TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracyc...TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.展开更多
A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic（PEC） oxidation system was established by o-phenanthroline-Fe（Ⅱ）（Fe（phen）3^2＋） spectrophotometr...A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic（PEC） oxidation system was established by o-phenanthroline-Fe（Ⅱ）（Fe（phen）3^2＋） spectrophotometry and using anion exchange membrane. Fe （phen）3^2＋ can be oxidized to o-phenanthroline-Fe（Ⅲ）（Fe（phen）3^3＋） by strong oxidization of hydroxyl radicals（·OH）. Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe（phen）3^3＋ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 （isoelectric point）, and the change direction of pH after illumination tended to nearby isoelectric point.展开更多
A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· rad...A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.展开更多
The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun（n=1-6） clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the ab...The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun（n=1-6） clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the absorption of CH2 on Cu clusters is stronger than the case of CH3. The vibrational frequencies of C-H bonding agree with the experimental results obtained for CH2 and CH3 absorbed on Cu（111）. With the increase of cluster size, the softening （Einstein shift） of C-H vibrational modes become stronger.展开更多
Photolysis rate （J1） and reaction rate constants （kl） for the biacetyl （butane-2,3-dione） were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source...Photolysis rate （J1） and reaction rate constants （kl） for the biacetyl （butane-2,3-dione） were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source. The OH radicals was generated by H2OE/UV process and biacetyl （CH3C（O）C（O）CH3） concentrations were monitored using 2,4-DNPH derivatization method. 2,3-butanedione molecule is widely present in the atmosphere, it have been detected in hydrometeors （fogs, rain, and clouds） and at a significant yield （up to 10μmolar）. The measurements were performed at 294 K and with free pH values. Our results lead to the following obtained values： J1= 3×10^-4 S^-1 and k1 = （6.17±0.95）×10^8 M^-1·s^-1.The uncertainty listed above is ±15%.展开更多
Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discha...Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discharge of a mixture of PHa and SF6 in argon. Seven vibronic bands with fine rotational structures have been observed and assigned as 0 0^, 2 0^n, and 2 1^n （n=1- 3） bands of the A^2A1- X~ 2B1 electronic transition. Rotational assignments and rotational term values for each band were re-identified, and the molecular parameters including rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also improved with reasonably high precision. In addition, large perturbations observed in each quantum number of total angular momentum of the a axis level of the excited vibronic states were briefly discussed.展开更多
In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several o...In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (co =30 mg·1-1) is completely converted within 2h at 30℃ and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.展开更多
Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical p...Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.展开更多
文摘TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.
文摘A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic（PEC） oxidation system was established by o-phenanthroline-Fe（Ⅱ）（Fe（phen）3^2＋） spectrophotometry and using anion exchange membrane. Fe （phen）3^2＋ can be oxidized to o-phenanthroline-Fe（Ⅲ）（Fe（phen）3^3＋） by strong oxidization of hydroxyl radicals（·OH）. Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe（phen）3^3＋ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 （isoelectric point）, and the change direction of pH after illumination tended to nearby isoelectric point.
文摘A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals （HOC2H4O2·） in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.
文摘The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun（n=1-6） clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the absorption of CH2 on Cu clusters is stronger than the case of CH3. The vibrational frequencies of C-H bonding agree with the experimental results obtained for CH2 and CH3 absorbed on Cu（111）. With the increase of cluster size, the softening （Einstein shift） of C-H vibrational modes become stronger.
文摘Photolysis rate （J1） and reaction rate constants （kl） for the biacetyl （butane-2,3-dione） were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source. The OH radicals was generated by H2OE/UV process and biacetyl （CH3C（O）C（O）CH3） concentrations were monitored using 2,4-DNPH derivatization method. 2,3-butanedione molecule is widely present in the atmosphere, it have been detected in hydrometeors （fogs, rain, and clouds） and at a significant yield （up to 10μmolar）. The measurements were performed at 294 K and with free pH values. Our results lead to the following obtained values： J1= 3×10^-4 S^-1 and k1 = （6.17±0.95）×10^8 M^-1·s^-1.The uncertainty listed above is ±15%.
基金This work was supported by the National Natural Science Foundation of China （No.20673107）, the National Key Basic Research Special Foundation of China （No.2007CB815203）, and the Chinese Academy of Sciences （No.KJCX2-SW-H08）.
文摘Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discharge of a mixture of PHa and SF6 in argon. Seven vibronic bands with fine rotational structures have been observed and assigned as 0 0^, 2 0^n, and 2 1^n （n=1- 3） bands of the A^2A1- X~ 2B1 electronic transition. Rotational assignments and rotational term values for each band were re-identified, and the molecular parameters including rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also improved with reasonably high precision. In addition, large perturbations observed in each quantum number of total angular momentum of the a axis level of the excited vibronic states were briefly discussed.
基金The project supported in part by the Project of Key Science and Technology of Education Ministry (00250)the Nature Science Foundation of Gansu Province (3ZS041-A25-028)the Invention Project of Science and Technology (KJCXGC-01, NWNU), 2000
文摘In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (co =30 mg·1-1) is completely converted within 2h at 30℃ and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.
文摘Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.
