In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performa...In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.展开更多
The effect of sodium pyrophosphate (SPH) on the separation of chalcopyrite from galena was examined through flotation, adsorption, electrokinetic studies and infrared spectral analysis. Differential flotation tests ...The effect of sodium pyrophosphate (SPH) on the separation of chalcopyrite from galena was examined through flotation, adsorption, electrokinetic studies and infrared spectral analysis. Differential flotation tests indicate that satisfactory separation can be achieved within the pH range from 2.5 to 6 using SPH to depress the galena, but not the chalcopyrite when O-isopropyl-N-ethyl thionocarbamate (IPETC) is used as the collector. The electrophoretic mohilities of both the minerals dramatically become negatively charged following SPH adsorption in the pH range from 2.5 to 12, The infrared spectral analysis suggests that chemical adsorption occurs on galena surface treated by SPH, indicating that a chelate complex has formed. At weakly acidic pH values, the adsorption density of IPETC onto galena is significantly reduced in the presence of SPH. However, the amount of IPETC adsorbed onto chalcopyrite almost remains at the same level. Since the observed adsorption density of IEPTC onto chalcopyrite is quite high compared to galena, the observed flotation results are explained. A possible mechanism for the interaction between the two sulphide minerals and SPH is discussed.展开更多
The influence of mischmetal addition on physicochcmical properties of PtSnNa/ZSM-5 catalyst was studied by means of XRF, H2 chemisorption, XRD, TPR, NH3-TPD and TPO techniques. The results showed that the presence of ...The influence of mischmetal addition on physicochcmical properties of PtSnNa/ZSM-5 catalyst was studied by means of XRF, H2 chemisorption, XRD, TPR, NH3-TPD and TPO techniques. The results showed that the presence of mischmetal had an obvious impact on the catalytic performance of the PtSnNa/ZSM-5 catalyst. A suitable content of mischmetal not only could enhance the interactions between Pt species and the support, but also inhibit the formation of coke during the reaction, thus improving the catalytic activity and stability. In our experiments, when the content of mischmetal was 3m%, the catalyst exhibited best catalytic performance. However, the continuous addition of mischmetal could promote the reduction of Sn species to metallic tin, which was disadvantageous to the reaction.展开更多
Single-molecule tip-enhanced Raman spectroscopy(TERS)has emerged as an important technique for structural analysis at sub-molecular scale.Here in this work,we report a TERS study of an isolated free-base porphyrin mol...Single-molecule tip-enhanced Raman spectroscopy(TERS)has emerged as an important technique for structural analysis at sub-molecular scale.Here in this work,we report a TERS study of an isolated free-base porphyrin molecule adsorbed on the Ag(100)surface at cryogenic temperature(~7 K).Site-dependent TERS spectra reveal distinct local vibrational information for the chemical constituents within a single molecule.Moreover,distinct spatial features among different Raman peaks can be resolved from the TERS mapping images.These images are found to associate with related vibrational modes,enabling to resolve the mode associated with N-H bonds at the sub-nanometer level.This study will provide deep insights into the symmetry of adsorption configurations and local vibrational information within a single molecule.展开更多
In order to quantify the effect of matrix shrinkage on reservoir permeability during coalbed methane production, coal samples from Huozhou, Changzhi and Jincheng areas in Shanxi province (classified as high-volatile ...In order to quantify the effect of matrix shrinkage on reservoir permeability during coalbed methane production, coal samples from Huozhou, Changzhi and Jincheng areas in Shanxi province (classified as high-volatile bituminous coal, low-volatile bituminous coal and anthracite, respectively) were collected, and adsorption-induced coal swelling in methane were determined by an optical method at 40 ℃ and pressure up to 12 MPa. All three coals showed similar behavior-that swelling increased as a function of pressure up to about 10 MPa but thereafter no further increase