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  • Shule Li, Keding Lu, Xuefei Ma, Xinping Yang, Shiyi Chen, Yuanhang Zhang
    Chinese Chemical Letters. 2020, 31(10): 2799-2802.

    A low-pressure reactor (LPR) was developed for the measurement of ambient organic peroxy (RO2) radicals with the use of the laser-induced fluorescence (LIF) instrument. The reactor converts all the ROx (=RO2 + HO2 + RO + OH) radicals into HO2 radicals. It can conduct different measurement modes through altering the reagent gases, achieving the speciated measurement of RO2 and RO2# (RO2 radicals derived from the long-chain alkane, alkene and aromatic hydrocarbon). An example of field measurement results was given, with a maximum concentration of 1.88×108 molecule/cm3 for RO2 and 1.18×108 molecule/cm3 for RO2#. Also, this instrument quantifies the local ozone production rates directly, which can help to deduce the regional ozone control strategy from an experimental perspective. The new device can serve as a potent tool for both the exploration of frontier chemistry and the diagnosis of the control strategies.

  • Gong Chen, Li-Chao Nengzi, Yingjie Gao, Guixian Zhu, Jianfeng Gou, Xiuwen Cheng
    Chinese Chemical Letters. 2020, 31(10): 2730-2736.

    In this study, Fe2O3/Mn2O3 composite was synthesized by a facile two-step technique, and several methods were carried out to characterize it. Then, the decomposition experiments of tartrazine (TTZ), a kind of refractory organic pollutant, were conducted under various environmental condition to detect the catalyst performance, such as reaction system, the dosage of catalyst, peroxymonosulfate (PMS) concentration, initial pH, different natural water substances. The results exhibited that Fe2O3/Mn2O3 composite with the mole rate 2:3 had the best PMS activation performance and the removal efficiency was 97.3% within 30 min. Besides, the optimum degradation conditions of TTZ were also discussed, that is catalyst dosage (0.6 g/L), PMS concentration (0.8 g/L) and the initial pH 11. In addition, proved by the natural water substances adding experiments, HPO42-, HCO3-, NO3- and NOM (nature organic matter) could slow down the experiments progressing, but Cl- could boost it. Then inhibitor experiments indicated both the HO· and SO4·- played a vital role in the experiments. Reusability and ions leaching experiments as well as the used catalyst physical characterization images exhibited the excellent stability and cyclicity of the Fe2O3/Mn2O3 composite. Finally, based on the XPS (X-ray photoelectron spectroscopy) and the experiments results, the possible mechanism of TTZ degradation was proposed. This system might provide a novel thought for the decomposition of refractory organic pollutant and had potential in promotion of actual sewage treatment technology.

  • Qian Chen, Xuanrui Cheng, Huimin Long, Yongfang Rao
    Chinese Chemical Letters. 2020, 31(10): 2583-2590.

    Bi/semiconductor photocatalysts have extensively been applied in the production of hydrogen, CO2 reduction and environmental remediation in recent years. This short review summarizes the role of Bi metal as a plasma photocatalyst and cocatalyst. As a cocatalyst, Bi metal can be electron/hole trappers, charge transfer mediators, or oxygen vacancy coordinators. In addition, the preparation methods of the Bi/semiconductor photocatalysts are also reviewed. Challenges and future research directions related to Bi/semiconductor photocatalysts are discussed and summarized, including the use of advanced characterization techniques to refine the reaction mechanism, the difficulties of preparing Bi single atom catalyst, and the improvement of the reduction ability of Bi-based photocatalysts. This review helps understand the reaction mechanisms of the composite photocatalytic systems containing Bi metal and proposes new perspectives for designing the photocatalysts which can control air pollution via a reductive process.

  • Jiazhen Liao, Kanglu Li, Hao Ma, Fan Dong, Xiaolan Zeng, Yanjuan Sun
    Chinese Chemical Letters. 2020, 31(10): 2737-2741.

    One of the core issues in the photocatalytic oxidation of nitric oxide is the effective conversion of NO into the final product (nitrate). More than just improving the visible light photocatalytic performance of BiOCl, we aim to inhibit the generation of toxic by-product NO2 during this process. In this study, we demonstrate that the oxygen vacancies (OVs) modulate its surface photogenerated carrier transfer to inflect the NO conversion pathway by a facile mixed solvent method to induce OVs on the surface of BiOCl. The photocatalytic NO removal efficiency under visible light increased from 5.6% to 36.4%. In addition, the production rate of NO2 is effectively controlled. The effects of OVs on the generation of reactive oxygen species, electronic transfer, optical properties, and photocatalytic NO oxidation are investigated by combining density functional theory (DFT) theoretical calculations, the in situ FTIR spectra and experimental characterization. The OVs on the surface of BiOCl speed the trapping and transfer of localized electrons to activate the O2, producing O2·-, which avoid NO2 formation, resulting in complete oxidation of NO (NO + O2·- → NO3-). These findings can serve as the basis for controlling and blocking the generation of highly toxic intermediates through regulating the reactive species during the NO oxidation. It also can help us to understand the role of OV on the BiOCl surface and application of photocatalytic technology for safe air purification.

