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光催化作用

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It can be used in wastewater treatment including papermaking, leather making, coking, printing and dyeing, heavy metals, pesticide and oil pollution with principles of absorption, flocculus and photocatalysis.

空心微珠在水处理方面的研究涉及造纸废水、制革废水、焦化废水、印染废水、重金属废水、农药废水、石油污染等,其作用原理包括吸附作用,絮凝作用,光催化作用三大方面。

Part two was degradation of organic species in the water by producing porous glass which has the photocatalysis.

第二部分是具有光催化作用的多孔质玻璃球的制备的研究。

Shijiazhuang 050018, ChinaOxidation desulfurization via photocatalysis was investigated by using thiophene in xylol as the model compound, and hydrogen peroxide is used as the oxidant. The effects of hydrogen peroxide mass fraction, high shear agitation time, titanium dioxide mass on the desulfurization efficiency of FCC gasoline were also investigated.

以噻吩的二甲苯溶液作为FCC汽油的模型化合物,双氧水为氧化剂,研究了在光催化作用下,双氧水体积分数、高速均质时间和二氧化钛的加入量等工艺条件对脱硫率的影响,在适宜条件下,模型化合物的脱硫率可达到80%以上。

The results showed that the application of photocatalytic oxidation to the treatment of wastewater was feasible and efficient, but it was affected by the operation conditions.There existed optimum value of the dosage of catalyst, initial benzamide concentration and pH value for the photocatalytic oxidation performance.H2PO-4,Cl-, Cu2+ and Al3+ showed obvious inhibition to the photocatalytic oxidation.

结果表明,循环式浆态光催化反应器中光催化剂的用量、污染物的初始浓度和初始pH值对模拟污染物光催化降解性能的影响存在适宜值;体系中H2PO-4、Cl-、Cu2+、Al3+对其光催化降解过程有明显的抑制作用。

The structural and photocatalytic properties of TiO〓 as well as surface acidity were greatly improved by sulfation. SO〓〓/TiO〓 solid superacid with Hammett constant Ho less than -12.14 was prepared by treating the TiO〓 with 1.0mol. L〓 sulfuric acid solution and then calcining at 450℃ for 3h. When compared to unmodified TiO〓, the SO〓〓/TiO〓 superacid catalyst exhibited higher anatase content, smaller crystal size, higher specific surface area, centralized pore size distribution, and the blue-shifted band edge of uv-vis adsorption spectra. Furthermore, the SO〓〓/TiO〓 superacid also showed excellent reaction activity and stability for CH〓Br photocatalytic decomposition even under the moist reaction conditions. The apparent quantum efficiency of SO〓〓/TiO〓 was 10 times of that of TiO〓 catalyst for the photocatalytic degradation of bromomethane. Therefore, the SO〓〓/TiO〓 superacid catalyst is promising for practical application in environmental remediation.It was found that both L and B acid sites exist on SO〓〓/TiO〓 photocatalyst while only L acid sites on TiO〓 photocatalyst. On the basis of experimental results, the synergistic model of superacidic centers was proposed for SO〓〓/TiO〓 photocatalyst to explain the photocatalytic behavior and the mechanism of superacidifing effects, assuming that the adjacent L and B acid sites induced by SO〓〓 comprise cooperatively the superacidic center on superacid photocatalyst. The group cooperation of the superacidic center could strengthen the surface acidity, increase surface acid sites and the adsorbtion of O〓, promote separation of photogenerated electron-hole pair, enhance the interfacial transfer of charges and reversibility of water adsorption. Consequently the excellent photocatalytic activity, reaction stability and resistibility to humidity of SO〓〓/TiO〓 superacid photocatalyst may attributed to the group cooperated effect of the superacidic center on the photocatalyst.

