A series of functional,tungsten-containing mesoporous silica materials(W-SiO2) have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and m...A series of functional,tungsten-containing mesoporous silica materials(W-SiO2) have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction(XRD),transmission electron microscopy(TEM),Raman spectroscopy,Fourier transform infrared spectra(FTIR),diffuse reflectance spectra(DRS),and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm(2.9 nm).The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene(DBT),which is able to achieve deep desulfurization within 40 min under the optimal conditions(Catalyst(W-SiO2-20)= 0.01 g,temperature = 60℃,oxidant(H2O2)= 20 μL).For the removal of different organic sulfur compounds within oil,the ability of the catalyst(W-SiO2-20) under the same conditions to remove sulfur compounds decreased in the order:4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.展开更多
Electrochemically treated nanoporous TiO2 was employed as a novel electrode to assist in the pho- toelectrochemical degradation of acetaminophen and valacyclovir. The prepared electrode was characterized by scanning e...Electrochemically treated nanoporous TiO2 was employed as a novel electrode to assist in the pho- toelectrochemical degradation of acetaminophen and valacyclovir. The prepared electrode was characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Cyclic voltammetry (CV), Mott-Schottky plots, ultraviolet-visible light (UV-vis) absorbance spec- troscopy, and a total organic carbon (TOC) analyzer were employed to investigate the photoelec- trochemical degradation of acetaminophen and valacyclovir. The results indicated no obvious re- moval of acetaminophen and valacyclovir over 3 h when separate photochemical degradation and electrochemical oxidation were employed. In contrast, acetaminophen and valacyclovir were rapid- ly eliminated via photoelectrochemical degradation. In addition, electrochemically treated nanopo~ rous TiO2 electrodes significantly enhanced the efficacy of the photoelectrochemical degradation of acetaminophen and valacyclovir, by 86.96% and 53.12%, respectively, when compared with un- treated nanoporous TiO2 electrodes. This enhanced performance may have been attributed to the formation of Ti3~, Ti2~, and oxygen vacancies, as well as an improvement in conductivity during the electrochemical reduction process. The effect of temperature was further investigated, where the activation energy of the photoelectrochemical degradation of acetaminophen and valacyclovir was determined to be 9.62 and 18.42 kJ/mol, respectively.展开更多
Titania-based composite catalysts were prepared through a sol-gel route employing multi-walled carbon nanotubes with different diameters. The materials were characterized using thermogravimetric analysis, nitrogen ads...Titania-based composite catalysts were prepared through a sol-gel route employing multi-walled carbon nanotubes with different diameters. The materials were characterized using thermogravimetric analysis, nitrogen adsorption-desorption isotherm, powder X-ray diffraction, scanning electron microscopy, and diffuse reflectance UV-Vis absorption spectra. The application of the catalysts to photocatalytic degradation of phenol was tested under UV-Vis irradiation. A synergetic effect on phenol removal was observed in case of composite catalysts, which was evaluated in terms of apparent rate constant, total organic carbon removal and photonic efficiency.展开更多
For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at...For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.展开更多
Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability...Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability of severe acid rain. We present the effects of the regional precipitation trend change on the area and intensity of severe acid rain in southern China, and the spatio-temporal distribution characteristics of SO2 and NO2 concentrations are analyzed on the basis of SO2 and NO2 column concentration data. The results are as follows. (1) The emission levels of SO2 and NO2 have reached or passed the precipitation scavenging capacity in parts of southern China owing to the emission totals of SOz and NO2 increasing from 1993 to 2004. (2) Notable changes in the proportion of cities subject to severe acid rain occurred mainly in the south of the middle-lower reaches of the Yangtze River during 1993-2004. With an abrupt change in 1999, the severe acid rain regions were mainly located in central and western China during 1993-1999 and moved obviously eastward to the south of the lower-middle reaches of the Yangtze River with the proportion of cities subject to severe acid rain increasing significantly from 2000 to 2004. (3) The spatial distribution and variation in the seasonal precipitation change rate of more than 10 mm/10a are similar to those of severe acid rain in southern China. An abrupt change in 1999 is seen for winter and summer precipitation, the same as for the proportion of cities subject to severe acid rain in southern China. The significant increase in summer storm precipitation from 1991 to 1999 mitigated the annual precipitation acidity in the south of the Yangtze River and reduced the area of severe acid rainfall. On the other hand, the decrease in storm rainfall in summer expanded the area of severe acid rainfall in the south of the Yangtze River in 2000-2006. Therefore, the change in seasonal precipitation is an important factor in the severe acid rain regions moving eastward and expanding in southern China.展开更多