in swelling was observed. Swelling in the direction perpendicular to the bedding plane is greater than that parallel to the bedding plane, and the differences are about 7.77-8.33%. The maximum volumetric swelling ranges from 2.73% to 3.21 %-increasing with increasing coal rank. The swelling data can be described by a modified DR model. In addition, swelling increases with the amount of adsorption. However, the increase shows a relatively slower stage followed by a relatively faster stage instead of a linear increase. Based on the assumption that sorption-induced swelling/shrinkage of coal in methane is reversible, the permeability increases induced by coal shrinkage during methane desorption was analyzed, and the results indicate that the permeability change is larger for higher rank coal in the same unit of pressure depletion.展开更多
This paper studies the adsorption of diethyl phthalate (DEP,an environmental hormone) on the surface of nanoscale TiO2, effects of pH value of solutions, initial concentrations of DEP and additive surfactant on phot...This paper studies the adsorption of diethyl phthalate (DEP,an environmental hormone) on the surface of nanoscale TiO2, effects of pH value of solutions, initial concentrations of DEP and additive surfactant on photocatalytic degradation and dynamics of DEP. Under ultra violet illumination, the interaction between DEP and surfactants including DBS (sodium dodecylbenzenesulfonate), CTAB (cetyltrimethylammonium bromide), and OP-10 (nonylphenol polyoxyethylene ether) was exploited from the perspective of degradation speed calculated by the data of high pressure liquid chromatography (HPLC) and UV-Vis spectra, respectively. Photocatalytic degradation of DEP followed pseudo first-order reaction kinetics. DEP as substrate degraded fast when its initial concentration was 130 mg/L. TiO2 had certain adsorption ability of DEP. TiO2 could adsorb the most DEP at the approximately neutral pH of 6.91. Degradation of DEP was not affected obviously by additives OP-10 and DBS. Degradation rate of DEP was not enhanced greatly in the presence of surfactants, but degradation of DBS was sped up. Degradation rate of DEP was depressed in the presence of additive CTAB. The more CTAB was added, the less DEP was degraded. Degradation rate of CTAB became slow with the increase of initial CTAB concentration. The possible adsorption models among TiO2, DEP and surfactants were given.展开更多
A continuous online in situ attenuated total reflection Fourier-transform infrared(ATR-FTIR)spectroscopic technique was used to investigate the adsorption and desorption kinetics of heptyl xanthate(KHX)on the surface ...A continuous online in situ attenuated total reflection Fourier-transform infrared(ATR-FTIR)spectroscopic technique was used to investigate the adsorption and desorption kinetics of heptyl xanthate(KHX)on the surface of ZnO and Cu(Ⅱ)activated ZnO.The results showed that Cu(Ⅱ)facilitated the xanthate adsorption process on the surface,and led to the formation of cuprous xanthate(CuX),dixanthogen(X_(2))and xanthate aggregates.The adsorption of xanthate on the surface of ZnO and Cu(Ⅱ)activated ZnO was found to both follow the pseudo-first-order kinetic model.When the NaOH solution was used as a desorption agent,the adsorbed xanthate can largely be removed due to the competition between OH^(−)and HX−.However,for Cu(Ⅱ)activated ZnO,the peak intensities at 1197 and 1082 cm^(−1) had no obvious weakening,and the absorption intensities at 1261 and 1026 cm^(−1) increased in the first 5 min,indicating an ion-exchange reaction between OH^(−)and surface zinc bonded xanthate HX−and the reorganization of adsorbed xanthate.展开更多
The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by ma...The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by mathematical models. Chemical modification experiments and Fourier transform infrared spectra indicated that carboxyl and amine groups were the important functional groups for adsorption of Cd. The maximum contribution of physical adsorption in the overall adsorption process was evaluated as 5.5%. These results indicated that chemisorption was the dominating mechanism of Cd biosorption by C.reinhardtii.展开更多
Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis in...Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis indicated that the AIGHS were hetero-porous.Boehm titrations and Fourier-transform infrared spectra demonstrated the chemical heterogeneity of the AIGHS surface.Batch biosorption studies were used to examine the effects of process parameters in the following range:pH 2-12,temperature 293-313 K,contact time 1-5 h and initial concentration 200-600 mg·L^(-1).The matching of equilibrium data with the Langmuir-Freundlich form of isotherms indicated that the BV10 was adsorbed via chemisorption and pore diffusion.Kinetic investigation indicated multiple order chemisorption through an Avrami kinetic model.Film diffusion controlled the rate of BV10 biosorption onto AIGHS.The spontaneous and endothermic nature of sorption was corroborated by thermodynamic study.Continuous biosorption experiments were performed using a fixed-bed column and the influence of operating parameters was explored for different ranges of initial concentration 100-300 mg·L^(-1),bed height 5-10 cm,and flow rate 2.5-4.5 ml·min^(-1).A dose response model accurately described the fixed-bed biosorption data.An external mass transfer correlation was formulated explaining BV10-AIGHS sorption.展开更多
Quantum-sized CdS-coated TiO2 nanotube array (Q-CdS-TiO2 NTA) was fabricated by the modified successive ionic layer absorption and reaction method. Scanning electron microscope and transmission electron microscope i...Quantum-sized CdS-coated TiO2 nanotube array (Q-CdS-TiO2 NTA) was fabricated by the modified successive ionic layer absorption and reaction method. Scanning electron microscope and transmission electron microscope images showed the regular structure of TiO2 NTA, where quantum-sized CdS (diameter 〈10nm) deposited on both the inside and outside of TiO2 nanotube wall. Fabrication conditions including immersing cycles, calcination temperature and drying process were well optimized, and the Q-CdS-TiO2 NTA and its photoelectrochemical (PEC) properties were characterized by X-ray fluorescence spectrometer, UV-Vis diffuse reflectance spectra and photovoltage. Distinct increases in visible light absorption and photocurrent were observed as the immersing cycle was increased from 5 to 20 times. The additional drying process accelerated the CdS crystal growth rate, and thus, the fabrication time could be shortened accordingly. Calcination temperature influenced the PEC property of Q-CdS-TiO2 NTA deeply, and the optimized calcination temperature was found as 500 ℃. As the Q-CdS-TiO2 NTA was fabricated under such condition, the visible photocurrent density increased to 2.8 mA/cm and the photovoltage between 350 and 480 nm was enhanced by 2.33 times than that without calcination. This study is expected to optimize Q-CdS-TiO2 NTA fabrication conditions for the purpose of improving its PEC performance.展开更多
基金supported by the National Natural Science Foundation of China (21377084)Special Fund for Agro-scientific Research in the Public Interest (201503107)~~
文摘In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.
基金Financial support from the Foundation of the State Key Laboratory of Comprehensive Utilization of Low-Grade Ores (Zijin Mining Group Co., Ltd.)the National Basic Research Program of China(No. 2010CB630905)
文摘The effect of sodium pyrophosphate (SPH) on the separation of chalcopyrite from galena was examined through flotation, adsorption, electrokinetic studies and infrared spectral analysis. Differential flotation tests indicate that satisfactory separation can be achieved within the pH range from 2.5 to 6 using SPH to depress the galena, but not the chalcopyrite when O-isopropyl-N-ethyl thionocarbamate (IPETC) is used as the collector. The electrophoretic mohilities of both the minerals dramatically become negatively charged following SPH adsorption in the pH range from 2.5 to 12, The infrared spectral analysis suggests that chemical adsorption occurs on galena surface treated by SPH, indicating that a chelate complex has formed. At weakly acidic pH values, the adsorption density of IPETC onto galena is significantly reduced in the presence of SPH. However, the amount of IPETC adsorbed onto chalcopyrite almost remains at the same level. Since the observed adsorption density of IEPTC onto chalcopyrite is quite high compared to galena, the observed flotation results are explained. A possible mechanism for the interaction between the two sulphide minerals and SPH is discussed.
