Crystalline carbon nitride(CCN)prepared by a molten-salt method is attracting increased attention because of its promising properties and excellent photocatalytic activity.In this work,we further improve the crystalli...Crystalline carbon nitride(CCN)prepared by a molten-salt method is attracting increased attention because of its promising properties and excellent photocatalytic activity.In this work,we further improve the crystallinity of CCN through synthesis by the molten-salt method under the action of aqueous hydrochloric acid(HCl)solution.Our results showed that the crystallinity of the as-prepared samples increased with increasing HCl concentration and reached the maximum value at 0.1 mol L^-1.This can be attributed to the removal of some potassium ions(K+)from the terminal amino groups of CCN by the aqueous HCl solution,which results in a release of the polymerization sites.As a result,the crystallinity of the as-prepared samples further increased.Moreover,the obtained 0.1 highly crystalline carbon nitride(0.1HCCN;treated with 0.1 mol L^-1 aqueous HCl solution)exhibited an excellent photocatalytic hydrogen evolution of 683.54μmol h^-1 g^-1 and a quantum efficiency of 6.6%at 420 nm with triethanolamine as the sacrificial agent.This photocatalytic hydrogen evolution was 2 and 10 times higher than those of CCN and bulk carbon nitride,respectively.The enhanced photocatalytic activity was attributed to the improved crystallinity and intercalation of K+into the xHCCN interlayer.The improved crystallinity can decrease the number of surface defects and hydrogen bonds in the as-prepared sample,thereby increasing the mobility of the photoinduced carriers and reducing the recombination sites of the electron-hole pairs.The K+intercalated into the xHCCN interlayer also promoted the transfer of the photoinduced electrons because these ions can increase the electronic delocalization and extend theπ-conjugated systems.This study may provide new insights into the further development of the molten-salt method.展开更多
As an important part of the soil phosphorus(P)pool,organic P(OP)is widely found in terrestrial and aquatic environments(e.g.,soils and sediments).The interfacial behavior of OP on natural minerals affects the transpor...As an important part of the soil phosphorus(P)pool,organic P(OP)is widely found in terrestrial and aquatic environments(e.g.,soils and sediments).The interfacial behavior of OP on natural minerals affects the transport,transformation,and bioavailability of P in the environment.This paper reviews the processes involving adsorption-desorption,dissolution-precipitation,and enzymatic/mineral-mediated hydrolysis of OP at the mineral-water interface,and their subsequent effects on OP speciation and mineral colloidal stability/reactivity.The sorption mechanisms of OP on natural minerals mainly include surface complexation and precipitation,which are controlled by factors such as mineral identity and crystallinity,the relative molecular weight of OP,reaction pH,ionic strength,temperature,and co-existing ligands or ions.The desorption amount and rate of OP from minerals are determined by the mineral identity,desorbent type,pre-sorption time,OP species,reaction pH,number of desorption cycles,and redox status.The interactions between OP and minerals affect the sorption of co-existing metal ions and the stability of the minerals.The effect of minerals on the enzymatic hydrolysis of OP sorbed on mineral surfaces depends on the mineral identity and OP species.Some minerals also exhibit catalytic activity to promote the cleavage of C–O–P bonds and OP hydrolysis.We provide an overview of state-of-the-art techniques currently applied in environmental OP research.The main challenges and future research directions are also summarized to further explore OP interactions with natural minerals in complex environmental settings.展开更多
