Density functional theory study of the reaction paths of reactions of CH3C(O)O2 radicals with HO2 in the gas phase

A DFT study on the reactions between CH₃C(O)O₂ and HO₂ radicals has been carried out. It is suggested that both the triplet and singlet potential surfaces involve a complex mechanism with the formation of loosely bound intermediate complexes of reactants and products. The reaction prefers to occur on the triplet surface to produce peracetic acid (CH₃C(O)O₂H) and triplet O₂ molecule. The CH₃C(O)O₂H can further convert into CH₃C(O)O and HO radicals.     

Density functional theory study of the reaction paths of reactions of CH_3C(O)O_2 radicals with HO_2 in the gas phase

Acetyl peroxyradicals play a major roleinthe at-mospheric degradation of organic compounds .In pol-luted atmospheres ,the reaction between CH3C(O)O2radical and NO2forms the well-known PAN(peroxy-acetyl nitrate , CH3C(O)OONO2) ,an i mportant or-ganic contributor to photochemical smog.Inless pol-luted atmospheres ,the reactions between CH3C(O)O2and HO2radicals become critical as NOxlevels maybe low[1 ,2]. Niki et al . were the first to examine thereactions of CH3C(O)O2with HO2radic…     

纳米Al2O3颗粒对Cu-Al2O3性能的影响

采用溶胶-凝胶法制备纳米Al₂O₃颗粒,通过粉末冶金法制备氧化铝铜（Cu-Al₂O₃）。采用X射线光电子能谱仪、扫描电子显微镜、洛氏硬度仪和涡流计分别测试了Cu-Al₂O₃的结合能、微观组织、硬度和导电率。结果表明：随Al₂O₃颗粒含量的增加,Cu-Al₂O₃的硬度先升高后降低,当Al₂O₃颗粒的质量分数达到0.084%时,Cu-Al₂O₃的硬度达到最大值75.73（HRB）。Cu-Al₂O₃的导电率随着Al₂O₃颗粒含量的增加逐渐下降。Al₂O₃颗粒的质量分数为0.084%时为最佳值,Cu-Al₂O₃的硬度达到最大值,导电率达到69.1% IACS。     

氧化吸收法同步脱除燃烧烟气中SO2，NOx和CO2的化学热力学及其评价

湿化学法同步脱除烟气中气态污染物是燃烧源大气污染控制的重要方法之一,为探究采用不同氧化吸收策略同时脱除燃烧烟气中SO_2,NO_x和CO_2的可行性,基于化学热力学原理,分析了9种联合氧化吸收策略的性能,具体的氧化吸收策略包括:H_2O_2-NH_3·H_2O,H_2O_2-MDEA,H_2O_2-NaOH,O3-NH_3·H_2O,O3-MDEA,O3-NaOH,NaClO_2-NH_3·H_2O,NaClO_2-MDEA和NaClO_2-NaOH,并提出新的动态加权法对其性能进行综合评价。结果表明:上述所有策略均具有SO_2,NO_x和CO_2捕获的可行性。O3-NaOH,NaClO_2-MDEA和NaOH做吸收剂的氧化吸收溶液分别对单一脱硫、脱硝和脱碳效果最好。当综合考虑同步脱除SO_2,NO_x和CO_2时,NaClO_2-MDEA优于其他策略,其结果可为燃烧烟气中的气体污染物的联合脱除提供参考。     

Fe_2O_3/TiO_2复合纳米管阵列的制备及其可见光催化性能研究

在氟化铵-乙二醇体系中,采用阳极氧化法在铁基体上制备Fe_2O_3纳米管阵列,然后以氟钛酸铵为钛源,利用水热法在Fe_2O_3纳米管阵列上负载TiO_2纳米片,制得Fe_2O_3/TiO_2复合纳米管阵列,利用SEM、EDS、XRD、TEM、UV-Vis等手段,对所制Fe_2O_3/TiO_2纳米管阵列的表面形貌、物相结构及光催化性能进行表征,并分析Fe_2O_3/TiO_2纳米结构对亚甲基蓝的可见光降解能力。结果表明,Fe_2O_3/TiO_2复合纳米管阵列具有良好的可见光响应;NH_4F浓度为0.4%、水热反应3h制备的Fe_2O_3/TiO_2复合结构具有最佳的光催化性能,对亚甲基蓝的降解率可达90%。     

