In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited...In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.展开更多
A novel fluorescent probe 9-（4-（1,2-diamine）benzene-N1-phenyl）acridine（DABPA） was synthesized for the detection of nitric oxide（NO） and characterized by IR, 1H-NMR and EI-MS spectroscopy. Based on a photoelect...A novel fluorescent probe 9-（4-（1,2-diamine）benzene-N1-phenyl）acridine（DABPA） was synthesized for the detection of nitric oxide（NO） and characterized by IR, 1H-NMR and EI-MS spectroscopy. Based on a photoelectron transfer mechanism, the fl uorescence intensities of DABPA were investigated with the different concentrations of NO. Under the optimal experimental conditions, the fl uorescence intensity of DABPA had a good linear relationship（R2=0.9977） with NO concentration in the range from 1×10-7 to 1.5×10-6 mol/L with a detection limit of 1×10-8 mol/L. The cytotoxicity induced by DABPA was evaluated by the MTT（3-（4,5-dimethylthiazol-2-yl）-2,5diphenyl tetrazolium bromide） assay for biological application. Furthermore, the probe DABPA had also been successfully applied to real-time image NO produced in PC12 cells in the presence of L-arginine.展开更多
A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one ...A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of(Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and(Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of(Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.展开更多
Photoionization/dissociation of 1,2 propylene oxide are performed by using a time of flight mass spectrometer(TOF MS) with vacuum ultraviolet photons from Hefei synchrotron radiation source. The photoionization TOF ma...Photoionization/dissociation of 1,2 propylene oxide are performed by using a time of flight mass spectrometer(TOF MS) with vacuum ultraviolet photons from Hefei synchrotron radiation source. The photoionization TOF mass spectrum and photoionization efficiency(PIE) curves of fragment ions are measured.The appearance potentials(AP) of these ions are obtained from their PIE curves. From these data, the formation enthalpies of the observed ions have been evaluated, and their possible channels have been analyzed. The mechanism of dissociative photoionization of 1,2 propylene oxide has been discussed.展开更多
基金supported by the National Natural Science Foundation of China(32371407,82160421)the Natural Science Foundation of Jiangsu Province(BK20211322)。
文摘In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.
基金Funded by the National Natural Science Foundation of China(Nos.50802069,81100890,51272191)the Fundamental Research Funds for the Central Unversities(WUT:2013-IV-010)the Students Innovation and Entrepreneurship Training Program of WHUT(20141049701012)
文摘A novel fluorescent probe 9-（4-（1,2-diamine）benzene-N1-phenyl）acridine（DABPA） was synthesized for the detection of nitric oxide（NO） and characterized by IR, 1H-NMR and EI-MS spectroscopy. Based on a photoelectron transfer mechanism, the fl uorescence intensities of DABPA were investigated with the different concentrations of NO. Under the optimal experimental conditions, the fl uorescence intensity of DABPA had a good linear relationship（R2=0.9977） with NO concentration in the range from 1×10-7 to 1.5×10-6 mol/L with a detection limit of 1×10-8 mol/L. The cytotoxicity induced by DABPA was evaluated by the MTT（3-（4,5-dimethylthiazol-2-yl）-2,5diphenyl tetrazolium bromide） assay for biological application. Furthermore, the probe DABPA had also been successfully applied to real-time image NO produced in PC12 cells in the presence of L-arginine.
基金supported by the National Key R&D Program of China(2016YFC0204300)the National Natural Science Foundation of China(21477109)~~
文摘A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of(Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and(Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of(Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.
文摘Photoionization/dissociation of 1,2 propylene oxide are performed by using a time of flight mass spectrometer(TOF MS) with vacuum ultraviolet photons from Hefei synchrotron radiation source. The photoionization TOF mass spectrum and photoionization efficiency(PIE) curves of fragment ions are measured.The appearance potentials(AP) of these ions are obtained from their PIE curves. From these data, the formation enthalpies of the observed ions have been evaluated, and their possible channels have been analyzed. The mechanism of dissociative photoionization of 1,2 propylene oxide has been discussed.
