- Catalytic Aerobic Oxidation of Lignocellulose-Derived Levulinic Acid in Aqueous Solution: A Novel Route to Synthesize Dicarboxylic Acids for Bio-Based Polymers
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The world is facing grand and ever-increasing pressures on energy and environmental issues. Using carbon-neutral biomass to prepare monomers such as dicarboxylic acids for degradable polymers is of great significance and an urgent but challenging task. Herein, we report a catalytic route for the synthesis of 2-hydroxy-2-methylsuccinic acid, an excellent monomer: e.g., it is able to remarkably enhance the comprehensive properties of polybutylene succinate as shown herein. By catalytic aerobic oxidation of levulinic acid, a bulk platform chemical derived from lignocellulose, the target product was obtained with a very high selectivity of up to ca. 95%. The mild reaction conditions below 100 °C in water and the low-cost reusable heterogeneous catalyst further make the process highly attractive for applications. This process was also found to be effective for the conversion of homologues of levulinic acid to dicarboxylic acids. We studied the C-C bond rearrangement and the roles of catalysts in the reaction that are highly likely involved in a superoxide anion radical mechanism. This study may provide inspiration for the synthesis of bio-based dicarboxylic acids via alternative routes.
- Che, Li,Jiang, Min,Jiang, Yu,Pang, Jifeng,Song, Lei,Wang, Rui,Zhang, Tao,Zhao, Yu,Zheng, Mingyuan,Zhou, Guangyuan,Zhou, Mo
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p. 11588 - 11596
(2021/09/22)
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- Efficient photodegradation of 2-chloro-4-nitrophenol over Fe-doped BiOCl nanosheets with oxygen vacancy
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Photodegradation of organic pollutants emerged as a promising route for environmental remediation. Due to abundant localized electrons, oxygen vacancies (OVs) over BiOCl could promote the adsorption of organic pollutants and activation of oxygen to produce more reactive oxygen species (ROS) during the photocatalytic reaction. Considering the high oxidation potential (E0 = 1.8-2.7 V vs. NHE) of the hydroxyl radicals (OH), we introduced Fe dopant in the OV-associated BiOCl system (Fe-BOC) to build Fenton-like catalysts, which converted the H2O2 generated in the photoreaction to produce more OH for the photodegradation of 2-chloro-4-nitrophenol. Experimental results revealed that the concentration of H2O2 in the undoped BiOCl (BOC) photoreaction system was higher, while much more OH was detected in Fe-BOC, indicating that the Fenton-like reaction occurred for the conversion of H2O2 into OH over Fe-BOC. In addition, the better charge separation of Fe-BOC could motivate more surface e- for O2 activation into O2-. Thus, the more reactive oxygen species (OH and O2-) produced over Fe-BOC resulted in 3.1 times higher photocatalytic activity in contrast to that of BOC.
- Liu, Xiangming,Wu, Haoyuan,Xu, Hua,Yang, Xinmin,Ye, Jinhua
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p. 5119 - 5124
(2021/08/16)
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- Constructing an Acidic Microenvironment by MoS2 in Heterogeneous Fenton Reaction for Pollutant Control
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Although Fenton or Fenton-like reactions have been widely used in the environment, biology, life science, and other fields, the sharp decrease in their activity under macroneutral conditions is still a large problem. This study reports a MoS2 cocatalytic heterogeneous Fenton (CoFe2O4/MoS2) system capable of sustainably degrading organic pollutants, such as phenol, in a macroneutral buffer solution. An acidic microenvironment in the slipping plane of CoFe2O4 is successfully constructed by chemically bonding with MoS2. This microenvironment is not affected by the surrounding pH, which ensures the stable circulation of Fe3+/Fe2+ on the surface of CoFe2O4/MoS2 under neutral or even alkaline conditions. Additionally, CoFe2O4/MoS2 always exposes “fresh” active sites for the decomposition of H2O2 and the generation of 1O2, effectively inhibiting the production of iron sludge and enhancing the remediation of organic pollutants, even in actual wastewater. This work not only experimentally verifies the existence of an acidic microenvironment on the surface of heterogeneous catalysts for the first time, but also eliminates the pH limitation of the Fenton reaction for pollutant remediation, thereby expanding the applicability of Fenton technology.
