Based on the criteria for additional surface acidity generation in composite oxides and composite fluorides proposed by Tanabe and Kemnitz et al.A hypothesis for the origin of additional surface acidity in solid compo...Based on the criteria for additional surface acidity generation in composite oxides and composite fluorides proposed by Tanabe and Kemnitz et al.A hypothesis for the origin of additional surface acidity in solid composites with the same metal cations is proposed.The surface acidsites of We analyze three types of solid composite systems,that is,CrF_(3)/Cr_(2)O_(3),MgF_(2)/MgO,and ZnF_(2)/ZnO,is systematically analyzed,which agrees with experimental results.Accordingly,the origin of additional surface acidity in these solid composites is reasonably explained,and the types of acidic sites are also predicted.展开更多
The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the rea...The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous AI hydroxide rapidly transformed to crystalline bayerite at the alkaline condition （pH〉10）. The solution analyses after and during the titration Ksp=^aAl^3＋/aH^＋^3 ,was 10^10.3. The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved AI species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.展开更多
Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.He...Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.Herein,we have designed a highly active VOx-MnOx/CeO_(2) material based on the intrinsic requirement of SCR reaction for catalyst,namely redox sites and surface acid sites.The vanadium oxide and manganese oxide are highly dispersed over the ceria mesosphere via simple incipient wetness impregnation.The loading of manganese could introduce acid sites and enhance the redox property remarkably,while the loading of vanadium increases acid sites and weakens redox property.Through tentatively controlling the appropriate loading ratio of the two components,the optimal catalyst achieves a balance between redox property and surface acidity.The work shed light on the development of new SCR catalyst with superior low temperature activity,wide work temperature window and good hydrothermal stability.展开更多
The sorption of a triazol derivative, 1-(4-chlorophenyl)- 4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)penten-3-ol with a common name of S3307D, on fifteen soils and three H_2O_2-treated soils was investigated. The sorption ...The sorption of a triazol derivative, 1-(4-chlorophenyl)- 4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)penten-3-ol with a common name of S3307D, on fifteen soils and three H_2O_2-treated soils was investigated. The sorption isotherm for each untreated and treated soil was non-linear, and was best fitted to Freundlich sorption equation. Soils containing high amount of clay content or organic matter or both sorbed much higher amounts of the chemical than soils that had low contents of these soil constituents. H_2O_2-treated soils showed considerable sorptive affinity for S3307D. It was concluded that both organic matter and mineral fraction in natural soils contributed to the sorption of the basic compound. Sorption by the H_2O_2 treated soils increased as suspension pH decreased, but all suspension pHs exceeded the pKa of the compound by more than two units. This implies that organic base protonation can occur on surfaces of soil components, and surface acidity (exchangeable acidity ) is important in sorption process of the organic base rather than suspension pH.展开更多
The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity a...The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity and SO2/H2 O durability of the Ce O2-Ti O2 catalyst and an optimal loading of Mo was 4?wt.%. The best Mo O3/Ce O2-Ti O2 catalyst displayed over 90% NO conversion from 200 °C to 400 °C and obtained 4-fold increase in NO conversion compared to Ce O2-Ti O2 at 150 °C. The characterization results revealed that the number of Br?nsted acid sites over Mo O3/Ce O2-Ti O2 was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of Mo O3, which were favorable for the high NH3-SCR performance. It is believed that the Mo O3/Ce O2-Ti O2 catalyst is a suitable substitute for the NH3-SCR reaction.展开更多
NOx emission abatement catalysts V 2O 5 supported on various TiO 2 including anatase, rutile and mixture of both were investigated with various physico\|chemical measurements such as BET, NH\-3\|TPD, NARP, XRD and ...NOx emission abatement catalysts V 2O 5 supported on various TiO 2 including anatase, rutile and mixture of both were investigated with various physico\|chemical measurements such as BET, NH\-3\|TPD, NARP, XRD and so on, and the effect of TiO\-2 surface properties on the SCR(selective catalytic reduction) activity of V\-2O\-5/TiO\-2 catalysts was studied. It was found that the TiO\-2 surface properties had strong affect on the SCR activity of V\-2O\-5/TiO\-2 catalysts. The stronger acidic property resulted in the higher exposure of active sites as well as the higher SCR activity.展开更多