研究结果表明:SO〓〓与TiO〓表面的结合为螯合式双配位结构;TiO〓光催化剂表面经H〓SO〓浸渍处理后,提高了表面酸性,改善了催化剂结构和光催化性能,当H〓SO〓浸渍浓度为1.0mol.L〓、烧结温度为450℃时,可制得SO〓〓/TiO〓超强酸催化剂(H〓<-12.14),其结构和光催化活性得到明显改善,与TiO〓相比,SO〓〓/TiO〓光催化剂的锐钛矿含量高、晶粒小、BET比表面积大、孔径分布集中、光谱吸收边蓝移,具有优异的光催化氧化活性、稳定性及抗湿性能,光催化降解溴代甲烷的表观量子效率比TiO〓催化剂提高了一个数量级,是一种有实际应用前景的高效光催化剂;由此提出了SO〓〓/TiO〓超强酸催化剂表面集团协同作用的超强酸中心模型,认为在SO〓〓/TiO〓超强酸催化剂表面,由SO〓〓诱导的相邻L酸中心和B酸中心组成了集团协同作用的超强酸中心,其集团协同作用显著地增强了催化剂表面酸性、增大了表面酸量及O〓吸附量、促进了光生电子和空穴的分离及界面电荷转移,具有可逆吸附水的性能,是SO〓〓/TiO〓超强酸催化剂具有优异的光催化氧化活性、很好的活性稳定性及抗湿性能的重要原因。

The apparent quantum efficiency of SO〓〓/TiO〓 was 10 times of that of TiO〓 catalyst for the photocatalytic degradation of bromomethane. Therefore, the SO〓〓/TiO〓 superacid catalyst is promising for practical application in environmental remediation.It was found that both L and B acid sites exist on SO〓〓/TiO〓 photocatalyst while only L acid sites on TiO〓 photocatalyst. On the basis of experimental results, the synergistic model of superacidic centers was proposed for SO〓〓/TiO〓 photocatalyst to explain the photocatalytic behavior and the mechanism of superacidifing effects, assuming that the adjacent L and B acid sites induced by SO〓〓 comprise cooperatively the superacidic center on superacid photocatalyst. The group cooperation of the superacidic center could strengthen the surface acidity, increase surface acid sites and the adsorbtion of O〓, promote separation of photogenerated electron-hole pair, enhance the interfacial transfer of charges and reversibility of water adsorption. Consequently the excellent photocatalytic activity, reaction stability and resistibility to humidity of SO〓〓/TiO〓 superacid photocatalyst may attributed to the group cooperated effect of the superacidic center on the photocatalyst.

研究结果表明:SO〓〓与TiO〓表面的结合为螯合式双配位结构;TiO〓光催化剂表面经H〓SO〓浸渍处理后,提高了表面酸性,改善了催化剂结构和光催化性能,当H〓SO〓浸渍浓度为1.0mol.L〓、烧结温度为450℃时,可制得SO〓〓/TiO〓超强酸催化剂(H〓<-12.14),其结构和光催化活性得到明显改善,与TiO〓相比,SO〓〓/TiO〓光催化剂的锐钛矿含量高、晶粒小、BET比表面积大、孔径分布集中、光谱吸收边蓝移,具有优异的光催化氧化活性、稳定性及抗湿性能,光催化降解溴代甲烷的表观量子效率比TiO〓催化剂提高了一个数量级,是一种有实际应用前景的高效光催化剂;由此提出了SO〓〓/TiO〓超强酸催化剂表面集团协同作用的超强酸中心模型,认为在SO〓〓/TiO〓超强酸催化剂表面,由SO〓〓诱导的相邻L酸中心和B酸中心组成了集团协同作用的超强酸中心,其集团协同作用显著地增强了催化剂表面酸性、增大了表面酸量及O〓吸附量、促进了光生电子和空穴的分离及界面电荷转移,具有可逆吸附水的性能,是SO〓〓/TiO〓超强酸催化剂具有优异的光催化氧化活性、很好的活性稳定性及抗湿性能的重要原因。

Based on a brief review of semiconductor photocatalytic mechanism and researches in the past 30 years on TiO2 heterogeneous photocatalysis, this paper emphasizes that the natural vanadiferous rutile and its modified products, which have not been investigated by either Chinese or foreign research groups, degrade halogenated organic contaminants. By means of grinding, heating in situ, heating, quenching and electron irradiation, the natural rutile could be modified.