- Huang, Kai,Lian, Cheng,Liang, Lihong,Xing, Mingyang,Yan, Qingyun,Yin, Pengcheng,Yu, Haoran,Zhang, Jinlong
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supporting information
p. 17155 - 17163
(2021/07/06)
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- Lignin-fueled photoelectrochemical platform for light-driven redox biotransformation
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The valorization of lignin has significant potential in producing commodity chemicals and fuels from renewable resources. However, the catalytic degradation of lignin is kinetically challenging and often requires noble metal catalysts to be used under harsh and toxic conditions. Here, we report the bias-free, solar reformation of lignin coupled with redox biotransformation in a tandem structure of a BiVO4 photoanode and perovskite photovoltaic. The tandem structure compensates for the potential gap between lignin oxidation and biocatalytic reduction through artificial Z-schematic absorption. We found that the BiVO4-catalyzed photoelectrochemical oxidation of lignin facilitated the fragmentation of higher molecular weight lignin into smaller carboxylated aliphatic and aromatic acids. Lignin oxidation induced photocurrent generation at the photoanode, which enabled efficient electroenzymatic reactions at the cathode. This study successfully demonstrates the oxidative valorization of lignin as well as biocatalytic reductions (e.g., CO2-to-formate and α-ketoglutarate-to-l-glutamate) in an unbiased biocatalytic PEC platform, which provides a new strategic approach for photo-biocatalysis using naturally abundant renewable resources.
- Boonmongkolras, Passarut,Choi, Eun-Gyu,Han, Seunghyun,Kim, Jinhyun,Kim, Kayoung,Kim, Yong Hwan,Lee, Sahng Ha,Lee, Yang Woo,Park, Chan Beum,Shin, Byungha,Trang, Nguyen Vu Thien,Wang, Ding
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supporting information
p. 5151 - 5160
(2020/08/25)
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- Electrochemical oxidation of amoxicillin on carbon nanotubes and carbon nanotube supported metal modified electrodes
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The electrolysis of amoxicillin (AMX) was carried out on CNT, Pt/CNT and Ru/CNT modified electrodes based on Carbon Toray in 0.1 M NaOH, 0.1 M NaCl and 0.1 M Na2CO3/NaHCO3 buffer (pH 10) media with the aim of studying the significance of two factors, electrode material and pH, on the oxidative degradation and mineralization of AMX. For this purpose, the electrolysis products were identified by HPLC-MS and GC–MS, and quantified by HPLC-UV-RID and IC. The highest carbon mineralization efficiency, corresponding to 30% of the oxidized AMX, was found for Pt/CNT modified electrode in carbonate buffer medium. Regarding to the AMX conversion, the results show that the effect of pH is higher than that of the electrode material. Principal component analysis allowed to determine the experimental parameters vs. product distribution relationship and to elucidate the oxidation pathways for the studied electrodes. The results show that the hydroxylation of the aromatic ring and the nitrogen atom play an important role on the efficient degradation of AMX.
- Ferreira, Marta,Kuzniarska-Biernacka, Iwona,Fonseca, António M.,Neves, Isabel C.,Soares, Olívia S.G.P.,Pereira, Manuel F.R.,Figueiredo, José L.,Parpot, Pier
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p. 322 - 331
(2019/07/10)
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- Integrated photocatalytic-biological treatment of triazine-containing pollutants
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The degradation of triazine-containing pollutants including simazine, Irgarol 1051 and Reactive Brilliant Red K-2G (K-2G) by photocatalytic treatment was investigated. The effects of titanium dioxide (TiO2) concentration, initial pH of reaction mixture, irradiation time and ultraviolet (UV) intensity on photocatalytic treatment efficiency were examined. Complete decolorization of K-2G was observed at 60 min photodegradation while only 15 min were required to completely degrade simazine and Irgarol 1051 under respective optimized conditions. High-performance liquid chromatography (HPLC), gas chromatography/mass spectrometry (GC/MS) and ion chromatography (IC) were employed to identify the photocatalytic degradation intermediates and products. Dealkylated intermediates of simazine, deisopropylatrazine and deethyldeisopropylatrazine, and Irgarol 1051 were detected by GC/MS in the initial phase of degradation. Complete mineralization could not be achieved for all triazine-containing pollutants even after prolonged (>72 h) UV irradiation due to the presence of a photocatalysis-resistant end product, cyanuric acid (CA). The toxicities of different compounds before and after photocatalytic treatment were also monitored by three bioassays. To further treat the photocatalysis-resistant end product, a CA-degrading bacterium was isolated from polluted marine sediment and further identified as Klebsiella pneumoniae by comparing the substrate utilization pattern (Biolog microplate), fatty acid composition and 16S rRNA gene sequencing. K. pneumoniae efficiently utilized CA from 1 to 2000 mg/L as a good nitrogen source and complete mineralization of CA was observed within 24 h of incubation. This study demonstrates that the biodegradability of triazine-containing pollutants was significantly improved by the photocatalytic pre-treatment, and this proposed photocatalytic-biological integrated system can effectively treat various classes of triazine-containing pollutants.