The core-shell structured TiO2/SiO2 @Fe3O4 photocatalysts were prepared using Fe3O4 as magnetic core,tetraethoxysilane(TEOS) as silica source and tetrabutyl titanate(TBOT) as titanium sources.The as-obtained struc...The core-shell structured TiO2/SiO2 @Fe3O4 photocatalysts were prepared using Fe3O4 as magnetic core,tetraethoxysilane(TEOS) as silica source and tetrabutyl titanate(TBOT) as titanium sources.The as-obtained structure was composed of a SiO2@Fe3O4 core and a porous TiO2 shell.The diameter of SiO2@Fe3O4 core was about 205 nm with thickness of porous TiO2 of about 5-6 nm.The 9%TiO2/6%SiO2@Fe3O4 microspheres possess the highest BET surface area and the BJH pore volume,which are 373.5 m2.g-1 and 0.28 cm3.g-1,respectively.The 9%TiO2/6%SiO2@Fe3O4 photocatalyst exhibited an excellent performance for the degradation of methyl orange and methylene blue dyes.Two different dyes were completely decolorized in 60 min under UV irradiation.The photocatalytic activity and the amount of catalyst were almost not decrease after recycling for 6 times by using external magnetic field.展开更多
The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O va...The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.展开更多
Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the gree...Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the greenhouse gas effect and countering energy crisis,which is an attractive and challenging topic.Hence,various types of photocatalysts have been developed successively to meet the requirements of these photocatalysis.Among them,cobalt‐based heterogeneous catalysts emerge as one of the most promising photocatalysts that open up alluring vistas in the field of solar‐to‐fuels conversion,which can effectively enhance photocatalytic efficiency by extending light absorption range,promoting charge separation,providing active sites,and lowering reaction barrier.In this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation.Second,five efficient strategies including surface modification,morphology modulation,crystallinity controlling,crystal engineering and doping,are discussed for improving the photocatalytic performance with different types cobalt‐based catalysts(cobalt nanoparticles and single atom,oxides,sulfides,phosphides,MOFs,COFs,LDHs,carbide,and nitrides).Third,we outline the applications for the state‐of‐the‐art photocatalytic CO_(2) reduction and water splitting,and nitrogen fixation over cobalt‐based heterogeneous catalysts.Finally,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are presented.The purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.展开更多
Hexagonal porous Nb2O5 was synthesized for the first time via a facile solid-state reaction.The structure and electrochemical properties have been optimized through tuning heating temperature.X-ray diffraction results...Hexagonal porous Nb2O5 was synthesized for the first time via a facile solid-state reaction.The structure and electrochemical properties have been optimized through tuning heating temperature.X-ray diffraction results indicate that pseudo hexagonal Nb2O5(TT-Nb2O5)and orthorhombic Nb2O5 have been synthesized at different temperatures.Hexagonal sheet and porous structure of Nb2O5 were characterized by scanning electron microscopy and N2-adsorption-desorption isotherms.The as-prepared TT-Nb2O5(heated at 600℃)shows the best performance with a remarkable charge capacity of 178 mA∙h/g at 0.2C,which is higher than that of T-Nb2O5.Even at 20℃,TT-Nb2O5 offers unprecedented rate capability up to 86 mA∙h/g.The high rate capacity is due to pseudocapacitive Li+intercalation mechanism of TT-Nb2O5.The reported results demonstrate that Nb2O5 with good crystal structure and high specific surface area is a powerful composite design for high-rate and safe anode materials.展开更多
A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was charac...A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.展开更多
We reported the fabrication of highly porous graphene/TiO2 composite nanofibers in the form of a nonwoven mat by electrospinning followed by calcination in air at 450°C.The graphene can uniformly disperse in high...We reported the fabrication of highly porous graphene/TiO2 composite nanofibers in the form of a nonwoven mat by electrospinning followed by calcination in air at 450°C.The graphene can uniformly disperse in highly porous TiO2 nanofibers.The highly porous graphene/TiO2 composite nanofibers exhibited excellent catalytic activities.The new method for producing graphene/TiO2 composite nanofibers is versatile and can be extended to fabricate various types of metal oxide and graphene nanocomposites.展开更多