Experiments on proton dissociation from the surfaces of goethite, amorphous Al oxide, kaolinite and latosolwere carried out, showing amphoteric behavior with reactions of proton dissociation-association on the surface...Experiments on proton dissociation from the surfaces of goethite, amorphous Al oxide, kaolinite and latosolwere carried out, showing amphoteric behavior with reactions of proton dissociation-association on the surfaces andbuffering capacity in such a sequence as amorphous Al oxide > latosol > kaolinite > goethite. Dissociation con-stants of surface proton, pK_(sa) are significantly correlated with surface charge density, which has been proved with anelectrochemical model. Tbe intrinsic constants of proton dissociation, K_(sa)(int), gained by extrapolation to zero charconditions of plots of pK_(sa) against σ_o, could be used to estimate the acidity strength of variable charge surfaces. Thevalue of pK_(sa)(int) is 8.08 for goethite, 1 .2 for amorphous Al oxide, 6.62 for kaolinite and 5 .32 for latosol.展开更多
In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity ...In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity of 300,000 hr-1,the ozone conversion over the pH=7 catalyst under dry conditions and relative humidity of 65%over a period of 6 hr was 100%and 96%,respectively.However,the ozone decomposition activity of the pH=2 and 4 catalysts distinctly decreased under relative humidity of 65%compared to that under dry conditions.Detailed physical and chemical characterization demonstrated that the residual sulfate ions on the pH=2 and 4 catalysts decreased their hydrophobicity and then restrained humid ozone decomposition activity.The pH=2 and 4 catalysts had inferior resistance to high space velocity under dry conditions,because the residual sulfate ion on their surface reduced their adsorption capacity for ozone molecules and increased their apparent activation energies,which was proved by temperature programmed desorption of O2 and kinetic experiments.Long-term activity testing,X-ray photoelectron spectroscopy and density functional theory calculations revealed that there were two kinds of oxygen vacancies on the manganese dioxide catalysts,one of which more easily adsorbed oxygen species and then became deactivated.This study revealed the detrimental effect of surface acid ions on the activity of catalysts under humid and dry atmospheres,and provided guidance for the development of highly efficient catalysts for ozone decomposition.展开更多
In this study,the cytotoxicity of two different crystal phases of TiO2 nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO2 nanoparticles ...In this study,the cytotoxicity of two different crystal phases of TiO2 nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO2 nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO2 nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC50=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC50of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO2 nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O2^-）.Data suggested that O2^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O2^- on rutile,but increased O2^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.展开更多
Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carri...Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.展开更多
Polypeptide brushes are attractive platforms to generate functional and responsive interfaces that are of potential interest due to their possible biodegradability, biocompatibility and tunable secondary structures. S...Polypeptide brushes are attractive platforms to generate functional and responsive interfaces that are of potential interest due to their possible biodegradability, biocompatibility and tunable secondary structures. Surface-initiated ringopening polymerization（SI-ROP） of α-amino acid N-carboxyanhydrides represents a powerful and versatile strategy to generate polypeptide brushes. This review is an attempt to capture the state-of-the-art in this field and highlights the latest developments in several selected areas. In addition to presenting an overview of the synthetic methods that have been used to generate polypeptide brushes via SI-ROP, this article will discuss the preparation of patterned polypeptide brushes, the conformational properties of surface-tethered polypeptides, ways to control chain orientation at surfaces as well as properties and applications of these thin polymer films.展开更多
One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,...One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.展开更多
Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-am...Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-aminonicotinic acid：perchloric acid：H2O and salt 2 with 2：1：3 stoichiometry of 2-aminonicotinic acid：sulfuric acid：H2O. Their crystal structures were characterized by single-crystal X-ray diffraction,differential scanning calorimetry（DSC） and thermogravimetric analyses（TGA）. The structure determination shows that two salts are both primarily stabilized by the strong N–H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice,a three-dimensional hydrogen-bonded network is observed,including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H,O–H…O and C–O…π intermolecular interactions.展开更多
Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes（EAOPs） to treat it. Surface activation of the electrode used in such treatment is ...Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes（EAOPs） to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process.The performance of boron-doped nanocrystalline diamond（BD-NCD） film electrode for decolorization of Acid Yellow（AY-36） azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic.Due to the oxidation of surface functional groups and some portion of sp2 carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation（EO） capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand（COD） removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.展开更多
Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric ac...Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric acid corrosion in conjunction with flotation separation was proposed,and the efficient separation of galena and chalcopyrite was successfully realized.Contact angle test results showed a substantial decrease in surface contact angle and a selective inhibition of surface floatability for corroded galena.Meanwhile,the contact angle and floatability of corroded chalcopyrite remained almost unaffected.Scanning electron microscope results confirmed that sulfuric acid corrosion led to the formation of a dense oxide layer on the galena surface,whereas the chalcopyrite surface remained unaltered.X-ray photoelectron spectroscopy results showed that the chemical state of S^(2-)on the surface of corroded galena was oxidized to SO_(4)^(2-).A layer of hydrophilic PbSO4was formed on the surface,leading to a sharp decrease in galena floatability.Meanwhile,new hydrophobic CuS_(2),CuS,and Cu_(1-x)Fe_(1-y)S_(2-z)species exhibiting good floatability were generated on the chalcopyrite surface.Finally,theoretical analysis results were further verified by corrosion–flotation separation experiments.The galena–chalcopyrite mixture was completely separated via flotation separation under appropriate corrosion acidity,corrosion temperature,and corrosion time.A novel approach has been outlined in this study,providing potential applications in the efficient separation of refractory copper–lead sulfide ore.展开更多
This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simu...This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.展开更多
Fibrous brucite,a kind of brucite with unique structure and physical properties,was modified with stearic acid as a surface modifier.In order to investigate the mechanism of surface modification,the fixation of steari...Fibrous brucite,a kind of brucite with unique structure and physical properties,was modified with stearic acid as a surface modifier.In order to investigate the mechanism of surface modification,the fixation of stearic acid on fibrous brucite and the induced changes in surface properties were studied by using X-ray diffraction（XRD）,scanning electron microscopy（SEM）,infrared spectroscopy（IR）,Raman spectroscopy and thermo-gravimetric analysis（TGA）.XRD analysis indicates that the modification of fibrous brucite with stearic acid does not cause any changes in the structure of fibrous brucite mineral.Spectroscopy and thermal analysis show that the surfactant molecules are not only directly adsorbed on the surface of the mineral,but also chemisorbed on mineral surface by forming chemical bonds between the modifier and magnesium hydroxide.展开更多
This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature....This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.展开更多
A series of sulfated CeO2 catalysts were synthesized by impregnation and sol-gel methods and used for selective catalytic reduction （SCR） of NOx by NH3. The results showed that the sulfated CeO2 catalysts prepared b...A series of sulfated CeO2 catalysts were synthesized by impregnation and sol-gel methods and used for selective catalytic reduction （SCR） of NOx by NH3. The results showed that the sulfated CeO2 catalysts prepared by sol-gel method showed excellent catalytic activity at 150-50 ℃, and more than 90% NOx conversion was obtained at 232-450 ℃ with a gas hourly space velocity of 60000 h-1. The catalysts were characterized by X-ray diffraction （XRD）, N2 adsorption, Raman, thermogravimetry （TG）, H2-tem- perature-programmed reduction （H2-TPR） and Py-infrared spectroscopy （Py-IR）. The excellent SCR performance was associated with the surface acidity and the micro-structure. The introduction of sulfate acid into CeO2 could increase the amount of BrOnsted and Lewis acid sites over the catalysts, resulting in the improvement of the low temperature activity. The sulfated CeO2 catalysts prepared by sol-gel method possessed lower crystallization degree, excellent redox property and larger specific surface areas, which were responsible for the superior SCR performance.展开更多
