共查询到20条相似文献，搜索用时 15 毫秒
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An efficient method has been developed for the catalytic oxidation of pollutants that are not easily degraded. The products of the hydrogen peroxide (H(2)O(2)) oxidation of 2,4,6,-trichlorophenol (TCP) catalyzed by the iron complex 2,9,16,23-tetrasulfophthalocyanine (FePcS) were observed to be chloromaleic, chlorofumaric, maleic, and fumaric acids from dechlorination and aromatic cycle cleavage, as well as additional products that resulted from oxidative coupling. Quantitative analysis of the TCP oxidation reaction revealed that up to two chloride ions were released per TCP molecule. This chemical system, consisting of an environmentally safe oxidant (H(2)O(2)) and an easily accessible catalyst (FePcS), can perform several key steps in the oxidative mineralization of TCP, a paradigm of recalcitrant pollutants. 相似文献
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Enache DI Edwards JK Landon P Solsona-Espriu B Carley AF Herzing AA Watanabe M Kiely CJ Knight DW Hutchings GJ 《Science (New York, N.Y.)》2006,311(5759):362-365
The oxidation of alcohols to aldehydes with O2 in place of stoichiometric oxygen donors is a crucial process for the synthesis of fine chemicals. However, the catalysts that have been identified so far are relatively inactive with primary alkyl alcohols. We showed that Au/Pd-TiO2 catalysts give very high turnover frequencies (up to 270,000 turnovers per hour) for the oxidation of alcohols, including primary alkyl alcohols. The addition of Au to Pd nanocrystals improved the overall selectivity and, using scanning transmission electron microscopy combined with x-ray photoelectron spectroscopy, we showed that the Au-Pd nanocrystals were made up of a Au-rich core with a Pd-rich shell, indicating that the Au electronically influences the catalytic properties of Pd. 相似文献
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[目的]研究UV/Fenton法降解水中1,4对苯二酚的最佳工艺条件及其动力学。[方法]采用UV/Fenton法处理1,4对苯二酚模拟废水,考察了nH2O2∶nFe2+、反应时间、H2O2用量、初始pH、紫外光强对1,4对苯二酚降解效果的影响,并初步探讨了1,4对苯二酚的降解动力学规律。[结果]UV/Fenton法降解1,4对苯二酚的最佳工艺条件:nH2O2∶nFe2+为5∶1,反应时间为60 min,H2O2投加量为3.5ml/L,初始pH为3,紫外光强度为500 W。在此条件下,浓度为1 000 mg/L的1,4对苯二酚的COD和浓度去除率分别可达93.19%和87.75%。UV辐射和Fenton氧化对1,4对苯二酚的降解具有协同效应。UV/Fenton法对1,4对苯二酚的降解符合准一级反应动力学方程,其表观速率常数为0.005 1 min-1。[结论]该研究为1,4对苯二酚污染治理提供了新途径。 相似文献
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Realizing the extraordinary potential of unactivated sp3 C-H bond oxidation in organic synthesis requires the discovery of catalysts that are both highly reactive and predictably selective. We report an iron (Fe)-based small molecule catalyst that uses hydrogen peroxide (H2O2) to oxidize a broad range of substrates. Predictable selectivity is achieved solely on the basis of the electronic and steric properties of the C-H bonds, without the need for directing groups. Additionally, carboxylate directing groups may be used to furnish five-membered ring lactone products. We demonstrate that these three modes of selectivity enable the predictable oxidation of complex natural products and their derivatives at specific C-H bonds with preparatively useful yields. This type of general and predictable reactivity stands to enable aliphatic C-H oxidation as a method for streamlining complex molecule synthesis. 相似文献