A systematic strategy for retrofit of the multi-period heat exchanger network (HEN) on the basis of the multi- objective optimization is developed. In this three-stage procedure, a simplified multi-objective optimiz...A systematic strategy for retrofit of the multi-period heat exchanger network (HEN) on the basis of the multi- objective optimization is developed. In this three-stage procedure, a simplified multi-objective optimization model of the multi-period lIEN is first established and then solved to target the retrofit, aiming to minimizing the total annual cost and total annual CO2 emissions. The obtained Pareto front represents series of retrofit targets under different emission limitations, from which the most desirable one can be selected. The matching of the existing and the required heat exchangers is further implemented to finalize the retrofit, which will meet the practical retrofit requirements and matching restrictions. The application of the proposed procedure is illustrated through a case study of a HEN in a vacuum gas oil hydro-treating unit.展开更多
Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have ...Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have been devoted to exploring the reaction path and developing the photocatalysts.In heterogeneous photocatalysis,among the semiconductor-based photocatalysts,titania(TiO_(2)),as an inexpensive and practically sustainable metal oxides,remains the most extensively studied photocatalyst over the past decades.In this review,we summarize the most recent advances in the solar-driven CO_(2) reduction using TiO_(2)-based photocatalysts,which include the fabrication of heterojunction,surface functional modification,band structure engineering,and morphology design,aiming to improve the CO_(2) conversion efficiency and selectivity to the desired product.Additionally,photoelectrochemical and photothermal approaches are introduced and the fundamental principles to activate and enhance the performance of TiO_(2) for the specific reaction are discussed.The exploration of the solar-driven approaches and discussion on the underlying mechanism allow the comprehensive understanding of CO_(2) photoreduction,that can lead to a rational design and synthesis of TiO_(2)-based photocatalysts.展开更多
Electrochemical CO_(2)reduction to value-added fuels and chemicals is recognized as a promising strategy to alleviate energy shortages and global warming owing to its high efficiency and economic feasibility.Recently,...Electrochemical CO_(2)reduction to value-added fuels and chemicals is recognized as a promising strategy to alleviate energy shortages and global warming owing to its high efficiency and economic feasibility.Recently,understanding the activity origin,selectivity regulation,and reaction mechanisms of CO_(2)reduction reactions(CO_(2)RRs)has become the focus of efficient electrocatalyst design.Polyoxometalates(POMs),a unique class of nanosized metal-oxo clusters,are promising candidates for the development of efficient CO_(2)RR electrocatalysts and,owing to their well-defined structure,remarkable electron/proton storage and transfer ability,and capacities for adsorption and activation of CO_(2),are ideal models for investigating the activity origin and reaction mechanisms of CO_(2)RR electrocatalysts.In this review,we focus on the activity origin and mechanism of CO_(2)RRs and survey recent advances that were achieved by employing POMs in electrocatalytic CO_(2)RRs.We highlight the significant roles of POMs in the electrocatalytic CO_(2)RR process and the main factors influencing selectivity regulation and catalytic CO_(2)RR performance,including the electrolyte,electron-transfer process,and surface characteristics.Finally,we offer a perspective of the advantages and future challenges of POM-based materials in electrocatalytic CO_(2)reduction that could inform new advancements in this promising research field.展开更多
The cycloaddition of epoxides and carbon dioxide represents a straightforward and atom-efficient method for synthesis of cyclic carbonates and utilization of CO2. So far, homogeneous metal complexes have been mainly a...The cycloaddition of epoxides and carbon dioxide represents a straightforward and atom-efficient method for synthesis of cyclic carbonates and utilization of CO2. So far, homogeneous metal complexes have been mainly applied for such transformations. Here, we describe the synthesis of novel heterogeneous Zn-based catalysts, which were conveniently prepared by pyrolysis of an active- carbon-supported phenanthroline-ligated Zn(OAc)2 complex. Detail structural characterizations proved the existence of single zinc sites in the active material. Compared to a Zn-based nanoparticle (Zn-NP) catalyst, the resulting single metal atom catalyst (SAC) displayed improved activity and stability for the cycloaddition of epoxides. By applying the optimal catalyst, a variety of carbonates were successfully obtained in high yields with good functional group tolerance.展开更多