钴掺杂Mn3O4作为模板制备锂离子电池正极LiMn2O4

以水热合成的钴掺杂Mn₃O₄作为模板,通过固相反应制备尖晶石LiMn₂O₄。XRD谱图和SEM照片显示制备的LiMn₂O₄具有岩石状结构并呈现良好的结晶性,同时Co的引入能够引起LiMn₂O₄晶格的收缩。作为锂离子电池正极材料,Co含量的增加能够提高循环稳定性但降低材料放电比容量,3% Co掺杂的LiMn₂O₄在0.5 C的电流密度下,经过100次循环后,剩余放电比容量达101.6 mAh·g^-1;在10 C的电流密度下,放电比容量可维持在81.0 mAh·g^-1,优于未掺杂的LiMn₂O₄。这是由于Co的引入能够稳定LiMn₂O₄晶体结构并抑制循环中的姜-泰勒扭曲。     

Al2O3/WO3/ZrO2催化剂的制备及在酯交换反应中的研究

以松木为模板,采用模板法将不同含量的Al₂O₃添加到WO₃/ZrO₂复合氧化物中,采用X射线衍射、BET比表面积分析、拉曼光谱和NH₃等温吸附测试等手段对其进行表征,以评估其改进结果。将Al₂O₃/WO₃/ZrO₂催化剂应用到甲醇与乌桕油（非食用油）的酯交换反应中,在其他反应条件相同,Al₂O₃质量分数为3%时,生物柴油最高产率达到83.1%。结果表明：添加Al₂O₃稳定了ZrO₂的四方相结构,使得催化剂比表面积更大、孔数量增加;模板法制备的催化剂孔径分布均匀,WO₃呈高度分散无定型状态;引入Al₂O₃增加了WO₃/ZrO₂催化剂的中强酸性,对弱酸性和强酸性无明显改变。     

纳米Fe2O3-Al2O3复合材料的制备

采用溶胶-凝胶表面包覆法制备了纳米Fe₂O₃-Al₂ O₃复合材料, 利用X射线衍射和透射电镜对样品的物相、 粒度和形貌进行了研 究. 结果表明, α-Fe₂O₃掺杂降低了Al₂O₃相变温度, 在900 ℃可以得到稳定的α-Al₂O₃相.     

Y_2O_3/GeO_2/环氧树脂基辐射防护材料的制备及性能研究

用表面处理稀土氧化物Y_2O_3,GeO_2的方法制备了Y_2O_3/GeO_2/环氧树脂辐射防护材料.采用X射线衍射仪(XRD)研究了材料的微观结构;用多道γ谱仪测试并分析了材料的辐射防护能力.结果表明,制得的材料中的Y_2O_3和GeO_2粒子并未与环氧树脂发生键和反应,Y_2O_3与GeO_2粉末的加入明显提升了材料防护射线的效果.     

Involvement of NADPH oxidase NtrbohD in the rapid production of H2O2 induced by ABA in cultured tobacco cell line BY-2

The mechanisms for the production of hydrogen peroxide (H₂O₂) induced by abscisic acid (ABA) were investigated in suspension culture cells of tobacco BY-2 cells. The results showed that the immediate generation of H₂O₂, which was mainly derived from superoxide dismutase-catalyzed dismutation of superoxide radical, was significantly induced by ABA. Furthermore, treatment of the cultured tobacco cells with ABA resulted in a time-dependent quick increase in plasma membrane (PM) NADPH oxidase activity, which coincided on time and magnitude with the elevation in ABA-induced accumulation of H₂O₂. Moreover, these enhanced effects were pronouncedly inhibited by two NADPH oxidase inhibitor, diphenylene iodonium and imidazole, suggesting that PM NADPH oxidase is involved in the rapid accumulation of ₂O₂ in cultured tobacco cells. In addition, analysis of the expression level of NtrbohD, a PM NADPH oxidase gene in tobacco, by RT-PCR and protein gel blot revealed that the gene at both mRNA and protein levels was upregulated by ABA, indicating that NtrbohD participates in the ABA-stimulated rapid production of H₂O₂ in tobacco culture cells. Taken together, these findings suggest that ABA induces the rapid accumulation of reactive oxygen species via NADPH oxidase in suspension culture cells of tobacco, and that NADPH oxidase and H₂O₂ appear to be important components in ABA signal transduction pathway in plants.     

