,5 MPa下的裂解态正癸烷的点火延迟时间比3 MPa下更短。此外,与无自由基的裂解正癸烷相比,裂解正癸烷中自由基的存在可以加速着火过程,转化率小于40%时,着火延迟时间缩短15%以上。     

The role of an interfacial interpenetrating polymer network formation on the adhesion of resin composite layers in immediate dentin sealing

The aim of this study was to evaluate the influence of chemical and physical processes at the resin-composite and composite-cement interface as a function of the resin composite's water exposure on the bond strength (BS) between these two components. The free-radical concentration was studied using electron paramagnetic resonance (EPR), while the chemical changes at the resin composite's surface were studied using attenuated total-reflection FTIR spectroscopy (ATR-FTIR). The free-radical concentration in the studied samples dropped to 10% in 24 h, indicating that prolonged BS values do not correlate with the free-radical concentration. An alternative bonding mechanism between the resin composite and the composite cement was proposed, based on the formation of an interpenetrating polymer network (IPN) layer at the interface. As proven using ATR-FTIR spectroscopy, changes occurred at the resin composite's surface as a consequence of water exposure, comprising the diffusion of water molecules into the resin composite. These changes reduced the diffusion rate of the composite cement's phosphorus-containing monomers into the resin composite, as shown by the linescan SEM-EDS analysis of phosphorus, thus reducing the thickness of the IPN layer at the interface and consequently reducing the BS between both components.This study reveals that the concentration of free radicals at the surface of the resin composite is only relevant immediately after the polymerisation to the bond strength between the resin composite and the composite cement. Therefore, an alternative explanation is given by applying the theory of the formation of a gradient IPN at the interface between the resin composite and the adhesive cement by changes in the rate of diffusion of the adhesive cement's monomers into the resin composite as a function of the resin composite's exposure to water.     

Acid Hydrogen Peroxide Treatment of Norway Spruce TMP: The Effect of an Extended pH Range when Catalyzed by Free Ferrous and Free or EDG/EDTA-Chelated Ferric Ions

The influence of different types of iron salts (i.e., ferrous or ferric cations with sulphate, nitrate or chloride anions) on the reaction between coarse thermomechanical pulp and acid hydrogen peroxide (Fenton chemistry) was studied when the initial pH was 3.2 and 5.3. Also, ferric ions chelated with EDTA or EDG at different molar ratios were compared with ferrous sulphate when the initial pH was extended from about 3 to 8. Different anions of ferric ion salt gave a similar catalytic effect. At an initial pH of 7–8, the ferric-EDTA catalyzed reaction resulted in similar or higher hydrogen peroxide consumption and more detectable hydroxyl radicals than the ferrous sulphate catalyzed reaction, but less reaction with the pulp was indicated. Between pH 5–8, using Fe-EDG as a catalyst gave higher hydrogen peroxide consumption and more detectable hydroxyl radicals than if using ferrous sulphate; however, the measured effect on the pulp was similar or less.     

Copper‐Catalyzed Aerobic Formation of Unstable Sulfinyl Radicals for the Synthesis of Sulfinates and Thiosulfonates

Copper‐catalyzed aerobic coupling of thiols and alcohols affords sulfinates and thiosulfonates. These products are assumed to form via sulfinyl radicals which are not commonly found in oxidative coupling reactions of thiols. A reaction mechanism involving sulfinyl radicals is proposed, and mass and electron paramagnetic resonance (EPR) experimental results are provided.

     

Metal-doped carbon aerogels as catalysts during ozonation processes in aqueous solutions

The efficiency of Co(II)-, Mn(II)-, and Ti(IV)-doped carbon aerogels for the transformation of ozone into (*)OH radicals was investigated. The carbon aerogels had a markedly acid surface character (pH(PZC approximately equal) congruent with 3-4) with very high surface oxygen concentrations (O approximately equal with 20%). X-ray photoelectron spectroscopy (XPS) analyses of the samples showed the oxidation state of the metals was +2 for Co and Mn and +4 for Ti. The presence of Mn(II)-doped carbon aerogel enhanced ozone transformation into (*)OH radicals, whereas the presence of Co(II) and Ti(IV) carbon aerogels presented no activity in this process. Moreover, it was observed that an increase in the concentration of Mn in the surface of the aerogel increases its efficiency to transform ozone into (*)OH radicals, with an Rct value ([OH]/[O(3)]) of 5.36 x 10(-8) for the aerogel doped with 16% of surface Mn(II) compared to an R(ct) of 2.68 x 10(-9) for conventional ozonation. Regardless of the aerogel used, XPS analysis of the ozonated aerogel samples showed an increase in the concentration of surface oxygen when the exposure to ozone was longer. However, presence of oxidized metal species after ozone treatment was only detected in the case of the Mn-doped aerogel, (Mn(III) and Mn(IV)). CO(2) activation of carbon aerogel produced a marked increase in its efficiency to transform ozone into (*)OH radicals compared with non-activated sample. The efficiency of Mn activated carbon aerogel to transform ozone into (*)OH radicals was greater than that of Witco commercial activated carbon or H(2)O(2) in the ozonation of water from Lake Zurich (Zurich, Switzerland).