This work proved that biomass-based polyols (sorbitol, xylitol, erythritol, glycerol and ethanediol) were able to be converted into high-value chemical (p-xylene) by catalytic cracking of polyols, alkylation of aromat...This work proved that biomass-based polyols (sorbitol, xylitol, erythritol, glycerol and ethanediol) were able to be converted into high-value chemical (p-xylene) by catalytic cracking of polyols, alkylation of aromatics, and the isomerization of xylenes over the SiO2-modified zeolites. Compared to the conventional HZSM-5 zeolite, the SiO2-containing zeolites considerably increased the selectivity and yield of p-xylene due to the reduction of external surface acidity and the narrowing of pore entrance. The influences of the methanol additive, reaction temperature, and types of polyols on the selectivity and yield of p-xylene were investigated in detail. Catalytic cracking of polyols with methanol significantly enhanced the production of p-xylene by the alkylation of toluene with methanol. The highest p-xylene yield of 10.9 C-mol% with a p-xylene/xylenes ratio of 91.1% was obtained over the 15wt%SiO2/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene was addressed according to the study of the key reactions and the characterization of catalysts.展开更多
A rational integration of multiple reactive centers into a combined unit to facilitate their cooperative effects is a smart approach for accelerating the catalytic activity.Here,to achieve this goal,linear imidazolium...A rational integration of multiple reactive centers into a combined unit to facilitate their cooperative effects is a smart approach for accelerating the catalytic activity.Here,to achieve this goal,linear imidazolium-based ionic polymers were confined into the nanopores of mesoporous silica nanospheres anchored with homogeneously distributed zinc salts.Owing to the flexible character and the reinforced cooperative effects of the ionic liquid(nucleophile)and zinc species(Lewis acid)in the confined mesoporous structure,the resultant composite exhibited dramatically improved catalytic performance in the cycloaddition of CO2 with epoxides to form cyclic carbonates.This was in contrast to that observed for the individual catalytic components.Moreover,such a solid catalyst could be easily recovered and reused four times without a significant loss of activity.展开更多
The water extract of dry mycelium ofPenicillium chrysogenum (DME) was used to induce resistance in Virginia tobacco plants against Phtophthora parasitica var. nicotianae. Results showed that the efficacy of DME in c...The water extract of dry mycelium ofPenicillium chrysogenum (DME) was used to induce resistance in Virginia tobacco plants against Phtophthora parasitica var. nicotianae. Results showed that the efficacy of DME in controlling black shank disease depended on both DME solution concentration and its' treatment methodology. Soil application of 1.5-5% DME 72 hr before inoculation with Phtophthora parasitica vat. nicotianae provided highly significant protection against black shank, relative to the control without DME treatment. Optimized tobacco plant treatment with 2.5% DME significantly increased peroxidase (POD) and polyphenol oxidase (PPO) activity levels in the upper leaf sections of the tobacco plants. DME had no direct antifungal activity on the growth of Phtophthora parasitica var. nicotianae in vitro, suggesting that disease control with DME treatment resulted from the induced propagation of natural defense mechanisms in the tobacco plants.展开更多
In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activate...In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activated components(MgO,Al_(2)O_(3),and Fe_(2)O_(3))were selectively leached by acid solution,resulting in the formation of nanopores in situ.The morphology,structure,surface area and pore-size distribution of the material were characterized by XRD,TG/DSC,^(27)Al MAS NMR,SEM,TEM and N2 adsorption−desorption isotherms.The highest specific surface area(SBET=333 m^(2)/g)was obtained by selectively leaching the 600℃ calcined chlorite from 3 mol/L HCl at 90℃ for 2 h.The pore sizes and specific surface areas can be controlled by calcination and leaching conditions.The ^(27)Al MAS NMR spectra of the samples revealed the relationship between structural transformation and the selective acid leaching properties of thermal-activated chlorite,demonstrating that AlVI transfers into AlV when chlorite changes into activated chlorite during thermal activation,and the coordinations of Al has a significant effect on acid solubility of chlorite.The as-prepared porous silica showed favorable adsorption abilities with capacity of 148.79 mg/g for methylene blue at pH of about 7 and temperature of 25℃,indicating its promising potential in adsorption application.展开更多
基金supported by the National Nature Science Foundation of China(21276117,21376111,21406092)~~
文摘A series of functional,tungsten-containing mesoporous silica materials(W-SiO2) have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction(XRD),transmission electron microscopy(TEM),Raman spectroscopy,Fourier transform infrared spectra(FTIR),diffuse reflectance spectra(DRS),and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm(2.9 nm).The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene(DBT),which is able to achieve deep desulfurization within 40 min under the optimal conditions(Catalyst(W-SiO2-20)= 0.01 g,temperature = 60℃,oxidant(H2O2)= 20 μL).For the removal of different organic sulfur compounds within oil,the ability of the catalyst(W-SiO2-20) under the same conditions to remove sulfur compounds decreased in the order:4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.
