Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catal...Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catalyst (Fe-PEI-CN) by codoping graphitic carbon nitride (CN) with polyethyleneimine ethoxylated (PEI) and Fe species, which demonstrated high activity during p-chlorophenol (p-ClPhOH) degradation via H_(2)O_(2) from the photocatalytic process. The relationship between the catalytic efficiency and the structure was explored using diff erent characterization methods. The Fe modification of CN was achieved through Fe-N coordination, which ensured high dispersion of Fe species and strong stability against leaching during liquid- phase reactions. The Fe modification initiated the Fenton reaction by activating H_(2)O_(2) into ·OH radicals for deep degradation of p-ClPhOH. In addition, it eff ectively promoted light absorption and photoelectron-hole (e-h ^(+) ) separation, corresponding to improved photocatalytic activity. On the other hand, PEI could significantly improve the ability of CN to generate H_(2)O_(2) through visible light photocatalysis. The maximum H_(2)O_(2) yield reached up to 102.6 μmol/L, which was 22 times higher than that of primitive CN. The cooperation of photocatalysis and the self-Fenton reaction has led to high-activity mineralizing organic pollutants with strong durability, indicating good potential for practical application in wastewater treatment.展开更多
ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are sti...ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are still not well understood.Herein,we investigate the activations of CO_(2),O_(2)and CO on single crystalline ZnO polar surfaces at room temperature,through in-situ near-ambient-pressure X-ray photoelectron spectroscopy(NAP-XPS).It is revealed that O_(2)and CO_(2)can undergo chemisorption on ZnO polar surfaces at elevated pressures.On the ZnO(0001)surface,molecular CO_(2)(O_(2))can chemically interact with the top layer Zn atoms,leading to the formation of CO_(2)^(δ-)(O_(2)^(δ-))or partially dissociative atomic oxygen(O-)and hence the electron depletion layer in ZnO.Therefore,an apparent upward band-bending in ZnO(0001)is observed under the CO_(2)and O_(2)exposure.On the ZnO(0001)surface,the molecular chemisorbed CO_(2)(O_(2))mainly bond to the surface oxygen vacancies,which also results in an upward bandbending in ZnO(0001).In contrast,no band-bending is observed for both ZnO polar surfaces upon CO exposure.The electron-acceptor nature of the surface bounded molecules/atoms is responsible for the reversible binding energy shift of Zn 2 p_(3/2)and O 1 s in ZnO.Our findings can shed light on the fundamental understandings of CO_(2)and O_(2)activation on ZnO surfaces,especially the role of ZnO in heterogeneous catalytic reactions.展开更多
Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported...Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide(FTG) nanocomposite synthesized by a facile solvothermal method. The TiO_(2)in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe^(3+)-Fe^(2+)recycle. Meanwhile, the Fe_(2)O_(3)rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectronhole recombination. The high distribution of TiO_(2)and Fe_(2)O_(3)on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.展开更多
A facile approach was developed for synthesizing Au-SH@SO_(3)H-SBA-15 with ordered mesoporous channels by reducing Au^(3+)to Au nanoparticles with SH-group bonded to silica support,followed by in situ coordinating Au ...A facile approach was developed for synthesizing Au-SH@SO_(3)H-SBA-15 with ordered mesoporous channels by reducing Au^(3+)to Au nanoparticles with SH-group bonded to silica support,followed by in situ coordinating Au with the unreacted SH-groups.This catalyst exhibited high efficiency in alkyne hydration owing to the high activity of uniformly dispersed ultrasmall Au nanoparticles,the diminished diffusion limit due to the mesoporous structure,and the promoting effect of acidic SO_(3)H-groups resulting from oxidation of the SH-group by Au^(3+).Meanwhile,the catalyst could be easily recycled and displayed strong durability owing to the strong hydrothermal stability of mesoporous structure and the enhanced stability against Au leaching due to the Au-SH coordination bond.展开更多
A primary amine functionalized ordered mesoporous phenolic resin(NH2-MPR)was obtained by an evaporationinduced self-assembly method.The as-prepared NH2-MPR material possessed large surface area and ordered twodimensio...A primary amine functionalized ordered mesoporous phenolic resin(NH2-MPR)was obtained by an evaporationinduced self-assembly method.The as-prepared NH2-MPR material possessed large surface area and ordered twodimensional hexagonal mesoporous structure.Also,the amine groups were well-dispersed in the mesoporous channels.It can act as an efficient solid base to promote Knoevenagel condensation of various aldehydes with ethyl cyanoacetate in water with high conversion and selectivity.This excellent performance was attributed ordered mesopores and hydrophobic pore surface,which resulted in the decreased the interference of water solvent and the increased active sites accessibility.Noted that it was comparable with homogenous base catalysts in the water-medium Knoevenagel condensation reaction,and it can be reused for at least five times without significant reduction in the catalytic efficiency.展开更多
Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,di...Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.展开更多
A solar-light double illumination photoelectrocatalytic cell(SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II(PS-II, an efficient light-driven water-oxidized enzy...A solar-light double illumination photoelectrocatalytic cell(SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II(PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires(Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate(41.94 mmol/hr), owing to fast electron transfer from PS-II to Cu foam.Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage(0.5 V), and a suitable conduction band potential of Si(-0.6 e V) allowed CO2 to be easily reduced to CH3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2(8.03 mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.展开更多
In the presence of the inexpensive and non-toxic polymethylhydrosiloxane, the combination of copper(II) acetateand a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series...In the presence of the inexpensive and non-toxic polymethylhydrosiloxane, the combination of copper(II) acetateand a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series ofaromatic ketones in air atmosphere and at room temperature. (R)-1-Arylethanols were obtained with up to 99%yield and 93% enantiomeric excess. Meanwhile, the electron effect and steric hindrance of substituents on the aromaticring had an interesting influence on both the yields and enantioselectivities. Furthermore, a possible mechanismwas presented to explain the influence of some key factors on the reaction.展开更多
基金the National Key Research and Development Program of China (No. 2020YFA0211004)Key Grant of Nation Science Funding of China (No. 22236005)+5 种基金Nation Science Funding of China (No. 22376141)Ministry of Education of China (No. PCSIRT_IRT_16R49)“111” Innovation and Talent Recruitment Base (D18020)Shanghai Government (No. 20ZR1440700)Shanghai Engineering Research Center of Green Energy Chemical Engineering (No. 18DZ2254200)Scientific and Technological Innovation Team for Green Catalysis and Energy Materialien Yunnan Institutions of Higher Learning, and Surface project of Yunnan Province science and technology Department (No. 20210 A070001-050).
文摘Deep degradation of organic pollutants by sunlight-induced coupled photocatalytic and Fenton (photo-Fenton) reactions is of immense importance for water purification. In this work, we report a novel bifunctional catalyst (Fe-PEI-CN) by codoping graphitic carbon nitride (CN) with polyethyleneimine ethoxylated (PEI) and Fe species, which demonstrated high activity during p-chlorophenol (p-ClPhOH) degradation via H_(2)O_(2) from the photocatalytic process. The relationship between the catalytic efficiency and the structure was explored using diff erent characterization methods. The Fe modification of CN was achieved through Fe-N coordination, which ensured high dispersion of Fe species and strong stability against leaching during liquid- phase reactions. The Fe modification initiated the Fenton reaction by activating H_(2)O_(2) into ·OH radicals for deep degradation of p-ClPhOH. In addition, it eff ectively promoted light absorption and photoelectron-hole (e-h ^(+) ) separation, corresponding to improved photocatalytic activity. On the other hand, PEI could significantly improve the ability of CN to generate H_(2)O_(2) through visible light photocatalysis. The maximum H_(2)O_(2) yield reached up to 102.6 μmol/L, which was 22 times higher than that of primitive CN. The cooperation of photocatalysis and the self-Fenton reaction has led to high-activity mineralizing organic pollutants with strong durability, indicating good potential for practical application in wastewater treatment.
基金financial supports from the National Natural Science Foundation of China(Grant no.91645102 and 22002031)the Singapore National Research Foundation under the grant of NRF2017NRF-NSFC001-007the NUS Flagship Green Energy Programme。
文摘ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are still not well understood.Herein,we investigate the activations of CO_(2),O_(2)and CO on single crystalline ZnO polar surfaces at room temperature,through in-situ near-ambient-pressure X-ray photoelectron spectroscopy(NAP-XPS).It is revealed that O_(2)and CO_(2)can undergo chemisorption on ZnO polar surfaces at elevated pressures.On the ZnO(0001)surface,molecular CO_(2)(O_(2))can chemically interact with the top layer Zn atoms,leading to the formation of CO_(2)^(δ-)(O_(2)^(δ-))or partially dissociative atomic oxygen(O-)and hence the electron depletion layer in ZnO.Therefore,an apparent upward band-bending in ZnO(0001)is observed under the CO_(2)and O_(2)exposure.On the ZnO(0001)surface,the molecular chemisorbed CO_(2)(O_(2))mainly bond to the surface oxygen vacancies,which also results in an upward bandbending in ZnO(0001).In contrast,no band-bending is observed for both ZnO polar surfaces upon CO exposure.The electron-acceptor nature of the surface bounded molecules/atoms is responsible for the reversible binding energy shift of Zn 2 p_(3/2)and O 1 s in ZnO.Our findings can shed light on the fundamental understandings of CO_(2)and O_(2)activation on ZnO surfaces,especially the role of ZnO in heterogeneous catalytic reactions.