Oxidation of Mn (Ⅱ) or As(Ⅲ) by molecular oxygen is slow at pH<9,while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water.However,the reaction mechanisms...Oxidation of Mn (Ⅱ) or As(Ⅲ) by molecular oxygen is slow at pH<9,while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water.However,the reaction mechanisms on simultaneous oxidation of Mn(Ⅱ) and As (Ⅲ)on oxide mineral surface and their accompanied removal efficiency remain unclear.This study compared Mn (Ⅱ) oxidation on four common metal oxides (γ-Al_(2)O_(3),CuO,α-Fe2O_(3)and ZnO) and investigated the simultaneous oxidation and removal of Mn (Ⅱ) and As (Ⅲ) through batch experiments and spectroscopic analyses.Among the tested oxides,CuO and α-Fe2O_(3)possess greater catalytic activity toward Mn (Ⅱ) oxidation.Oxidation and removal kinetics of Mn (Ⅱ) and As (Ⅲ) on CuO indicate that O_(2)is the terminal electron acceptor for Mn (Ⅱ) and As (Ⅲ) oxidation on CuO,and Mn (Ⅱ) acts as an electron shuttle to promote As (Ⅲ) oxidation and removal.The main oxidized product of Mn (Ⅱ) on CuO is high-valent MnO_(x)species.This newly formed Mn (Ⅲ) or Mn (IV) phases promote As (Ⅲ) oxidation on CuO at circumneutral pH 8 and is reduced to Mn (Ⅱ),which may be then released into solution.This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn (Ⅱ) and As (Ⅲ) and suggests that CuO should be considered as an efficient material to remediate Mn (Ⅱ) and As(Ⅲ)contamination.展开更多
Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese ox...Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese oxides,i.e,acidic birnessite (BIR-H),alkaline birnessite (BIR-OH),cryptomelane (CRY) and todorokite (TOD),were comparatively investigated.To elucidate phenol degradation mechanisms,X-ray diffraction (XRD),ICP-AES (inductively coupled plasma-atomic emission spectroscopy),TEM (transmission electronic microscope),N 2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS) were employed to characterize the structural,compositional,morphological,specific surface area and optical absorption properties of the manganese oxides.After 12 hr of UV-Vis irradiation,the total organic carbon (TOC) removal rate reached 62.1%,43.1%,25.4%,and 22.5% for cryptomelane,acidic birnessite,todorokite and alkaline birnessite,respectively.Compared to the reactions in the dark condition,UV- Vis exposure improved the TOC removal rates by 55.8%,31.9%,23.4% and 17.9%.This suggests a weak ability of manganese oxides to degrade phenol in the dark condition,while UV-Vis light irradiation could significantly enhance phenol degradation.The manganese minerals exhibited photocatalytic activities in the order of:CRY BIR-H TOD BIR-OH.There may be three possible mechanisms for photochemical degradation:(1) direct photolysis of phenol;(2) direct oxidation of phenol by manganese oxides;(3) photocatalytic oxidation of phenol by manganese oxides.Photocatalytic oxidation of phenol appeared to be the dominant mechanism.展开更多
A four-year project,entitled"The mechanisms of fraction transformation and high use efficiency of P fertilizer in Chinese cropping systems"commenced in 2017.The project was established to answer three key qu...A four-year project,entitled"The mechanisms of fraction transformation and high use efficiency of P fertilizer in Chinese cropping systems"commenced in 2017.The project was established to answer three key questions and looked at 17 cropping systems on ten soils.First,we asked what are the dynamics of transformation,fixation and mobilization of P fertilizers in soil-cropping systems?Second,what are the mechanisms of soil-cropmicrobe interactions by which P fertilizer can be efficiently used?Third,how to manipulate the processes of P use in cropping systems?The targets of this project are(1)to explore the mechanisms of P fixation,the pathways of loss of P availability and the threshold of migration of fertilizer P in the field;(2)to uncover mechanisms by which soil legacy P is mobilized through root physiological and morphological processes and through arbuscular mycorrhizal fungi and P-solubilizing bacteria in rhizosphere and hyphosphere;(3)to estimate the biological potential of crops for high efficiency P absorption and use;(4)to innovate new approaches for improving the efficiency of P fertilizers.The outcomes will provide theoretical support for setting standards for limitation of P fertilizer application rate in the main cropping zones of China.展开更多
Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterize...Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterized by powder X-ray diffraction(XRD), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), Fourier transform infrared spectroscopy(FT-IR) and extended X-ray absorption fine structure(EXAFS)spectroscopy. The adsorption behavior of these samples towards PO43-was also investigated. Characterization results demonstrated that increasing Al content in goethite led to a reduction in crystallinity, increase in specific surface area(SSA), and morphology change from needle-like to granular. Rietveld structure refinement revealed that the lattice parameter a remained almost constant and b slightly decreased, but c was significantly reduced, and the calculated crystal density increased. EXAFS analysis demonstrated that the Fe(Al)–O distance in the structure of the doped goethites was almost the same, but the Fe–Fe(Al) distance decreased with increasing Al content. Surface analysis showed that, with increasing Al content, the content of OH groups on the mineral surface increased. The adsorption of phosphate per unit mass of Al-doped goethite increased, while adsorption per unit area decreased owing to the decrease of the relative proportion of(110) facets in the total surface area of the minerals. The results of this research facilitate better understanding of the effect of Al substitution on the structure and properties of goethite and the cycling of phosphate in the environment.展开更多
Cryptomelane is a reactive Mn oxide and has been used in removal of heavy metal from wastewaters. Co-doped cryptomelane was synthesized by refluxing at ambient pressure and characterized by powder X-ray diffraction, s...Cryptomelane is a reactive Mn oxide and has been used in removal of heavy metal from wastewaters. Co-doped cryptomelane was synthesized by refluxing at ambient pressure and characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and extended X-ray absorption fine structure spectroscopy, and its performances for removal of Pb^2+ and Cr^3+ from aqueous solutions were investigated. Co doping has a negligible effect on the structure and morphology of cryptomelane but increases the specific surface area and Mn average oxidation state. Mn and Co K-edge extended X-ray absorption fine structure spectroscopy(EXAFS) analysis shows that Co barely affects the atomic coordination environments of Mn, and distances of edge- and corner-sharing Co–Me(Me_Co, Mn) pairs are shorter than those of the corresponding Mn–Me pairs, implying the replacement of framework Mn(III) by Co(III). These Co-doped cryptomelanes can quickly oxidize Cr3+to be HCr O4-and remove 45%–66% of the total Cr in the reaction systems by adsorption and fixation, and they have enhanced Pb2+adsorption capacities. Thus these materials are promising adsorbents for heavy metal remediation. The results demonstrate the design and modification of environmental friendly Mn oxide materials and can help us understand the interaction mechanisms of transition metals with Mn oxides.展开更多
基金supported by the National Natural Science Foundation of China(51672099,21403079)Sichuan Science and Technology Program(2019JDRC0027)Fundamental Research Funds for the Central Universities(2017-QR-25)~~
文摘Crystalline carbon nitride(CCN)prepared by a molten-salt method is attracting increased attention because of its promising properties and excellent photocatalytic activity.In this work,we further improve the crystallinity of CCN through synthesis by the molten-salt method under the action of aqueous hydrochloric acid(HCl)solution.Our results showed that the crystallinity of the as-prepared samples increased with increasing HCl concentration and reached the maximum value at 0.1 mol L^-1.This can be attributed to the removal of some potassium ions(K+)from the terminal amino groups of CCN by the aqueous HCl solution,which results in a release of the polymerization sites.As a result,the crystallinity of the as-prepared samples further increased.Moreover,the obtained 0.1 highly crystalline carbon nitride(0.1HCCN;treated with 0.1 mol L^-1 aqueous HCl solution)exhibited an excellent photocatalytic hydrogen evolution of 683.54μmol h^-1 g^-1 and a quantum efficiency of 6.6%at 420 nm with triethanolamine as the sacrificial agent.This photocatalytic hydrogen evolution was 2 and 10 times higher than those of CCN and bulk carbon nitride,respectively.The enhanced photocatalytic activity was attributed to the improved crystallinity and intercalation of K+into the xHCCN interlayer.The improved crystallinity can decrease the number of surface defects and hydrogen bonds in the as-prepared sample,thereby increasing the mobility of the photoinduced carriers and reducing the recombination sites of the electron-hole pairs.The K+intercalated into the xHCCN interlayer also promoted the transfer of the photoinduced electrons because these ions can increase the electronic delocalization and extend theπ-conjugated systems.This study may provide new insights into the further development of the molten-salt method.
基金supported by the National Natural Science Foundation of China(Nos.42030709 and 42167031).