基金supported by a Discovery Grant from the Natural Sciences and Engineering Research Council of Canada(NSERC).G.H.Xie thanks the State Scholarship Fund of China Scholarship Council(CSC)the Natural Science Foundation of Henan Province(122300410177).A.C.Chen ac-knowledges NSERCthe Canada Foundation for Innovation for the Canada Research Chair Award~~
文摘Electrochemically treated nanoporous TiO2 was employed as a novel electrode to assist in the pho- toelectrochemical degradation of acetaminophen and valacyclovir. The prepared electrode was characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Cyclic voltammetry (CV), Mott-Schottky plots, ultraviolet-visible light (UV-vis) absorbance spec- troscopy, and a total organic carbon (TOC) analyzer were employed to investigate the photoelec- trochemical degradation of acetaminophen and valacyclovir. The results indicated no obvious re- moval of acetaminophen and valacyclovir over 3 h when separate photochemical degradation and electrochemical oxidation were employed. In contrast, acetaminophen and valacyclovir were rapid- ly eliminated via photoelectrochemical degradation. In addition, electrochemically treated nanopo~ rous TiO2 electrodes significantly enhanced the efficacy of the photoelectrochemical degradation of acetaminophen and valacyclovir, by 86.96% and 53.12%, respectively, when compared with un- treated nanoporous TiO2 electrodes. This enhanced performance may have been attributed to the formation of Ti3~, Ti2~, and oxygen vacancies, as well as an improvement in conductivity during the electrochemical reduction process. The effect of temperature was further investigated, where the activation energy of the photoelectrochemical degradation of acetaminophen and valacyclovir was determined to be 9.62 and 18.42 kJ/mol, respectively.
基金ACKNOWLEDGMENT This work was supported Science Foundation of China by the National Natural (No.20703042).
文摘Titania-based composite catalysts were prepared through a sol-gel route employing multi-walled carbon nanotubes with different diameters. The materials were characterized using thermogravimetric analysis, nitrogen adsorption-desorption isotherm, powder X-ray diffraction, scanning electron microscopy, and diffuse reflectance UV-Vis absorption spectra. The application of the catalysts to photocatalytic degradation of phenol was tested under UV-Vis irradiation. A synergetic effect on phenol removal was observed in case of composite catalysts, which was evaluated in terms of apparent rate constant, total organic carbon removal and photonic efficiency.
基金supported by the National Natural Science Foundation of China(91745106,21633013)the Major Projects of the National Natural Science Foundation of Gansu,China(18JR4RA001)+1 种基金the Youth Innovation Promotion Association CAS(2019409)Fujian Institute of Innovation,CAS and Key Research Program of Frontier Sciences of CAS(QYZDJ-SSW-SLH051)~~
文摘For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.
基金Concentrated fund item of national science and technology foundation work, No.2005DKA31700-06-20Special fund from China Meteorological Administration,No.CCSF2006-32
文摘Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability of severe acid rain. We present the effects of the regional precipitation trend change on the area and intensity of severe acid rain in southern China, and the spatio-temporal distribution characteristics of SO2 and NO2 concentrations are analyzed on the basis of SO2 and NO2 column concentration data. The results are as follows. (1) The emission levels of SO2 and NO2 have reached or passed the precipitation scavenging capacity in parts of southern China owing to the emission totals of SOz and NO2 increasing from 1993 to 2004. (2) Notable changes in the proportion of cities subject to severe acid rain occurred mainly in the south of the middle-lower reaches of the Yangtze River during 1993-2004. With an abrupt change in 1999, the severe acid rain regions were mainly located in central and western China during 1993-1999 and moved obviously eastward to the south of the lower-middle reaches of the Yangtze River with the proportion of cities subject to severe acid rain increasing significantly from 2000 to 2004. (3) The spatial distribution and variation in the seasonal precipitation change rate of more than 10 mm/10a are similar to those of severe acid rain in southern China. An abrupt change in 1999 is seen for winter and summer precipitation, the same as for the proportion of cities subject to severe acid rain in southern China. The significant increase in summer storm precipitation from 1991 to 1999 mitigated the annual precipitation acidity in the south of the Yangtze River and reduced the area of severe acid rainfall. On the other hand, the decrease in storm rainfall in summer expanded the area of severe acid rainfall in the south of the Yangtze River in 2000-2006. Therefore, the change in seasonal precipitation is an important factor in the severe acid rain regions moving eastward and expanding in southern China.