The CeO2‐TiO2(CeTi)and CeO2/WO3‐TiO2(CeWTi)catalysts were prepared by a sol‐gel precipitation method and their NH3‐NO/NO2 selective catalytic reduction(SCR)performance was studied.N2O formation and effect of oxyge...The CeO2‐TiO2(CeTi)and CeO2/WO3‐TiO2(CeWTi)catalysts were prepared by a sol‐gel precipitation method and their NH3‐NO/NO2 selective catalytic reduction(SCR)performance was studied.N2O formation and effect of oxygen concentration on SCR performance over CeWTi catalyst were also investigated while varying the NO2/NOx ratio.Results indicate that fast SCR behavior of CeWTi catalyst has the best NH3‐NO/NO2 SCR performance due to the catalyst reoxidation rate by NO2 higher than by O2.Compared with CeTi catalyst,CeWTi catalyst exhibits higher de‐NOx performance under NH3‐NO/NO2 SCR conditions.As the CeTi and CeWTi catalysts exhibit similar redox property,addition of WO3 provides more acid sites which accelerate the reaction between NH4NO3 and NO to get a superior low‐temperature activity.Amount of N2O formation shows a peak at 250 oC mainly derived from NH4NO3 decomposition.展开更多
基金The Key Research and Development Program of Zhejiang Province(2021C01003)National Natural Science Foundation of China(52025011,51971202,51872260 and 52171019)The Zhejiang Provincial Natural Science Foundation of China(LD19B030001,Z4080070 and LR23B030004)。
文摘Based on the criteria for additional surface acidity generation in composite oxides and composite fluorides proposed by Tanabe and Kemnitz et al.A hypothesis for the origin of additional surface acidity in solid composites with the same metal cations is proposed.The surface acidsites of We analyze three types of solid composite systems,that is,CrF_(3)/Cr_(2)O_(3),MgF_(2)/MgO,and ZnF_(2)/ZnO,is systematically analyzed,which agrees with experimental results.Accordingly,the origin of additional surface acidity in these solid composites is reasonably explained,and the types of acidic sites are also predicted.
文摘The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous AI hydroxide rapidly transformed to crystalline bayerite at the alkaline condition （pH〉10）. The solution analyses after and during the titration Ksp=^aAl^3＋/aH^＋^3 ,was 10^10.3. The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved AI species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.
基金Project supported by the National Natural Science Foundation of China (21576054)Science and Technology Planning of Guangdong Province (2016B020241003)+1 种基金Natural Science Foundation of Guangdong Province(2018A030310563)Foundation of Higher Education of Guangdong Province(2018KZDXM031)。
文摘Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.Herein,we have designed a highly active VOx-MnOx/CeO_(2) material based on the intrinsic requirement of SCR reaction for catalyst,namely redox sites and surface acid sites.The vanadium oxide and manganese oxide are highly dispersed over the ceria mesosphere via simple incipient wetness impregnation.The loading of manganese could introduce acid sites and enhance the redox property remarkably,while the loading of vanadium increases acid sites and weakens redox property.Through tentatively controlling the appropriate loading ratio of the two components,the optimal catalyst achieves a balance between redox property and surface acidity.The work shed light on the development of new SCR catalyst with superior low temperature activity,wide work temperature window and good hydrothermal stability.
文摘The sorption of a triazol derivative, 1-(4-chlorophenyl)- 4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)penten-3-ol with a common name of S3307D, on fifteen soils and three H_2O_2-treated soils was investigated. The sorption isotherm for each untreated and treated soil was non-linear, and was best fitted to Freundlich sorption equation. Soils containing high amount of clay content or organic matter or both sorbed much higher amounts of the chemical than soils that had low contents of these soil constituents. H_2O_2-treated soils showed considerable sorptive affinity for S3307D. It was concluded that both organic matter and mineral fraction in natural soils contributed to the sorption of the basic compound. Sorption by the H_2O_2 treated soils increased as suspension pH decreased, but all suspension pHs exceeded the pKa of the compound by more than two units. This implies that organic base protonation can occur on surfaces of soil components, and surface acidity (exchangeable acidity ) is important in sorption process of the organic base rather than suspension pH.
