Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition me...Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.展开更多
A novel heterogeneous catalytic ozonation process in water treatment was studied, with a copper-loaded activated carbon (Cu/AC) that was prepared by an incipient wetness impregnation method at low temperature and te...A novel heterogeneous catalytic ozonation process in water treatment was studied, with a copper-loaded activated carbon (Cu/AC) that was prepared by an incipient wetness impregnation method at low temperature and tested as a catalyst in the ozonation of phenol and oxalic acid. Cu/AC was characterized using XRD, BET and SEM techniques. Compared with ozonation alone, the presence of Cu/AC in the ozonation processes significantly improves the degradation of phenol or oxalic acid. With the introduction of the hydroxyl radical scavenger, i.e., turt-butanol alcohol (t-BuOH), the degradation efficiency of both phenol and oxalic acid in the Cu/AC catalyzed ozonation process decreases by 22% at 30 min. This indicates that Cu/AC accelerates ozone decomposition into certain concentration of hydroxyl radicals. The amount of Cu(II ) produced during the reaction of Cu/AC-catalyzed ozonation of phenol or oxalic acid is very small, which shows that the two processes are both heterogeneous catalytic ozonation reactions.展开更多
Cu2O is a promising photocatalyst,but it suffers from poor photocatalytic activity and stability,especially for Cu2O cubes.Herein,we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface h...Cu2O is a promising photocatalyst,but it suffers from poor photocatalytic activity and stability,especially for Cu2O cubes.Herein,we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface heterostructures(HCs)to improve photocatalytic activity and stability.The apparent quantum efficiency of Au/CuO/Cu2O HCs was ca.123 times that of pristine Cu2O.In addition,the Au/CuO/Cu2O HCs maintained nearly 80%of its original activity after eight cycles in contrast to five cycles for the Au/Cu2O material.Therefore,CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu2O cubes due to the synergistic effect of the HCs.展开更多
A novel biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to activated alumina based on oil shale ash via crosslinking. The adsorbent was characterized by various techni...A novel biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to activated alumina based on oil shale ash via crosslinking. The adsorbent was characterized by various techniques, such as Fourier transform infrared spectroscopy, scarming' elec.tron micros cop.y, the rmogravimetric-differentialthermal analysis, and X-ray photoelectron spectroscope. Batch isothermal equilibrium adsorption experiments were condcted to evaluate the adsorbent for the removal of Cu(Ⅱ) from wastewater. The effect of pH and agitation time on the adsorption capacity was also investigated, indicating that the optimum pH was 6.0. The equilibrium adsorp-tion data were correlated with Langmuir and Freundlich models. The maximum monolayer adsorption capacity of chitosan coated alumina sorbent as obtained from Langmuir adsorption isotherm was fotmd to be 315.46 mg.g-1 for Cu(Ⅱ). The adsorbent loaded with Cu(Ⅱ) was readily regenerated using 0.1 mol.L-1 sodium hydroxide solution. All these indicated that chitosan coated alumina adsorbent not only have high adsorption activity, but also had good stability in the wastewater treatment process.展开更多
A central composite experimental design and response surface method were used to investigate the combined effects of water temperature(18–34℃) and copper ion concentration(0.1–1.5 mg/L) on the catalase(CAT) activit...A central composite experimental design and response surface method were used to investigate the combined effects of water temperature(18–34℃) and copper ion concentration(0.1–1.5 mg/L) on the catalase(CAT) activity in the digestive gland of C rassostrea ariakensis. The results showed that the linear effects of temperature were significant(P <0.01), the quadratic effects of temperature were significant( P <0.05), the linear effects of copper ion concentration were not significant(P >0.05), and the quadratic effects of copper ion concentration were significant(P <0.05). Additionally, the synergistic effects of temperature and copper ion concentration were not significant(P >0.05), and the effect of temperature was greater than that of copper ion concentration. A model equation of CAT enzyme activity in the digestive gland of C. ariakensis toward the two factors of interest was established, with R 2, Adj. R 2 and Pred. R 2 values as high as 0.943 7, 0.887 3 and 0.838 5, respectively. These findings suggested that the goodness of fit to experimental data and predictive capability of the model were satisfactory, and could be practically applied for prediction under the conditions of the study. Overall, the results suggest that the simultaneous variation of temperature and copper ion concentration alters the activity of the antioxidant enzyme CAT by modulating active oxygen species metabolism, which may be utilized as a biomarker to detect the effects of copper pollution.展开更多
A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexa...A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexapods, were formed in high morphological yields (90%) by reducing cupric acetate with o-anisidine or o-phenetidine in the presence of carboxylic acids. The architectures of these Cu2O nanowire polyhedra were examined by electron microscopy, which revealed ordered, highly aligned CU2O nanowires within the polyhedral outlines. The growth of the Cu2O nanowire polyhedra is controlled by the orientation and growth rates of the nanowire branches which are adjusted by addition of carboxylic acids. Compared to the Cu2O samples reported in the recent literature, the Cu2O nanowire octahedra exhibit notably enhanced photocatalytic activities for dye degradation in the presence of H202 under visible light, probably due to the high-density charge carriers photoexcited from the branched nanowires with their special structures. Additionally, the discussion in the recent literature of the photocatalytic activity of Cu2O in the absence of H2O2 for direct photodegradation of dyes seems questionable.展开更多
文摘Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.