Acidic catalysis of microporous polyoxometalate H3PW12O40/Sio2 in acetal reaction between benzaldehyde and ethylene glycol

Microporous Keggin-type polyoxometalate material was synthesised by supporting H3PW12O40 into a silica matrix via a sol-gel technique. The silica-supported 12-tungstophosphoric acid ( H₃PW₁₂O₄₀/Sio₂ ) obtained is insoluble and readily separable porous materials with uniform micropores (0. 57 nm) and a high specific surface area (350. 5 m2/g) in oxygen-containing polar solvents. H3PW12 O4o/Si02 was characterized by infrared spectrophotometer (IR). ultraviolet-visible spectrophotometer (UV-vis). inductively coupled plasma (ICP)> thermogravimetric analysis (TGA) and Brunner-Emmett-Teller method (BET) measurements. H3PWi204o/Si02 obtained catalyzed the acetal reaction between benzaldehyde and ethylene glycol to produce 2-phenyl-l > 3-dioxolane more efficiently than the typical solid acids such as SO4 /ZrO2' Nafion-H and H-ZSM-5. Conversion was 93. 8% for benzaldehyde during the reaction period of 2 h. H₃PW₁₂O₄₀/Sio₂ kept its initial activity during three times of reuse. The initial acetal reaction follows a second-order kinetics model at 298 K.     

Involvement of NADPH oxidase NtrbohD in the rapid production of H2O2 induced by ABA in cultured tobacco cell line BY-2

The mechanisms for the production of hydrogen peroxide (H₂O₂) induced by abscisic acid (ABA) were investigated in suspension culture cells of tobacco BY-2 cells. The results showed that the immediate generation of H₂O₂, which was mainly derived from superoxide dismutase-catalyzed dismutation of superoxide radical, was significantly induced by ABA. Furthermore, treatment of the cultured tobacco cells with ABA resulted in a time-dependent quick increase in plasma membrane (PM) NADPH oxidase activity, which coincided on time and magnitude with the elevation in ABA-induced accumulation of H₂O₂. Moreover, these enhanced effects were pronouncedly inhibited by two NADPH oxidase inhibitor, diphenylene iodonium and imidazole, suggesting that PM NADPH oxidase is involved in the rapid accumulation of ₂O₂ in cultured tobacco cells. In addition, analysis of the expression level of NtrbohD, a PM NADPH oxidase gene in tobacco, by RT-PCR and protein gel blot revealed that the gene at both mRNA and protein levels was upregulated by ABA, indicating that NtrbohD participates in the ABA-stimulated rapid production of H₂O₂ in tobacco culture cells. Taken together, these findings suggest that ABA induces the rapid accumulation of reactive oxygen species via NADPH oxidase in suspension culture cells of tobacco, and that NADPH oxidase and H₂O₂ appear to be important components in ABA signal transduction pathway in plants.     

不同形貌LaBO_3型钙钛矿的制备及其催化H_2O_2分解反应性能

采用柠檬酸络合法制备了La BO3(B=Fe,Co,Ni)钙钛矿催化剂,通过X-射线粉末衍射(XRD)、傅立叶-红外光谱(FT-IR)、透射电镜(TEM)、X-射线光电子能谱(XPS)等对催化剂进行了表征,在室温下测定了其对H2O2的催化分解能力.结果表明:催化分解能力依次为La Ni O3>La Co O3>La Fe O3,说明Ni较Co和Fe能更好地分解H2O2.通过改变La Fe O3催化剂的形貌也能提高催化剂性能,如多孔状La Fe O3较负载在SBA-15上的La Fe O3具有更好的催化分解活性.     