  • Wenjie He, Xingxing Wu, Yifei Li, Jing Xiong, Zhiling Tang, Yuechang Wei, Zhen Zhao, Xiao Zhang, Jian Liu
    Chinese Chemical Letters. 2020, 31(10): 2774-2778.

    The rapid recombination of photoinduced electron-hole pairs as well as the deficiency of high-energy carriers restricted the redox ability and products selectivity. Herein, the heterojunction of SnS2-decorated three-dimensional ordered macropores (3DOM)-SrTiO3 catalysts were in-situ constructed to provide transmit channel for high-energy electron transmission. The suitable band edges of SnS2 and SrTiO3 contribute to the Z-scheme transfer of photogenerated carrier. The 3DOM structure of SrTiO3-based catalyst possesses the slow light effect for enhancing light adsorption efficiency, and the surface alkalis strontium is benefit to the boosting adsorption for CO2. The in-situ introduced SnS2 decorated on the macroporous wall surface of 3DOM-SrTiO3 altered the primary product from CO to CH4. The Z-scheme electron transfer from SnS2 combining with the holes in SrTiO3 occurred under full spectrum photoexcitation, which improved the excitation and utilization of photogenerated electrons for CO2 multi-electrons reduction. As a result, (SnS2)3/3DOM-SrTiO3 catalyst exhibits higher activity for photocatalytic CO2 reduction to CH4 compared with single SnS2 or 3DOM-SrTiO3, i.e., its yield and selectivity of CH4 are 12.5 μmol g-1 h-1 and 74.9%, respectively. The present work proposed the theoretical foundation of Z-scheme heterojunction construction for enhancing photocatalytic activity and selectivity for CO2 conversion.

  • Kena Qin, Liangliang Wei, Jianju Li, Bo Lai, Fengyi Zhu, Hang Yu, Qingliang Zhao, Kun Wang
    Chinese Chemical Letters. 2020, 31(10): 2603-2613.

    Antibiotic resistance genes (ARGs) in aquatic environments, which seriously endanger human health and ecological safety, have become a worldwide concern due to their easy diffusion and proliferation. Wastewater treatment plants (WWTPs), which receive resistant bacteria and ARGs from a wide variety of sources (i.e., livestock farms, hospitals, antibiotic manufactures, and households), are regarded as important emission sources of aquatic ARGs. This review presents a quantitative profile of the majority sources of ARGs in the influent of WWTPs and discusses the potential factors that affect the concentration distribution of ARGs. Specifically, a noteworthy existence of ARGs, which ranged from 1E + 05 to 1E + 11 copies/mL, was detected in livestock breeding wastewater, and household wastewater (caused by the unlimited utilization of antibiotics) was determined to be the predominant contributor of ARGs in WWTPs. We summarized the selective pressure on ARGs and determined the positive correlation of the concentration of ARGs and the existence of many containments, including antibiotics, heavy metals (Zn and Cu were frequently reported), quaternary ammonium compounds, etc. In the last section, physical, chemical, and biological treatments for the removal of ARGs and their effluent in WWTPs are discussed and prospective future studies are summarized.

  • MD Faysal Hossain, Nasrin Akther, Yanbo Zhou
    Chinese Chemical Letters. 2020, 31(10): 2525-2538.

    From emerging pollutants to emerged threat, researchers are continuously looking for promising technologies for wastewater treatment. Adsorption has been identified as the most convenient approach for treating wastewater at low-cost and with high-efficiency. Recently, graphene and its derivatives have gained heightened attention as novel adsorbents because of their unique molecular structure and outstanding physicochemical properties. Heavy metals, dyes, polycyclic aromatic hydrocarbons (PAHs) and other pollutants, which are widely concerned recently, all show different adsorption behaviors. Numerous functional groups, resonating and delocalized π-electron system of graphene derivatives lead to the formation of various adsorptive interactions i.e., π-π interactions, electrostatic interactions, H-bonding, etc. with these venomous pollutants, and quarantine them in solution. The pristine form of graphene subsidiaries tends to exhibit low sorption efficiency due to high propensity of agglomeration, lack of selectivity, hydrophobicity and difficulty in phase separation after treatment. Therefore, designing of efficient graphene composites through the surface modification with numerous functional groups, polymers or nanoparticles is an ongoing challenge. Complex graphene composites are increasingly reported, but the fate of pollutants and adsorption mechanisms are still far to be fully clarified. This review summarizes the recent progresses in the application of graphene-based adsorbents for eliminating a wide range of organic and inorganic pollutants from wastewater. A critical explanation is provided on the synthesis of graphene adsorbents, systematic adsorption and desorption mechanisms along with their pollutant removal performances under different experimental conditions. A brief perspective on upcoming research needs and challenges involved in the designing of high-quality graphene-based adsorbents are highlighted.