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High-resolution and in situ electron microscopy of vanadyl pyrophosphate catalysts reacted in alkane (n-butane) and other reducing environments have shown evidence for surface structure modifications accompanied by two sets of symmetry-related extended defects. Defect analysis reveals that the defects are formed by pure (glide) shear mechanism. The defect mechanism suggests the presence of basal (coplanar) anion vacancies, associated with Lewis acid centers, at oxygen sites linking corner-sharing phosphorus tetrahedra and vanadyl octahedra in the active plane. These in-plane defect sites may be key to the activation of the alkane, especially in the dehydrogenation. 相似文献
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A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase. 相似文献
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本文研究了Co(Ⅱ)在氢氧化钠介质中催化过氧化氢氧化4,5-二溴邻硝基苯基荧光酮(DBON - PF)褪色的新指示反应及影响反应速度的因素,建立了测定痕量钴的催化动力学光度新方法.方法检出限为8.5 ×10-12g/mL,Co(Ⅱ)含量在0ng/10mL～3.2ng/10mL范围内符合比尔定律,是光度法测定钴的高灵敏体系之一,本法选择性好,灵敏度高,应用于VB12中钴的测定,相对标准偏差为2.8％ ～3.4％,加标回收率为96％ ～ 104％,符合痕量分析的要求. 相似文献
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Lu J Fu B Kung MC Xiao G Elam JW Kung HH Stair PC 《Science (New York, N.Y.)》2012,335(6073):1205-1208
We showed that alumina (Al(2)O(3)) overcoating of supported metal nanoparticles (NPs) effectively reduced deactivation by coking and sintering in high-temperature applications of heterogeneous catalysts. We overcoated palladium NPs with 45 layers of alumina through an atomic layer deposition (ALD) process that alternated exposures of the catalysts to trimethylaluminum and water at 200°C. When these catalysts were used for 1 hour in oxidative dehydrogenation of ethane to ethylene at 650°C, they were found by thermogravimetric analysis to contain less than 6% of the coke formed on the uncoated catalysts. Scanning transmission electron microscopy showed no visible morphology changes after reaction at 675°C for 28 hours. The yield of ethylene was improved on all ALD Al(2)O(3) overcoated Pd catalysts. 相似文献
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[目的]探讨采用Fenton氧化预处理天然气净化检修废水的效果。[方法]对天然气净化检修废水进行Fenton试剂氧化预处理,研究了pH、H2O2浓度、n(H2O2)/n(Fe2+)比例、反应温度以及反应时间对COD去除率的影响,确定了反应的最佳条件,并考察了Fenton氧化前后检修废水的生物可降解性。[结果]Fenton氧化试验最佳反应条件为:H2O2投加量0.3 mol/L,n(H2O2)/n(Fe2+)=20∶1,初始pH值为3.0,温度70℃的条件下反应40 min。在此条件下,COD由18~22 g/L下降到3 852~4 708 mg/L,去除率可达78.6%。Fenton氧化预处理后废水的可生化性得到了大大提高,其作为UASB的预处理,效果非常显著。[结论]从环境经济角度分析,Fenton氧化与UASB联合处理后废水不仅处理效果好、成本低,而且控制了污水排污总量,具有广阔的应用前景。 相似文献
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过硫酸盐活化技术处理地下水中的BTEX及其动力学 总被引：2，自引：0，他引：2
利用模拟苯、甲苯、乙苯和二甲苯(BTEX)污染的地下水,研究过硫酸盐(Na2S2O8)活化氧化处理BTEX污染。结果表明,过硫酸盐对BTEX污染的地下水具有很好的处理能力。当Na2S2O8/BTEX(摩尔比)=20,Na2S2O8/Fe2+(摩尔比)=8的时候,BTEX的处理效果最好,甲苯、乙苯和二甲苯去除率均能达到80%以上;而苯的去除率稍低。整个试验过程中体系均处于强氧化环境,pH值降至3以下。过硫酸盐对苯、甲苯、乙苯和二甲苯(BTEX)的去除过程均符合二级反应动力学:1/ct=kt+1/c0。 相似文献
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Rancimat法比较茶多酚、迷迭香及BHA+BHT对棕榈油氧化稳定性的影响 总被引：1，自引：0，他引：1
比较天然迷迭香、茶多酚与复配BHA和BHT对油脂氧化稳定性的影响,通过Rancimat法快速测定了添加不同配比的迷迭香、茶多酚及复配BHA和BHT的棕榈油样品的诱导时间,结果表明:在棕榈油中抗氧化稳定效果分别为迷迭香150 mg/kg>茶多酚2 000mg/kg>迷迭香100 mg/kg>BHT 60 mg/kg+BHA 60 mg/kg>迷迭香50 mg/kg>迷迭香30 mg/kg>茶多酚500 mg/kg。迷迭香50 mg/kg的抗氧化性能与复配BHT和BHA效果相近,具备较好的应用前景。 相似文献
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基于O3的高级氧化工艺处理污水受制于O3的利用率,旋转填充床的应用能有效地提高臭氧吸收率和利用率。通过比较在旋转填充床中利用高级氧化工艺(O3,H2O2、O3/H2O2,O3/Fe2+,Fenton,O3/Fenton)对酸性红B进行脱色的效果,考察了O3/Fenton体系下H2O2和Fe2+的最佳摩尔比和Fe2+的最佳投加量,比较了在不同初始pH下各种氧化工艺的脱色效果以及在中性条件下各高级氧化工艺的脱色速率。结果表明,O3/Fenton体系下H2O2与Fe2+的最佳摩尔比为10∶1,Fe2+的最佳投加量为0.5 mmol·L-1。在低pH时O3/Fe2+与O3/Fenton相对于单独O3有着明显优势,中性时O3/Fenton体系有着最大的K值。 相似文献