文摘As an important part of the soil phosphorus(P)pool,organic P(OP)is widely found in terrestrial and aquatic environments(e.g.,soils and sediments).The interfacial behavior of OP on natural minerals affects the transport,transformation,and bioavailability of P in the environment.This paper reviews the processes involving adsorption-desorption,dissolution-precipitation,and enzymatic/mineral-mediated hydrolysis of OP at the mineral-water interface,and their subsequent effects on OP speciation and mineral colloidal stability/reactivity.The sorption mechanisms of OP on natural minerals mainly include surface complexation and precipitation,which are controlled by factors such as mineral identity and crystallinity,the relative molecular weight of OP,reaction pH,ionic strength,temperature,and co-existing ligands or ions.The desorption amount and rate of OP from minerals are determined by the mineral identity,desorbent type,pre-sorption time,OP species,reaction pH,number of desorption cycles,and redox status.The interactions between OP and minerals affect the sorption of co-existing metal ions and the stability of the minerals.The effect of minerals on the enzymatic hydrolysis of OP sorbed on mineral surfaces depends on the mineral identity and OP species.Some minerals also exhibit catalytic activity to promote the cleavage of C–O–P bonds and OP hydrolysis.We provide an overview of state-of-the-art techniques currently applied in environmental OP research.The main challenges and future research directions are also summarized to further explore OP interactions with natural minerals in complex environmental settings.
基金supported by the National Natural Science Foundation of China (Nos. 42030709, 42167031)the National Key Research and Development Program of China (No. 2017YFD0200201)Y.T. acknowledges support by the U.S. National Science Foundation (NSF) under Grant No. 2108688。
文摘Oxidation of Mn (Ⅱ) or As(Ⅲ) by molecular oxygen is slow at pH<9,while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water.However,the reaction mechanisms on simultaneous oxidation of Mn(Ⅱ) and As (Ⅲ)on oxide mineral surface and their accompanied removal efficiency remain unclear.This study compared Mn (Ⅱ) oxidation on four common metal oxides (γ-Al_(2)O_(3),CuO,α-Fe2O_(3)and ZnO) and investigated the simultaneous oxidation and removal of Mn (Ⅱ) and As (Ⅲ) through batch experiments and spectroscopic analyses.Among the tested oxides,CuO and α-Fe2O_(3)possess greater catalytic activity toward Mn (Ⅱ) oxidation.Oxidation and removal kinetics of Mn (Ⅱ) and As (Ⅲ) on CuO indicate that O_(2)is the terminal electron acceptor for Mn (Ⅱ) and As (Ⅲ) oxidation on CuO,and Mn (Ⅱ) acts as an electron shuttle to promote As (Ⅲ) oxidation and removal.The main oxidized product of Mn (Ⅱ) on CuO is high-valent MnO_(x)species.This newly formed Mn (Ⅲ) or Mn (IV) phases promote As (Ⅲ) oxidation on CuO at circumneutral pH 8 and is reduced to Mn (Ⅱ),which may be then released into solution.This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn (Ⅱ) and As (Ⅲ) and suggests that CuO should be considered as an efficient material to remediate Mn (Ⅱ) and As(Ⅲ)contamination.
基金supported by the National Natural Sci-ence Foundation of China(No.40830527,40771102)the New Century Excellent Talents in University of China(No.NCET-09-0399)
文摘Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese oxides,i.e,acidic birnessite (BIR-H),alkaline birnessite (BIR-OH),cryptomelane (CRY) and todorokite (TOD),were comparatively investigated.To elucidate phenol degradation mechanisms,X-ray diffraction (XRD),ICP-AES (inductively coupled plasma-atomic emission spectroscopy),TEM (transmission electronic microscope),N 2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS) were employed to characterize the structural,compositional,morphological,specific surface area and optical absorption properties of the manganese oxides.After 12 hr of UV-Vis irradiation,the total organic carbon (TOC) removal rate reached 62.1%,43.1%,25.4%,and 22.5% for cryptomelane,acidic birnessite,todorokite and alkaline birnessite,respectively.Compared to the reactions in the dark condition,UV- Vis exposure improved the TOC removal rates by 55.8%,31.9%,23.4% and 17.9%.This suggests a weak ability of manganese oxides to degrade phenol in the dark condition,while UV-Vis light irradiation could significantly enhance phenol degradation.The manganese minerals exhibited photocatalytic activities in the order of:CRY BIR-H TOD BIR-OH.There may be three possible mechanisms for photochemical degradation:(1) direct photolysis of phenol;(2) direct oxidation of phenol by manganese oxides;(3) photocatalytic oxidation of phenol by manganese oxides.Photocatalytic oxidation of phenol appeared to be the dominant mechanism.