基金Supported by the National Natural Science Foundation of China(21173018,20473009)
文摘The core-shell structured TiO2/SiO2 @Fe3O4 photocatalysts were prepared using Fe3O4 as magnetic core,tetraethoxysilane(TEOS) as silica source and tetrabutyl titanate(TBOT) as titanium sources.The as-obtained structure was composed of a SiO2@Fe3O4 core and a porous TiO2 shell.The diameter of SiO2@Fe3O4 core was about 205 nm with thickness of porous TiO2 of about 5-6 nm.The 9%TiO2/6%SiO2@Fe3O4 microspheres possess the highest BET surface area and the BJH pore volume,which are 373.5 m2.g-1 and 0.28 cm3.g-1,respectively.The 9%TiO2/6%SiO2@Fe3O4 photocatalyst exhibited an excellent performance for the degradation of methyl orange and methylene blue dyes.Two different dyes were completely decolorized in 60 min under UV irradiation.The photocatalytic activity and the amount of catalyst were almost not decrease after recycling for 6 times by using external magnetic field.
基金supported by the National Basic Research Program of China(973 Program,2014CB239302,2013CB632404)the Natural Science Foundation of Jiangsu Province(BK20130053)the National Natural Science Foundation of China(51272101,51202005,21473091)
文摘The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.
文摘Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the greenhouse gas effect and countering energy crisis,which is an attractive and challenging topic.Hence,various types of photocatalysts have been developed successively to meet the requirements of these photocatalysis.Among them,cobalt‐based heterogeneous catalysts emerge as one of the most promising photocatalysts that open up alluring vistas in the field of solar‐to‐fuels conversion,which can effectively enhance photocatalytic efficiency by extending light absorption range,promoting charge separation,providing active sites,and lowering reaction barrier.In this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation.Second,five efficient strategies including surface modification,morphology modulation,crystallinity controlling,crystal engineering and doping,are discussed for improving the photocatalytic performance with different types cobalt‐based catalysts(cobalt nanoparticles and single atom,oxides,sulfides,phosphides,MOFs,COFs,LDHs,carbide,and nitrides).Third,we outline the applications for the state‐of‐the‐art photocatalytic CO_(2) reduction and water splitting,and nitrogen fixation over cobalt‐based heterogeneous catalysts.Finally,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are presented.The purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.
基金Projects(51974137,51774150)supported by the National Natural Science Foundation of ChinaProject(2020M671361)supported by China Postdoctoral Science Foundation。
文摘Hexagonal porous Nb2O5 was synthesized for the first time via a facile solid-state reaction.The structure and electrochemical properties have been optimized through tuning heating temperature.X-ray diffraction results indicate that pseudo hexagonal Nb2O5(TT-Nb2O5)and orthorhombic Nb2O5 have been synthesized at different temperatures.Hexagonal sheet and porous structure of Nb2O5 were characterized by scanning electron microscopy and N2-adsorption-desorption isotherms.The as-prepared TT-Nb2O5(heated at 600℃)shows the best performance with a remarkable charge capacity of 178 mA∙h/g at 0.2C,which is higher than that of T-Nb2O5.Even at 20℃,TT-Nb2O5 offers unprecedented rate capability up to 86 mA∙h/g.The high rate capacity is due to pseudocapacitive Li+intercalation mechanism of TT-Nb2O5.The reported results demonstrate that Nb2O5 with good crystal structure and high specific surface area is a powerful composite design for high-rate and safe anode materials.
基金supported by the National Natural Science Foundation of China (21573099, 21601077, 21573100)~~
文摘A[H3AgI(H2O)PW11O39]3?‐TiO2/ITO electrode was fabricated by immobilizing a molecular polyoxometalate‐based water oxidation catalyst,[H3AgI(H2O)PW11O39]3?(AgPW11),on a TiO2electrode.The resulting electrode was characterized by X‐ray powder diffraction,scanning electron microscopy,and energy dispersive X‐ray spectroscopy.Linear sweep voltammetry,chronoamperometry,and electrochemical impedance measurements were performed in aqueous Na2SO4solution(0.1molL?1).We found that a higher applied voltage led to better catalytic performance by AgPW11.The AgPW11‐TiO2/ITO electrode gave currents respectively10and2.5times as high as those of the TiO2/ITO and AgNO3‐TiO2/ITO electrodes at an applied voltage of1.5V vs Ag/AgCl.This result was attributed to the lower charge transfer resistance at the electrode‐electrolyte interface for the AgPW11‐TiO2/ITO electrode.Under illumination,the photocurrent was not obviously enhanced although the total anode current increased.The AgPW11‐TiO2/ITO electrode was relatively stable.Cyclic voltammetry of AgPW11was performed in phosphate buffer solution(0.1mol L?1).We found that oxidation of AgPW11was a quasi‐reversible process related to one‐electron and one‐proton transfer.We deduced that disproportionation of the oxidized[H2AgII(H2O)PW11O39]3?might have occurred and the resulting[H3AgIIIOPW11O39]3?oxidized water to O2.