基金supported by the National Natural Science Foundation of China(21773106,21707066,21677069,and 21806077)the China Postdoctoral Science Foundation(2018M642206)~~
文摘The effect of molybdenum oxide on the activity and durability of Ce O2-Ti O2 catalyst for NO reduction by NH3 was examined. It was found that the introduction of Mo could improve the low-temperature NH3-SCR activity and SO2/H2 O durability of the Ce O2-Ti O2 catalyst and an optimal loading of Mo was 4?wt.%. The best Mo O3/Ce O2-Ti O2 catalyst displayed over 90% NO conversion from 200 °C to 400 °C and obtained 4-fold increase in NO conversion compared to Ce O2-Ti O2 at 150 °C. The characterization results revealed that the number of Br?nsted acid sites over Mo O3/Ce O2-Ti O2 was significantly increased, and the adsorption of nitrate species was dramatically weakened because of the coverage of Mo O3, which were favorable for the high NH3-SCR performance. It is believed that the Mo O3/Ce O2-Ti O2 catalyst is a suitable substitute for the NH3-SCR reaction.
文摘NOx emission abatement catalysts V 2O 5 supported on various TiO 2 including anatase, rutile and mixture of both were investigated with various physico\|chemical measurements such as BET, NH\-3\|TPD, NARP, XRD and so on, and the effect of TiO\-2 surface properties on the SCR(selective catalytic reduction) activity of V\-2O\-5/TiO\-2 catalysts was studied. It was found that the TiO\-2 surface properties had strong affect on the SCR activity of V\-2O\-5/TiO\-2 catalysts. The stronger acidic property resulted in the higher exposure of active sites as well as the higher SCR activity.
文摘Experiments on proton dissociation from the surfaces of goethite, amorphous Al oxide, kaolinite and latosolwere carried out, showing amphoteric behavior with reactions of proton dissociation-association on the surfaces andbuffering capacity in such a sequence as amorphous Al oxide > latosol > kaolinite > goethite. Dissociation con-stants of surface proton, pK_(sa) are significantly correlated with surface charge density, which has been proved with anelectrochemical model. Tbe intrinsic constants of proton dissociation, K_(sa)(int), gained by extrapolation to zero charconditions of plots of pK_(sa) against σ_o, could be used to estimate the acidity strength of variable charge surfaces. Thevalue of pK_(sa)(int) is 8.08 for goethite, 1 .2 for amorphous Al oxide, 6.62 for kaolinite and 5 .32 for latosol.
基金supported by the National Key R&D Program of China(Nos.2016YFC0207104 and 2017YFC0211802)the National Natural Science Foundation of China(NSFC)(No.21876191)the Youth Innovation Promotion Association,CAS(No.2017064)
文摘In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity of 300,000 hr-1,the ozone conversion over the pH=7 catalyst under dry conditions and relative humidity of 65%over a period of 6 hr was 100%and 96%,respectively.However,the ozone decomposition activity of the pH=2 and 4 catalysts distinctly decreased under relative humidity of 65%compared to that under dry conditions.Detailed physical and chemical characterization demonstrated that the residual sulfate ions on the pH=2 and 4 catalysts decreased their hydrophobicity and then restrained humid ozone decomposition activity.The pH=2 and 4 catalysts had inferior resistance to high space velocity under dry conditions,because the residual sulfate ion on their surface reduced their adsorption capacity for ozone molecules and increased their apparent activation energies,which was proved by temperature programmed desorption of O2 and kinetic experiments.Long-term activity testing,X-ray photoelectron spectroscopy and density functional theory calculations revealed that there were two kinds of oxygen vacancies on the manganese dioxide catalysts,one of which more easily adsorbed oxygen species and then became deactivated.This study revealed the detrimental effect of surface acid ions on the activity of catalysts under humid and dry atmospheres,and provided guidance for the development of highly efficient catalysts for ozone decomposition.