基金supported by the National Key Research and Development Program of China (No.2020YFA0211004)the National Natural Science Foundation of China (Nos.22176128 and 21876114)+4 种基金the Program of Shanghai Academic Research Leader (No. 21XD1422800)Shanghai Government (Nos. 19DZ1205102 and 19160712900)Chinese Education Ministry Key Laboratory and International Joint Laboratory on Resource Chemistry, and Shanghai Eastern Scholar Program, “111 Innovation and Talent Recruitment Base on Photochemical and Energy Materials” (No. D18020)Shanghai Engineering Research Center of Green Energy Chemical Engineering (No. 18DZ2254200)Shanghai Frontiers Science Center of Biomimetic Catalysis。
文摘Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide(FTG) nanocomposite synthesized by a facile solvothermal method. The TiO_(2)in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe^(3+)-Fe^(2+)recycle. Meanwhile, the Fe_(2)O_(3)rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectronhole recombination. The high distribution of TiO_(2)and Fe_(2)O_(3)on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.
基金the National Natural Science Foundation of China(21237003,21261140333)the Project from College Natural Science Research Plan of Jiangsu Province(13KJB150008)and Project of Huaian City(HAG2013077).
文摘A facile approach was developed for synthesizing Au-SH@SO_(3)H-SBA-15 with ordered mesoporous channels by reducing Au^(3+)to Au nanoparticles with SH-group bonded to silica support,followed by in situ coordinating Au with the unreacted SH-groups.This catalyst exhibited high efficiency in alkyne hydration owing to the high activity of uniformly dispersed ultrasmall Au nanoparticles,the diminished diffusion limit due to the mesoporous structure,and the promoting effect of acidic SO_(3)H-groups resulting from oxidation of the SH-group by Au^(3+).Meanwhile,the catalyst could be easily recycled and displayed strong durability owing to the strong hydrothermal stability of mesoporous structure and the enhanced stability against Au leaching due to the Au-SH coordination bond.
基金This work is supported by the National Natural Science Foundation of China(No.21677098)Shanghai government(Nos.19SG42,19520710700 and 18230742500)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(No.TP2016034).
文摘A primary amine functionalized ordered mesoporous phenolic resin(NH2-MPR)was obtained by an evaporationinduced self-assembly method.The as-prepared NH2-MPR material possessed large surface area and ordered twodimensional hexagonal mesoporous structure.Also,the amine groups were well-dispersed in the mesoporous channels.It can act as an efficient solid base to promote Knoevenagel condensation of various aldehydes with ethyl cyanoacetate in water with high conversion and selectivity.This excellent performance was attributed ordered mesopores and hydrophobic pore surface,which resulted in the decreased the interference of water solvent and the increased active sites accessibility.Noted that it was comparable with homogenous base catalysts in the water-medium Knoevenagel condensation reaction,and it can be reused for at least five times without significant reduction in the catalytic efficiency.
基金the National Key Technology R&D Program of China(No.2016YFA0202704)Beijing Municipal Science 8c Technology Commission(Nos.Z171100000317001,Z171100002017017,and Y3993113DF)the National Natural Science Foundation of China(Nos.51432005,5151101243,51561145021,and 21761142011).
文摘Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.
基金supported by the National Natural Science Foundation of China (No. 21477079, 21677099, 21237003)the Shanghai Government (No. 11ZR1426300, 13YZ054, 14ZR1430900)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT1269)the International Joint Laboratory on Resource Chemistry (No. IJLRC)
文摘A solar-light double illumination photoelectrocatalytic cell(SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II(PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires(Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate(41.94 mmol/hr), owing to fast electron transfer from PS-II to Cu foam.Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage(0.5 V), and a suitable conduction band potential of Si(-0.6 e V) allowed CO2 to be easily reduced to CH3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2(8.03 mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.
基金the National Natural Science Foundation of China(No.21402066)the Open Project of the Key Laboratory of the Chinese Ministry of Education in Resource Chemistry.
文摘In the presence of the inexpensive and non-toxic polymethylhydrosiloxane, the combination of copper(II) acetateand a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series ofaromatic ketones in air atmosphere and at room temperature. (R)-1-Arylethanols were obtained with up to 99%yield and 93% enantiomeric excess. Meanwhile, the electron effect and steric hindrance of substituents on the aromaticring had an interesting influence on both the yields and enantioselectivities. Furthermore, a possible mechanismwas presented to explain the influence of some key factors on the reaction.