基金Project(41271332)supported by the National Natural Science Foundation of China
文摘We reported the fabrication of highly porous graphene/TiO2 composite nanofibers in the form of a nonwoven mat by electrospinning followed by calcination in air at 450°C.The graphene can uniformly disperse in highly porous TiO2 nanofibers.The highly porous graphene/TiO2 composite nanofibers exhibited excellent catalytic activities.The new method for producing graphene/TiO2 composite nanofibers is versatile and can be extended to fabricate various types of metal oxide and graphene nanocomposites.
基金Supported by the National Natural Science Foundation of China(21376188,21676211)
文摘A systematic strategy for retrofit of the multi-period heat exchanger network (HEN) on the basis of the multi- objective optimization is developed. In this three-stage procedure, a simplified multi-objective optimization model of the multi-period lIEN is first established and then solved to target the retrofit, aiming to minimizing the total annual cost and total annual CO2 emissions. The obtained Pareto front represents series of retrofit targets under different emission limitations, from which the most desirable one can be selected. The matching of the existing and the required heat exchangers is further implemented to finalize the retrofit, which will meet the practical retrofit requirements and matching restrictions. The application of the proposed procedure is illustrated through a case study of a HEN in a vacuum gas oil hydro-treating unit.
文摘Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have been devoted to exploring the reaction path and developing the photocatalysts.In heterogeneous photocatalysis,among the semiconductor-based photocatalysts,titania(TiO_(2)),as an inexpensive and practically sustainable metal oxides,remains the most extensively studied photocatalyst over the past decades.In this review,we summarize the most recent advances in the solar-driven CO_(2) reduction using TiO_(2)-based photocatalysts,which include the fabrication of heterojunction,surface functional modification,band structure engineering,and morphology design,aiming to improve the CO_(2) conversion efficiency and selectivity to the desired product.Additionally,photoelectrochemical and photothermal approaches are introduced and the fundamental principles to activate and enhance the performance of TiO_(2) for the specific reaction are discussed.The exploration of the solar-driven approaches and discussion on the underlying mechanism allow the comprehensive understanding of CO_(2) photoreduction,that can lead to a rational design and synthesis of TiO_(2)-based photocatalysts.
文摘Electrochemical CO_(2)reduction to value-added fuels and chemicals is recognized as a promising strategy to alleviate energy shortages and global warming owing to its high efficiency and economic feasibility.Recently,understanding the activity origin,selectivity regulation,and reaction mechanisms of CO_(2)reduction reactions(CO_(2)RRs)has become the focus of efficient electrocatalyst design.Polyoxometalates(POMs),a unique class of nanosized metal-oxo clusters,are promising candidates for the development of efficient CO_(2)RR electrocatalysts and,owing to their well-defined structure,remarkable electron/proton storage and transfer ability,and capacities for adsorption and activation of CO_(2),are ideal models for investigating the activity origin and reaction mechanisms of CO_(2)RR electrocatalysts.In this review,we focus on the activity origin and mechanism of CO_(2)RRs and survey recent advances that were achieved by employing POMs in electrocatalytic CO_(2)RRs.We highlight the significant roles of POMs in the electrocatalytic CO_(2)RR process and the main factors influencing selectivity regulation and catalytic CO_(2)RR performance,including the electrolyte,electron-transfer process,and surface characteristics.Finally,we offer a perspective of the advantages and future challenges of POM-based materials in electrocatalytic CO_(2)reduction that could inform new advancements in this promising research field.
基金supported by the National Key R&D Program of China(2017YFA0403103)the state of Mecklenburg-Vorpommern and the Bundesministerium für Bildung und Forschung~~
文摘The cycloaddition of epoxides and carbon dioxide represents a straightforward and atom-efficient method for synthesis of cyclic carbonates and utilization of CO2. So far, homogeneous metal complexes have been mainly applied for such transformations. Here, we describe the synthesis of novel heterogeneous Zn-based catalysts, which were conveniently prepared by pyrolysis of an active- carbon-supported phenanthroline-ligated Zn(OAc)2 complex. Detail structural characterizations proved the existence of single zinc sites in the active material. Compared to a Zn-based nanoparticle (Zn-NP) catalyst, the resulting single metal atom catalyst (SAC) displayed improved activity and stability for the cycloaddition of epoxides. By applying the optimal catalyst, a variety of carbonates were successfully obtained in high yields with good functional group tolerance.