  • Meng Zhu, Yucheng Liu, Mingyan Chen, Dong Gan, Maoren Wang, Haojie Zeng, Maoqi Liao, Jie Chen, Wenwen Tu, Wen Niu
    Chinese Chemical Letters. 2020, 31(10): 2683-2688.

    Metal organic frameworks (MOFs) has broad application prospect in separation, catalysis, and adsorption. By a facile green method, we successfully fabricated prGO@cHKUST-1 composite membrane with the modification of dopamine and orientated growth of MOFs. Mg/Al-layered double hydroxides (Mg/Al-LDHs) was used as a modulator to obtain cubic HKUST-1 (cHKUST-1) with excellent morphology and special properties. Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) etc. characterization illustrated successful synthesis of cHKUST-1 and composite membranes. Cubic HKUST-1 can tune the inter-layer spacing of graphene oxide (GO) leading increase in hydrophilicity and flux of the membrane. Meanwhile, the reduction effect of PDA and intercalation effect of MOFs could change the stacked way of GO layers, forming several fuzzy pores and more active sites on membrane surface. The prGO@cHKUST-1 membrane has an excellent rejection for methylene blue (MB) (99.5%) and Congo red (CR) (71.2%). Moreover, the modified membrane exhibited 10 and 5 times higher permeation flux than that of original GO membrane and prGO membrane, respectively. Thus, using orientated growth of MOFs to synthesize GO based composite membrane will provide useful insights in ultrahigh permeation flux membranes of dye and oil-water emulsion separation.

  • Bin Yang, Longtai Li, Ziye Jia, Xiping Liu, Chunjie Zhang, Limin Guo
    Chinese Chemical Letters. 2020, 31(10): 2627-2633.

    Hydrogenation of CO2 to value-added chemicals has attracted much attention all through the world. In2O3 with cubic bixbyite-type (denoted as c-In2O3) is well known for its high CO2 hydrogenation activity and CH3OH selectivity at high temperature. However, the other structure of In2O3 with rhombohedral corundum-type (denoted as rh-In2O3) rarely been investigated as catalyst. Herein, c-In2O3 and rh-In2O3 were prepared and comparatively studied for CO2 hydrogenation. The results indicated that c-In2O3 showed higher CO2 conversion activity than rh-In2O3 due to the impressive reducibility and reactivity. Whereas rh-In2O3 had higher CH3OH selectivity due to weaker CH3OH and stronger CO adsorption on rh-In2O3. Although c-In2O3 and rh-In2O3 catalysts showed different CO2 hydrogenation performance, in-situ diffuse reflectance infrared Fourier transform spectroscopy showed CO2 can be reduced to CO through redox cycling and hydrogenation to CH3OH through formate path.

  • Chao Yang, Ming-Xia Zheng, Yuan Zhang, Bei-Dou Xi, Zai-Feng Tian, Xiao-Song He
    Chinese Chemical Letters. 2020, 31(10): 2693-2697.

    Composting can enhance the nutrient elements cycling and reduce carbon dioxide production. However, little information is available regarding the application of compost for the remediation of the contaminated soil. In this study, we assess the response of the redox capacities (electron accepting capacities (EAC) and electron donating capacities (EDC)) of compost-derived humic acids (HAs) to the bioreduction of hexavalent chromium (Cr(VI)), especially in presence of hematite. The result showed that the compost-derived HAs played an important role in the bioreduction of Cr(VI) in presence and absence of hematite under the anoxic, neutral (pH 7) and motionless conditions. Based on the pseudo-first order kinetic model, the rate constants of Cr(VI) reduction increased by 1.36–2.0 times when compost-derived HAs was added. The redox capacity originating from the polysaccharide structure of compost-derived HAs made them effective in the direct Cr(VI) reduction (without MR-1) at pH 7. Meanwhile, the reduction rates were inversely proportional to the composting treatment time. When iron mineral (Fe2O3) and compost-derived HAs were both present, the rate constants of Cr(VI) reduction increased by 2.35–5.09, which were higher than the rate of Cr(VI) reduction in HA-only systems, indicating that the hematite played a crucial role in the bioreduction process of Cr(VI). EAC and quinonoid structures played a major role in enhancing the bioreduction of Cr(VI) when iron mineral and compost-derived HAs coexisted in the system. The results can extend the application fields of compost and will provide a new insight for the remediation of Cr(VI)-contaminated soil.

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