基金supported in part by the NSF-REU program(National Science Foundation-Research Experiences for Undergraduates,No.#CHE-1156111)the NSF-CREST program(National Science Foundation-Centers of Research Excellencein Science and Technology,No.#HRD-0833178)
文摘In this study,the cytotoxicity of two different crystal phases of TiO2 nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO2 nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO2 nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC50=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC50of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO2 nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O2^-）.Data suggested that O2^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O2^- on rutile,but increased O2^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.
基金E.L.,K.L.,P.W.,and S.T.are supported by the SCCER-Heat and Energy Storage program
文摘Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.
基金financially supported by the Sino-Swiss Science and Technology Cooperation(No.EG41-092011)as well as the Chinese Academy of Sciences(Visiting Professorship for Senior International Scientists to H.A.K.)
文摘Polypeptide brushes are attractive platforms to generate functional and responsive interfaces that are of potential interest due to their possible biodegradability, biocompatibility and tunable secondary structures. Surface-initiated ringopening polymerization（SI-ROP） of α-amino acid N-carboxyanhydrides represents a powerful and versatile strategy to generate polypeptide brushes. This review is an attempt to capture the state-of-the-art in this field and highlights the latest developments in several selected areas. In addition to presenting an overview of the synthetic methods that have been used to generate polypeptide brushes via SI-ROP, this article will discuss the preparation of patterned polypeptide brushes, the conformational properties of surface-tethered polypeptides, ways to control chain orientation at surfaces as well as properties and applications of these thin polymer films.
基金Supported by the financial support of Fundamental Research Funds for the Central Universities(3207045420)Jiangsu Ainaji Neoenergy Science&Technology Co.,Ltd.(8507040091)
文摘One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.
基金supported by the prospective joint research project of Jiangsu province(BY20122193)the Fundamental Research Funds for the Central Universities(CXZZ12_0119)
文摘Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-aminonicotinic acid：perchloric acid：H2O and salt 2 with 2：1：3 stoichiometry of 2-aminonicotinic acid：sulfuric acid：H2O. Their crystal structures were characterized by single-crystal X-ray diffraction,differential scanning calorimetry（DSC） and thermogravimetric analyses（TGA）. The structure determination shows that two salts are both primarily stabilized by the strong N–H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice,a three-dimensional hydrogen-bonded network is observed,including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H,O–H…O and C–O…π intermolecular interactions.
基金financially supported by "National" Science Council of Taiwan by Grant NSC 99-2221-E-009-042Ministry of Economic Affairs of Taiwan by Grant 101-EC-17-A-08-S1-208
文摘Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes（EAOPs） to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process.The performance of boron-doped nanocrystalline diamond（BD-NCD） film electrode for decolorization of Acid Yellow（AY-36） azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic.Due to the oxidation of surface functional groups and some portion of sp2 carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation（EO） capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand（COD） removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.
基金financially supported by the National Natural Science Foundation of China(No.52064027)Yunnan Major Scientific and Technological Projects,China(No.202202AG050015)。
文摘Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric acid corrosion in conjunction with flotation separation was proposed,and the efficient separation of galena and chalcopyrite was successfully realized.Contact angle test results showed a substantial decrease in surface contact angle and a selective inhibition of surface floatability for corroded galena.Meanwhile,the contact angle and floatability of corroded chalcopyrite remained almost unaffected.Scanning electron microscope results confirmed that sulfuric acid corrosion led to the formation of a dense oxide layer on the galena surface,whereas the chalcopyrite surface remained unaltered.X-ray photoelectron spectroscopy results showed that the chemical state of S^(2-)on the surface of corroded galena was oxidized to SO_(4)^(2-).A layer of hydrophilic PbSO4was formed on the surface,leading to a sharp decrease in galena floatability.Meanwhile,new hydrophobic CuS_(2),CuS,and Cu_(1-x)Fe_(1-y)S_(2-z)species exhibiting good floatability were generated on the chalcopyrite surface.Finally,theoretical analysis results were further verified by corrosion–flotation separation experiments.The galena–chalcopyrite mixture was completely separated via flotation separation under appropriate corrosion acidity,corrosion temperature,and corrosion time.A novel approach has been outlined in this study,providing potential applications in the efficient separation of refractory copper–lead sulfide ore.