在简述半导体光催化理论及TiO2多相光催化作用近30年研究现状的基础上,重点对国内外一直处於空白状态的天然含钒金红石光催化性能进行研究。

On this basis, chosing 15w germicidal lamp with radiation centred at 253. 7nm or 15w blacklight fluorescent lamp with radiation centred at 365nm as the light source respectively, the destruction effects of trace impurities in water by photocatalytic oxidation method using TiO〓 as an immobile phase have been investigated, and the effects are contrasted with photolysis. The investigation is mounted into Phenol aqueous solution, Hydroquinone and Humic Acid aqueous solutions、three representative halohydrocarbons coexisting in main water、the comprehensive index removal of varied trace organic pollutants in main water、the removal of residual chlorine and the disinfecting action, etc..

在此基础上,选择主波长253.7nm的紫外线杀茵灯或主波长365nm的蓝黑管紫外线荧光灯作为光源,研究了TiO〓膜固定相光催化氧化法去除水中微污染物的效果,包括苯酚水溶液、对苯二酚水溶液和腐植酸水溶液的光催化氧化以及自来水中共存的三种典型的氯代烃水溶液三氯甲烷、四氯化碳和四氯乙烯的混合光催化氧化、自来水中有机物总体去除效果以及光催化去除自来水中余氯的作用和光催化的消毒作用等,并进行了光解对比实验。

Again quantised particles can photo-catalyse reactions that bulk semiconductors cannot.

还有,量子化的粒子具有光催化作用,整块的半导体则不能。

The following main results are obtained: The TiO_2 photocatalyst with small crystallite size, high surface area, narrow and uniform pore size distribution, and microporous frameworks could be prepared out by applying MW radiation in the preparation process. The microwave-induced fluorescence technique verified for the first time that microwave enhanced the formation rate of hydroxyl radical, leading to the increase in the photocatalytic efficiency. Compared with the conventional catalyst, TiO_2 prepared by MW dielectric heating owns a higher UV absorption ability, and its optical absorption edge and photovoltaic response are shifted toward the short wavelength region, resulting in increase of photooxidation efficiency. The photocatalytic conversion and the mineralization ratio of acetaldehyde are increased respectively by 30% and 40% over the TiO2 prepared by MW radiation when compared to the TiO2 prepared by the conventional heating. For the MW-assisted photocatalytic reaction over the MW-prepared TiO2, production of hydroxyl radicals is enhanced by 22.5%, and the photocatalytic conversion is accordingly increased by 20%. Similarlly, applying MW also increased the photocatalytic conversion and the mineralization ratio of acetaldehyde over TiO2/Al2O3 sample.

论文得到如下主要结果和结论:(1)微波介电加热TiO_2 溶胶可得到晶粒度小、光催化活性高、比表面积大和孔径分布窄而均一,且微孔发达的TiO_2光催化剂;在溶胶干燥处理过程中微波可使催化剂表面缺陷增加,进而导致光催化反应过程有更多的活性羟基自由基产生;(2)微波制备能显著增强TiO_2 样品的紫外光吸收率,并使其光吸收和光伏响应阈值发生蓝移,从而提高TiO_2的氧化还原能力;(3)与常规加热法所制TiO_2比较,微波法制备的TiO_2对乙醛的光催化降解转化率提高30%,CO_2生成率提高40%以上;(4)与未加微波辐射时相比,发现在光催化反应过程中施加微波,TiO_2 的羟基自由基生成速率提高了22.5%,相应CH_3CHO 光催化降解转化率提高了20%;对Al_2O_3/TiO_2催化剂,CH_3CHO 光催化降解转化率甚至提高了33%,同时CO_2 的生成率也都大幅度提高;(5)微波辐射可改变光催化降解乙醛的产物分布,推断施加微波时乙醛光催化降解按照羟基自由基引发的链式反应机理进行,微波&非热效应&起主要作用。

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