基金supported by the National Key R&D Program of China (No.2018YFB1501404)
文摘This work proved that biomass-based polyols (sorbitol, xylitol, erythritol, glycerol and ethanediol) were able to be converted into high-value chemical (p-xylene) by catalytic cracking of polyols, alkylation of aromatics, and the isomerization of xylenes over the SiO2-modified zeolites. Compared to the conventional HZSM-5 zeolite, the SiO2-containing zeolites considerably increased the selectivity and yield of p-xylene due to the reduction of external surface acidity and the narrowing of pore entrance. The influences of the methanol additive, reaction temperature, and types of polyols on the selectivity and yield of p-xylene were investigated in detail. Catalytic cracking of polyols with methanol significantly enhanced the production of p-xylene by the alkylation of toluene with methanol. The highest p-xylene yield of 10.9 C-mol% with a p-xylene/xylenes ratio of 91.1% was obtained over the 15wt%SiO2/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene was addressed according to the study of the key reactions and the characterization of catalysts.
基金supported by the National Natural Science Foundation of China(201573136,21603128,U1510105)the Natural Science Foundation for Young Scientists of Shanxi Province(2016021034)the Scientific Research Start-up Funds of Shanxi University(RSC723)~~
文摘A rational integration of multiple reactive centers into a combined unit to facilitate their cooperative effects is a smart approach for accelerating the catalytic activity.Here,to achieve this goal,linear imidazolium-based ionic polymers were confined into the nanopores of mesoporous silica nanospheres anchored with homogeneously distributed zinc salts.Owing to the flexible character and the reinforced cooperative effects of the ionic liquid(nucleophile)and zinc species(Lewis acid)in the confined mesoporous structure,the resultant composite exhibited dramatically improved catalytic performance in the cycloaddition of CO2 with epoxides to form cyclic carbonates.This was in contrast to that observed for the individual catalytic components.Moreover,such a solid catalyst could be easily recovered and reused four times without a significant loss of activity.
文摘The water extract of dry mycelium ofPenicillium chrysogenum (DME) was used to induce resistance in Virginia tobacco plants against Phtophthora parasitica var. nicotianae. Results showed that the efficacy of DME in controlling black shank disease depended on both DME solution concentration and its' treatment methodology. Soil application of 1.5-5% DME 72 hr before inoculation with Phtophthora parasitica vat. nicotianae provided highly significant protection against black shank, relative to the control without DME treatment. Optimized tobacco plant treatment with 2.5% DME significantly increased peroxidase (POD) and polyphenol oxidase (PPO) activity levels in the upper leaf sections of the tobacco plants. DME had no direct antifungal activity on the growth of Phtophthora parasitica var. nicotianae in vitro, suggesting that disease control with DME treatment resulted from the induced propagation of natural defense mechanisms in the tobacco plants.
基金Project(51772153)supported by the National Natural Science Foundation of China。
文摘In this study,porous silica with high surface area was prepared through selective leaching of thermally activated chlorite in HCl solution.In the process,chlorite was activated by pre-calcining treatment,then activated components(MgO,Al_(2)O_(3),and Fe_(2)O_(3))were selectively leached by acid solution,resulting in the formation of nanopores in situ.The morphology,structure,surface area and pore-size distribution of the material were characterized by XRD,TG/DSC,^(27)Al MAS NMR,SEM,TEM and N2 adsorption−desorption isotherms.The highest specific surface area(SBET=333 m^(2)/g)was obtained by selectively leaching the 600℃ calcined chlorite from 3 mol/L HCl at 90℃ for 2 h.The pore sizes and specific surface areas can be controlled by calcination and leaching conditions.The ^(27)Al MAS NMR spectra of the samples revealed the relationship between structural transformation and the selective acid leaching properties of thermal-activated chlorite,demonstrating that AlVI transfers into AlV when chlorite changes into activated chlorite during thermal activation,and the coordinations of Al has a significant effect on acid solubility of chlorite.The as-prepared porous silica showed favorable adsorption abilities with capacity of 148.79 mg/g for methylene blue at pH of about 7 and temperature of 25℃,indicating its promising potential in adsorption application.