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H_2O_2预处理对盐胁迫下黄瓜幼苗生长和K~+,Na~+,Cl~-分布的影响 总被引：2，自引：0，他引：2
以黄瓜品种津春2号为试材,采用营养液水培,研究了H2O2预处理对NaCl胁迫下幼苗植株不同器官中K+,Na+和Cl-含量的影响。结果表明,NaCl胁迫下黄瓜植株体内K+含量下降、Na+和Cl-含量升高、K/Na和Cl/Na比值降低;H2O2预处理抑制了盐胁迫下黄瓜幼苗植株体内K+含量的降低,减少了Na+和Cl-在叶片的积累,提高了K+,Na+吸收和运输的选择性及K/Na比值,缓解了盐胁迫的伤害,改善了盐胁迫下黄瓜幼苗的生长,显著提高了根、茎、叶的干重和幼苗株高。说明,叶面喷施外源H2O2可通过调控盐胁迫下植株体内离子在器官水平的区域化分布,进而提高黄瓜幼苗的耐盐性。 相似文献
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Kamata K Yonehara K Sumida Y Yamaguchi K Hikichi S Mizuno N 《Science (New York, N.Y.)》2003,300(5621):964-966
Epoxides are an important class of industrial chemicals that have been used as chemical intermediates. Catalytic epoxidation of olefins affords an interesting production technology. We found a widely usable green route to the production of epoxides: A silicotungstate compound, [gamma-SiW10O34(H2O)2]4-, is synthesized by protonation of a divacant, lacunary, Keggin-type polyoxometalate of [gamma-SiW10O36]8- and exhibits high catalytic performance for the epoxidation of various olefins, including propylene, with a hydrogen peroxide (H2O2) oxidant at 305 kelvin. The effectiveness of this catalyst is evidenced by >/=99% selectivity to epoxide, >/=99% efficiency of H2O2 utilization, high stereospecificity, and easy recovery of the catalyst from the homogeneous reaction mixture. 相似文献
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Kesavan L Tiruvalam R Ab Rahim MH bin Saiman MI Enache DI Jenkins RL Dimitratos N Lopez-Sanchez JA Taylor SH Knight DW Kiely CJ Hutchings GJ 《Science (New York, N.Y.)》2011,331(6014):195-199
Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites. 相似文献
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该文以半连续种子乳液聚合工艺合成了一种应用于麦秸/回收低密度聚乙烯（LDPE）复合材料的新型偶联剂——羟基丙烯酸酯共聚物,研究了聚合温度、引发体系对单体转化率及聚合反应稳定性的影响及合成的共聚物与复合材料性能间的关系.研究表明:同时引入较高比例的功能性官能团单体N 羟甲基丙稀酰胺（NMA）和丙烯酸 β 羟乙酯（HEA）,用K2S2O8或K2S2O8/FeSO4热引发聚合,近100％的单体转化率和无凝胶的乳液聚合不可兼得;使用助还原剂NaSO2的K2S2O8/FeSO4引发体系,单体转化率可接近100％,而且乳液的综合性能好.将合成的羟基丙烯酸酯共聚物与异氰酸酯PAPI复合偶联麦秸/回收LDPE复合材料,其物理及力学性能提高显著,达到GB/T4897-7—2003规定的在潮湿状态下使用的增强结构用板要求. 相似文献
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Of the processes for converting natural gas into a more useful chemical feedstock, the oxidative coupling of methane to form ethane and ethylene (C(2)) has perhaps been the most intensively investigated in recent years, but it has proved extremely difficult to obtain C(2) yields in excess of 20 to 25%. Methane oxidative coupling was carried out in a separative chemical reactor that simulated a countercurrent chromatographic moving-bed. This reaction gives 65% methane conversion, 80% C(2) selectivity, and a C(2) yield slightly better than 50% with Sm(2)O(3) catalyst at approximately 1000 K. 相似文献
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[目的]研究商洛黄芩氮磷钾不同配比的施肥效应.[方法]以商洛黄芩为研究材料,在探讨不同施肥处理的产量、品质及经济效益的基础上,采用3因素2次饱和-D最优设计方案进行田间试验,获取黄芩的产量数据;并采用超声提取比色法测定黄酮的含量,采用超声循环提取紫外分光光度法测定黄芩苷的含量;根据试验产量和肥料投入,计算增收率.[结果]依据黄芩产量并保证品质及经济效益得出氮磷钾配施优于单施和两两配施,处理8（折合N 53.13、P2O5224.89、K2O224.89 kg/hm^2）和处理10（折合N 149.93、P2O5224.89、K2O 79.7 kg/hm^2）为较优的2个施肥配比.[结论]该方法为商洛黄芩优质高产栽培提供了合理的施肥依据. 相似文献
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聚乙烯地膜降解过程与机理研究进展 总被引：2，自引：1，他引：1
为探讨聚乙烯地膜的降解过程及影响因素,从聚乙烯材料的分子结构与特性入手,结合国内外最新研究进展,系统论述了聚乙烯分子的降解过程、产物、机理与作用因素。文章指出聚乙烯分子较高的结晶度与相对分子质量、较强的疏水性与分子间作用力是导致其难以降解的主要因素;其中,聚乙烯分子间共价键的氧化断裂是整个降解过程的限速反应。环境中较强的光能、热能、机械作用力等能够促进聚乙烯分子键的氧化断裂,使聚乙烯分子非结晶区及小型结晶区域解聚成亲水性低聚物或小分子,并最终在微生物作用下完全分解为CO_2、H_2O、CH_4、生物质等微生物代谢产物。深入系统开展聚乙烯分子降解机理的系统研究,不仅可以科学评价残留地膜对环境的影响,而且能够指导聚乙烯地膜配方改进,降低聚乙烯地膜残留污染。 相似文献