- Chan, Cho Yin,Chan, Ho Shing,Wong, Po Keung
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p. 371 - 380
(2019/02/07)
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- Aqueous-Phase Oxidation of Furfural to Maleic Acid Catalyzed by Copper Phosphate Catalysts
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Abstract: This work describes catalytic aqueous-phase oxidation of furfural to maleic acid. The heterogeneous Cu-phosphate catalysts were prepared by coprecipitation method at different atomic ratios of precursors and characterized by various techniques.
- Soták, Tomá?,Hronec, Milan,Gál, Miroslav,Dobro?ka, Edmund,?kriniarová, Jaroslava
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p. 2714 - 2723
(2017/09/28)
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- Synthesis of SiO2 coated zero-valent iron/palladium bimetallic nanoparticles and their application in a nano-biological combined system for 2,2′,4,4′-tetrabromodiphenyl ether degradation
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Polybrominated diphenyl ethers (PBDEs) are emerging persistent organic pollutants and the degradation of PBDEs is still a significant challenge owing to their extreme persistence and toxicity. In this study, the remediation of 2,2′,4,4′-tetrabromodiphenyl ether (BDE47) was investigated by employing a nano-biological combined system with SiO2-coated zero-valent iron/palladium bimetallic nanoparticles (SiO2-nZVI/Pd) as a reductant and Pseudomonas putida as a biocatalyst. The SiO2-nZVI/Pd exhibited much lower toxicity to the P. putida strain and higher reactivity in debromination than nZVI/Pd. The strain could grow well when the dosage was up to 1.0 g L-1. During the combined process, BDE47 (5 mg L-1) was completely debrominated to diphenyl ether (DE) within 2 h by SiO2-nZVI/Pd (1.0 g L-1) and then DE was completely degraded by P. putida after 4 days in sequential aerobic biodegradation. All the possible intermediates in the whole process were identified by ultra performance liquid chromatography (UPLC) and gas chromatography-mass spectrometer (GC-MS) analyses. The detection of BDE17, BDE7, BDE1 and DE indicated that rapidly stepwise debromination preferentially occurred at para positions in the anaerobic stage. Moreover, during aerobic biodegradation by P. putida, a number of phenolic compounds, such as phenol, catechol and hydroquinone were generated via ring opening by dioxygenation and further mineralized through the tricarboxylic acid cycle (TCA). Importantly, this combined process achieved rapid mineralization of PBDEs and avoided the generation of some highly toxic products like bromophenols and HO-PBDEs, which might have promising application prospects in the remediation of halogenated POPs.
- Lv, Yuancai,Niu, Zhuyu,Chen, Yuancai,Hu, Yongyou
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p. 20357 - 20365
(2016/03/04)
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- Heterogeneous sono-Fenton-like process using nanostructured pyrite prepared by Ar glow discharge plasma for treatment of a textile dye
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The plasma-treated pyrite (PTP) nanostructures were prepared from natural pyrite (NP) utilizing argon plasma due to its sputtering and cleaning effects resulting in more active surface area. The NP and PTP were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET) and scanning electron microscopy (SEM) methods. The performance of the PTP was greater than NP for treatment of Reactive Red 84 (RR84) by the heterogeneous sono-Fenton process. The optimum amounts of main operational parameters were obtained as PTP of 4 g/L, initial dye concentration of 10 mg/L, pH of 5, and ultrasonic power of 300 W after 120 min of reaction time. Also, the effects of enhancers, and inorganic salts and t-butanol as hydroxyl radical scavengers on the degradation efficiency were investigated. Gas chromatography-mass spectroscopy analysis (GC-MS) was applied for detection of some degradation intermediates. Environmentally friendly plasma modification of the NP, in situ production of H2O2 and OH radicals, low leached iron concentration and repeated reusability at the milder pH are the significant benefits of the PTP utilization.
- Khataee, Alireza,Gholami, Peyman,Vahid, Behrouz
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p. 213 - 225
(2015/10/19)
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- Chlorine dioxide catalytic oxidation and online FTIR spectroscopic analysis of simulated o-chlorophenol wastewater
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An activated carbon-MnO2 catalyst was prepared and used for chlorine dioxide catalytic oxidation of simulated o-chlorophenol wastewater. The COD removal efficiencies of chemical oxidation and catalytic oxidation are 28.6 and 93.5%, respectively
- Shi, Laishun,Wang, Xiaomei,Li, Na,Huai, Chunlei,Liu, Jie
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p. 1781 - 1790
(2013/02/23)
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- A recyclable polymer-supported ruthenium catalyst for the oxidative degradation of bisphenol A in water using hydrogen peroxide
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A polypyridyl ruthenium(ii) complex, cis-[RuII(2,9-Me 2phen)2(H2O)2]2+, has been adsorbed onto the cation-exchange resins Dowex-50W and Chelex-100. The potential use of the supported ruthenium(ii) complex as catalyst for the oxidative degradation of organic pollutants in water has been investigated using bisphenol A, an emerging endocrine disruptor, as substrate; and the environmentally friendly H2O2 as oxidant. These solid-supported catalysts are found to be efficient for the degradation of bisphenol A in aqueous solution by H2O2 under ambient conditions. The intermediates and products formed during the oxidative degradation of bisphenol A by these catalytic systems have been identified and a mechanism is proposed. The supported catalysts are easily recovered by simple filtration and display no loss of activity when recycled. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011.