文摘This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.
基金Funded by National Natural Science Foundation of China(No.51274015)
文摘Fibrous brucite,a kind of brucite with unique structure and physical properties,was modified with stearic acid as a surface modifier.In order to investigate the mechanism of surface modification,the fixation of stearic acid on fibrous brucite and the induced changes in surface properties were studied by using X-ray diffraction（XRD）,scanning electron microscopy（SEM）,infrared spectroscopy（IR）,Raman spectroscopy and thermo-gravimetric analysis（TGA）.XRD analysis indicates that the modification of fibrous brucite with stearic acid does not cause any changes in the structure of fibrous brucite mineral.Spectroscopy and thermal analysis show that the surfactant molecules are not only directly adsorbed on the surface of the mineral,but also chemisorbed on mineral surface by forming chemical bonds between the modifier and magnesium hydroxide.
基金supported by the National Natural Science Foundation of China (No. 21507130)the Open Project Program of Beijing National Laboratory for Molecular Sciences (No. 20140142)+3 种基金the Open Project Program of Chongqing Key Laboratory of Environmental Materials and Remediation Technology from Chongqing University of Arts and Sciences (No. CEK1405)the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control (No. OVEC001)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University (1456029)the Chongqing Science & Technology Commission (Nos. cstc2016jcyj A0070, cstc2014pt-gc20002, cstckjcxljrc13)~~
文摘This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.
基金Project supported by the National Natural Science Foundation of China(U1137603,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(LYJ1309)Academic Newcomer Award of Yunnan Province
文摘A series of sulfated CeO2 catalysts were synthesized by impregnation and sol-gel methods and used for selective catalytic reduction （SCR） of NOx by NH3. The results showed that the sulfated CeO2 catalysts prepared by sol-gel method showed excellent catalytic activity at 150-50 ℃, and more than 90% NOx conversion was obtained at 232-450 ℃ with a gas hourly space velocity of 60000 h-1. The catalysts were characterized by X-ray diffraction （XRD）, N2 adsorption, Raman, thermogravimetry （TG）, H2-tem- perature-programmed reduction （H2-TPR） and Py-infrared spectroscopy （Py-IR）. The excellent SCR performance was associated with the surface acidity and the micro-structure. The introduction of sulfate acid into CeO2 could increase the amount of BrOnsted and Lewis acid sites over the catalysts, resulting in the improvement of the low temperature activity. The sulfated CeO2 catalysts prepared by sol-gel method possessed lower crystallization degree, excellent redox property and larger specific surface areas, which were responsible for the superior SCR performance.
基金supported by the National Natural Science Foundation of China(51775296,51375253)~~
文摘The CeO2‐TiO2(CeTi)and CeO2/WO3‐TiO2(CeWTi)catalysts were prepared by a sol‐gel precipitation method and their NH3‐NO/NO2 selective catalytic reduction(SCR)performance was studied.N2O formation and effect of oxygen concentration on SCR performance over CeWTi catalyst were also investigated while varying the NO2/NOx ratio.Results indicate that fast SCR behavior of CeWTi catalyst has the best NH3‐NO/NO2 SCR performance due to the catalyst reoxidation rate by NO2 higher than by O2.Compared with CeTi catalyst,CeWTi catalyst exhibits higher de‐NOx performance under NH3‐NO/NO2 SCR conditions.As the CeTi and CeWTi catalysts exhibit similar redox property,addition of WO3 provides more acid sites which accelerate the reaction between NH4NO3 and NO to get a superior low‐temperature activity.Amount of N2O formation shows a peak at 250 oC mainly derived from NH4NO3 decomposition.