基金financial support provided by the National Key Research and Development Program of China (2017YFD0200200)
文摘A four-year project,entitled"The mechanisms of fraction transformation and high use efficiency of P fertilizer in Chinese cropping systems"commenced in 2017.The project was established to answer three key questions and looked at 17 cropping systems on ten soils.First,we asked what are the dynamics of transformation,fixation and mobilization of P fertilizers in soil-cropping systems?Second,what are the mechanisms of soil-cropmicrobe interactions by which P fertilizer can be efficiently used?Third,how to manipulate the processes of P use in cropping systems?The targets of this project are(1)to explore the mechanisms of P fixation,the pathways of loss of P availability and the threshold of migration of fertilizer P in the field;(2)to uncover mechanisms by which soil legacy P is mobilized through root physiological and morphological processes and through arbuscular mycorrhizal fungi and P-solubilizing bacteria in rhizosphere and hyphosphere;(3)to estimate the biological potential of crops for high efficiency P absorption and use;(4)to innovate new approaches for improving the efficiency of P fertilizers.The outcomes will provide theoretical support for setting standards for limitation of P fertilizer application rate in the main cropping zones of China.
基金the National Natural Science Foundation of China (Nos. 41401250, 41271253)open fund (No. KLMM20150107) of CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of SciencesHuazhong Agricultural University doctoral start-up fund (No. 52902-0900206162) for financial support
文摘Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterized by powder X-ray diffraction(XRD), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), Fourier transform infrared spectroscopy(FT-IR) and extended X-ray absorption fine structure(EXAFS)spectroscopy. The adsorption behavior of these samples towards PO43-was also investigated. Characterization results demonstrated that increasing Al content in goethite led to a reduction in crystallinity, increase in specific surface area(SSA), and morphology change from needle-like to granular. Rietveld structure refinement revealed that the lattice parameter a remained almost constant and b slightly decreased, but c was significantly reduced, and the calculated crystal density increased. EXAFS analysis demonstrated that the Fe(Al)–O distance in the structure of the doped goethites was almost the same, but the Fe–Fe(Al) distance decreased with increasing Al content. Surface analysis showed that, with increasing Al content, the content of OH groups on the mineral surface increased. The adsorption of phosphate per unit mass of Al-doped goethite increased, while adsorption per unit area decreased owing to the decrease of the relative proportion of(110) facets in the total surface area of the minerals. The results of this research facilitate better understanding of the effect of Al substitution on the structure and properties of goethite and the cycling of phosphate in the environment.
基金supported by the National Natural Science Foundation of China (Nos.41271253 and 41401250)the Huazhong Agricultural University Doctoral Start-up Fund (Grant 52902-0900206162)
文摘Cryptomelane is a reactive Mn oxide and has been used in removal of heavy metal from wastewaters. Co-doped cryptomelane was synthesized by refluxing at ambient pressure and characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and extended X-ray absorption fine structure spectroscopy, and its performances for removal of Pb^2+ and Cr^3+ from aqueous solutions were investigated. Co doping has a negligible effect on the structure and morphology of cryptomelane but increases the specific surface area and Mn average oxidation state. Mn and Co K-edge extended X-ray absorption fine structure spectroscopy(EXAFS) analysis shows that Co barely affects the atomic coordination environments of Mn, and distances of edge- and corner-sharing Co–Me(Me_Co, Mn) pairs are shorter than those of the corresponding Mn–Me pairs, implying the replacement of framework Mn(III) by Co(III). These Co-doped cryptomelanes can quickly oxidize Cr3+to be HCr O4-and remove 45%–66% of the total Cr in the reaction systems by adsorption and fixation, and they have enhanced Pb2+adsorption capacities. Thus these materials are promising adsorbents for heavy metal remediation. The results demonstrate the design and modification of environmental friendly Mn oxide materials and can help us understand the interaction mechanisms of transition metals with Mn oxides.