- Hu, Zongmin,Leung, Chi-Fai,Tsang, Yat-Kwai,Du, Hongxia,Liang, Haojun,Qiu, Yongfu,Lau, Tai-Chu
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body text
p. 149 - 155
(2011/04/14)
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- Method and process of producing short chain fatty acids from waste stream containing phenolic lignin model compounds by controlled photocatalytic oxidation with titanium dioxide nanocatalyst in the presence of ultraviolet radiation
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A method of producing short chain carbon compounds from effluents that are rich in lignin-model compounds. The method is characterized by controlled photocatalytic degradation of lignin model compounds so as to produce short chain carbon compounds. The present invention provides converting recalcitrant and toxic organic compounds into chemicals which are of commercial value.
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Page/Page column 3
(2011/04/25)
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- Catalytic oxidation of furan and hydrofuran compounds 8. Synthesis of 5-ethoxycarbonyl-4-hydroxy-3-oxo-2(3H)-furanone by the oxidation of furfural in the system aqueous H2O2-VOSO4-ethanol
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The special features of the oxidation of furfural by aqueous hydrogen peroxide in the presence of vanadyl sulfate and ethanol has been studied for the first time. It has been established that this reaction proceeds with the formation of previously unknown
- Poskonin
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experimental part
p. 295 - 300
(2009/04/03)
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- Process for preparing R-(-) -carnitine from S-(-)-chlorosuccinic acid or from a derivative thereof
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An inner salt of L-carnitine is prepared by reduction, with a suitable reducing agent, of a compound of formula (I): where X1and X2, which may be the same or different, are hydroxy, C1-C4alkoxy, phenoxy, halogen, or X1and X2, when taken together are an oxygen atom and the resulting compound is a derivative of succinic anhydride; Y is halogen, the mesyloxy or the tosyloxy group: and subsequent treatment with water, then with a base and then with trimethylamine.
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Page column 9
(2008/06/13)
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- Method for production of acrylic acid
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In a method for producing acrylic acid by the steps of a reaction of catalytic gas phase oxidation, absorbing the acrylic acid with an absorbent, and dehydrating the acrylic acid-containing aqueous solution, the method is characterized that the step of dehydration comprises adding and an azeotropic solvent, distilling the resultant mixture, and adjusting the acrylic acid concentration at the top of the column in the range of 0.06-0.80 wt. %, thereby preventing the bottoms of the azeotropic dehydration column from substantially containing the azeotropic solvent and water. As results, the acrylic acid is kept from forming a polymer in any of the distillation columns involved in the production, and effective utilization of acrylic acid.
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Page column 12-14
(2008/06/13)
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- Catalytic oxidation of furan and hydrofuran compounds. 6. Oxidation of furan by hydrogen peroxide in the presence of vanadium compounds under the conditions of phase-transfer catalysis
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Oxidation of furan in system containing hydrogen peroxide, vanadium compound, chlorinated hydrocarbon, water, and phase-transfer catalyst was studied for the first time. In addition to the main product of this process - cis-β-formylacrylic acid - the form
- Poskonin,Badovskaya,Povarova,Ponomarenko
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p. 1143 - 1149
(2007/10/03)
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- Synthesis and thermal decomposition of derivatives of acyloxytetraphenylantimony
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Acyloxy derivatives of tetraphenylantimony of the general formula Ph4SbOC(O)R (R = Alk or Ar) have been synthesized by the reaction of pentaphenylantimony with carboxylic acids. Thermolysis of the compounds obtained affords phenyl carboxylates and triphenylstibine in quantitative yields. One of these compounds (R = CH=CHPh) has been studied by X-ray structural analysis. In this compound, the Sb atom has a trigonal-bipyramidal coordination. The Sb-O(Ph)eq distances are in the range 2.103(4)-2.140(5) A; the Sb-C(Ph)ax bond length is 2.167(5) A. The fragment of the residue of cinnamic acid has a delocalized double bond in the carboxylate group.
- Sharutina,Sharutin,Senchurin,Fukin,Zakharov,Yanovsky,Struchkov
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p. 186 - 190
(2007/10/03)
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