Effect of La2O3 on microstructure, mechanical and tribological properties of Ni-W coatings

In this paper, a Ni-W-La2O3 composite coating was prepared by the electrodeposition method. Microhardness tester and environmental scanning electron microscope equipped energy dispersive spectroscopy were employed to investigate the microhardness and the surface morphology of the composite coatings respectively, and the high temperature friction behavior and corrosion resistance of the coatings against molten glass were investigated by using a high temperature tribometer. The results show that La2O3 can refine the microstructure effectively, and make the element distribution uniform, which leads to the increase of average microhardness. La2O3 particulates can reduce the friction coefficient between the composite coating and glass during the sliding process at about 973 K largely, and the corrosion resistance of the La2O3 added Ni-W coatings is effectively improved compared with that of the non-added one, furthermore the mechanism of friction-reducing and anti-corrosion is also discussed.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

层状化合物K0.81Li0.27Ti1.73O4的合成

研究以K₂CO₃,Li₂CO₃和TiO₂为反应原料合成层状钛酸盐K_0.81Li_0.27Ti_1.73O₄过程中合成条件对产物的影响. 结果表明: 反应温度在
1 000~1 200 ℃, 反应原料配比为n(K₂CO₃) ∶n(Li₂CO₃) ∶n(TiO₂)=(0.405~0.42) ∶(0.135~0.165) ∶1.73时, 均可以得到产物K_0.81Li_0.27Ti_1.73O₄, 延长反应时间及升高反应温度均有利于产物的生成; 在1 200 ℃高温条件下, 使用刚玉坩埚为反应容
器时, 最佳的反应条件是： 反应温度为1 100 ℃, 反应原料配比为n(K₂CO₃) ∶n(Li₂CO₃) ∶n(TiO₂)=0.405 ∶0.135 ∶1.73, 反应24 h.     

Sb2O3对十二烷基硫酸钠的吸附及其悬浮液稳定性

The adsorption of sodium dodecyl sulfate (SDS) on the Sb₂O₃/H₂O interface and the stability of Sb₂O₃ suspension have been studied.The results show that the isotherm are of S type for SDS.and the stability of Sb₂O₃ suspension decrease in lower concentration of SDS solution.with increasing it's concentration,the Sb₂O₃ suspension has higher stability.Meanwhile the zeta potential of the suspension is measured and the thermodynamic funtion of the adsorption have been calculation.     

Nb_2O_5/CdS纳米粒子的制备及其光催化性能研究

通过简单的沉淀法合成了Nb2O5/Cd S纳米粒子,利用XRD、TEM、XPS对其进行了表征,采用制备的Nb2O5/Cd S纳米粒子在可见光照射下对罗丹明B进行了降解实验.结果表明:负载在Nb2O5表面上的Cd S粒径大小较均一,约为35 nm,在可见光照射下,Cd S质量比为20%的Nb2O5/Cd S纳米粒子光催化活性最佳,可见光照射下3 h对罗丹明B降解率为98%,经过3次循环利用,发现其具有良好的光催化稳定性.     

原位合成CNTs/Cu-Al2O3复合材料的性能研究

对Al的质量分数分别为0.20%,0.35%,0.60%的Cu-Al合金粉末进行内氧化,得到Cu-Al₂O₃粉末。采用化学气相沉积法在Cu-Al₂O₃粉末表面原位生长碳纳米管(carbon nano tubes, CNTs),采用放电等离子烧结工艺成功制备了CNTs/Cu-Al₂O₃复合材料。采用扫描电子显微镜和透射电子显微镜观察了CNTs/Cu-Al₂O₃复合粉末、复合材料断口的形貌。采用显微硬度计、微拉伸试验机、摩擦磨损试验机分别对纯Cu及复合材料的维氏硬度、抗拉强度、摩擦因数进行测试。采用电化学工作站测试复合材料在3.5%NaCl (质量分数)水溶液中的耐腐蚀性能。结果表明,随着Al的质量分数的增加,粉末表面合成的CNTs的数量也增多。Al的质量分数为0.35%时,CNTs/Cu-Al₂O₃复合材料的综合性能最佳,与纯Cu相比,复合材料的抗拉强度和腐蚀电势分别提高了86.4%和43.2%,分别为315 MPa和-0.268 V,摩擦因数降低了53.3%,仅为0.28。