基金Project(40973074) supported by the National Natural Science Foundation of China
文摘A novel heterogeneous catalytic ozonation process in water treatment was studied, with a copper-loaded activated carbon (Cu/AC) that was prepared by an incipient wetness impregnation method at low temperature and tested as a catalyst in the ozonation of phenol and oxalic acid. Cu/AC was characterized using XRD, BET and SEM techniques. Compared with ozonation alone, the presence of Cu/AC in the ozonation processes significantly improves the degradation of phenol or oxalic acid. With the introduction of the hydroxyl radical scavenger, i.e., turt-butanol alcohol (t-BuOH), the degradation efficiency of both phenol and oxalic acid in the Cu/AC catalyzed ozonation process decreases by 22% at 30 min. This indicates that Cu/AC accelerates ozone decomposition into certain concentration of hydroxyl radicals. The amount of Cu(II ) produced during the reaction of Cu/AC-catalyzed ozonation of phenol or oxalic acid is very small, which shows that the two processes are both heterogeneous catalytic ozonation reactions.
基金supported by National Natural Science Foundation of China(21573263,21872157,51402346)National Key Research and Development Program of China from Ministry of Science and Technology of China(2016YFE0105700)+2 种基金Jiangsu Provincial Fundamental Research Foundation of China(BK20151236)Henan provincial co-operation and open foundation(60)China Postdoctoral Science Foundation(2018M632984)~~
文摘Cu2O is a promising photocatalyst,but it suffers from poor photocatalytic activity and stability,especially for Cu2O cubes.Herein,we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface heterostructures(HCs)to improve photocatalytic activity and stability.The apparent quantum efficiency of Au/CuO/Cu2O HCs was ca.123 times that of pristine Cu2O.In addition,the Au/CuO/Cu2O HCs maintained nearly 80%of its original activity after eight cycles in contrast to five cycles for the Au/Cu2O material.Therefore,CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu2O cubes due to the synergistic effect of the HCs.
基金Supported by the National Innovative Projects with Cooperation in terms of Production,Study and Research (OSR-05)the National Science and Technology Major Projects (2008ZX05018-005)
文摘A novel biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to activated alumina based on oil shale ash via crosslinking. The adsorbent was characterized by various techniques, such as Fourier transform infrared spectroscopy, scarming' elec.tron micros cop.y, the rmogravimetric-differentialthermal analysis, and X-ray photoelectron spectroscope. Batch isothermal equilibrium adsorption experiments were condcted to evaluate the adsorbent for the removal of Cu(Ⅱ) from wastewater. The effect of pH and agitation time on the adsorption capacity was also investigated, indicating that the optimum pH was 6.0. The equilibrium adsorp-tion data were correlated with Langmuir and Freundlich models. The maximum monolayer adsorption capacity of chitosan coated alumina sorbent as obtained from Langmuir adsorption isotherm was fotmd to be 315.46 mg.g-1 for Cu(Ⅱ). The adsorbent loaded with Cu(Ⅱ) was readily regenerated using 0.1 mol.L-1 sodium hydroxide solution. All these indicated that chitosan coated alumina adsorbent not only have high adsorption activity, but also had good stability in the wastewater treatment process.
基金Supported by the Guangdong Province Science & Technology Project(No.2010B020201014)the Guangdong Province Education Department(No.GCZX-A0909)+2 种基金the Guangdong Province Ocean and Fisheries Science & Technology Extension Project(No.20120980)the Guangdong Province Industry-University-Science Partnership Project(No.20110908)the Sci & Tech Plan of Huaiyin Normal University(No.00wh0031)
文摘A central composite experimental design and response surface method were used to investigate the combined effects of water temperature(18–34℃) and copper ion concentration(0.1–1.5 mg/L) on the catalase(CAT) activity in the digestive gland of C rassostrea ariakensis. The results showed that the linear effects of temperature were significant(P <0.01), the quadratic effects of temperature were significant( P <0.05), the linear effects of copper ion concentration were not significant(P >0.05), and the quadratic effects of copper ion concentration were significant(P <0.05). Additionally, the synergistic effects of temperature and copper ion concentration were not significant(P >0.05), and the effect of temperature was greater than that of copper ion concentration. A model equation of CAT enzyme activity in the digestive gland of C. ariakensis toward the two factors of interest was established, with R 2, Adj. R 2 and Pred. R 2 values as high as 0.943 7, 0.887 3 and 0.838 5, respectively. These findings suggested that the goodness of fit to experimental data and predictive capability of the model were satisfactory, and could be practically applied for prediction under the conditions of the study. Overall, the results suggest that the simultaneous variation of temperature and copper ion concentration alters the activity of the antioxidant enzyme CAT by modulating active oxygen species metabolism, which may be utilized as a biomarker to detect the effects of copper pollution.
基金This work was financially supported by the National Natural Science Foundation of China (No. 21071079), the Research Fund of the State Key Laboratory of Materials-Oriented Chemical Engineering (2009), and the Young Teachers Fund of Nanjing University of Technology.
文摘A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexapods, were formed in high morphological yields (90%) by reducing cupric acetate with o-anisidine or o-phenetidine in the presence of carboxylic acids. The architectures of these Cu2O nanowire polyhedra were examined by electron microscopy, which revealed ordered, highly aligned CU2O nanowires within the polyhedral outlines. The growth of the Cu2O nanowire polyhedra is controlled by the orientation and growth rates of the nanowire branches which are adjusted by addition of carboxylic acids. Compared to the Cu2O samples reported in the recent literature, the Cu2O nanowire octahedra exhibit notably enhanced photocatalytic activities for dye degradation in the presence of H202 under visible light, probably due to the high-density charge carriers photoexcited from the branched nanowires with their special structures. Additionally, the discussion in the recent literature of the photocatalytic activity of Cu2O in the absence of H2O2 for direct photodegradation of dyes seems questionable.