基金the Specialized Research Fund for the Doctoral Program of Higher Education of China (No.20100092120047)the Production and Research Prospective Joint Research Project (No.BY2009153)the National Nature Science Foundation of China (No.50873026) for financial supports
文摘The influence of mischmetal addition on physicochcmical properties of PtSnNa/ZSM-5 catalyst was studied by means of XRF, H2 chemisorption, XRD, TPR, NH3-TPD and TPO techniques. The results showed that the presence of mischmetal had an obvious impact on the catalytic performance of the PtSnNa/ZSM-5 catalyst. A suitable content of mischmetal not only could enhance the interactions between Pt species and the support, but also inhibit the formation of coke during the reaction, thus improving the catalytic activity and stability. In our experiments, when the content of mischmetal was 3m%, the catalyst exhibited best catalytic performance. However, the continuous addition of mischmetal could promote the reduction of Sn species to metallic tin, which was disadvantageous to the reaction.
基金supported by the National Key R&D Program of China(No.2016YFA0200600)the National Natural Science Foundation of China,the Chinese Academy of Sciences+1 种基金Anhui Initiative in Quantum Information TechnologiesAtif Ghafoor acknowledges support by the China Scholarship Council
文摘Single-molecule tip-enhanced Raman spectroscopy(TERS)has emerged as an important technique for structural analysis at sub-molecular scale.Here in this work,we report a TERS study of an isolated free-base porphyrin molecule adsorbed on the Ag(100)surface at cryogenic temperature(~7 K).Site-dependent TERS spectra reveal distinct local vibrational information for the chemical constituents within a single molecule.Moreover,distinct spatial features among different Raman peaks can be resolved from the TERS mapping images.These images are found to associate with related vibrational modes,enabling to resolve the mode associated with N-H bonds at the sub-nanometer level.This study will provide deep insights into the symmetry of adsorption configurations and local vibrational information within a single molecule.
基金funded by the National Key Technology Support Program of China (No. 2014BAC18B02)the National Natural Science Foundation of China (Nos. 41272176 and 41202116)
文摘In order to quantify the effect of matrix shrinkage on reservoir permeability during coalbed methane production, coal samples from Huozhou, Changzhi and Jincheng areas in Shanxi province (classified as high-volatile bituminous coal, low-volatile bituminous coal and anthracite, respectively) were collected, and adsorption-induced coal swelling in methane were determined by an optical method at 40 ℃ and pressure up to 12 MPa. All three coals showed similar behavior-that swelling increased as a function of pressure up to about 10 MPa but thereafter no further increase in swelling was observed. Swelling in the direction perpendicular to the bedding plane is greater than that parallel to the bedding plane, and the differences are about 7.77-8.33%. The maximum volumetric swelling ranges from 2.73% to 3.21 %-increasing with increasing coal rank. The swelling data can be described by a modified DR model. In addition, swelling increases with the amount of adsorption. However, the increase shows a relatively slower stage followed by a relatively faster stage instead of a linear increase. Based on the assumption that sorption-induced swelling/shrinkage of coal in methane is reversible, the permeability increases induced by coal shrinkage during methane desorption was analyzed, and the results indicate that the permeability change is larger for higher rank coal in the same unit of pressure depletion.
基金Supported by Tianjin Natural Science Foundation (No. 033604711) and Science and Technology Foundation of Construction Ministry (No. 03-2-064).
文摘This paper studies the adsorption of diethyl phthalate (DEP,an environmental hormone) on the surface of nanoscale TiO2, effects of pH value of solutions, initial concentrations of DEP and additive surfactant on photocatalytic degradation and dynamics of DEP. Under ultra violet illumination, the interaction between DEP and surfactants including DBS (sodium dodecylbenzenesulfonate), CTAB (cetyltrimethylammonium bromide), and OP-10 (nonylphenol polyoxyethylene ether) was exploited from the perspective of degradation speed calculated by the data of high pressure liquid chromatography (HPLC) and UV-Vis spectra, respectively. Photocatalytic degradation of DEP followed pseudo first-order reaction kinetics. DEP as substrate degraded fast when its initial concentration was 130 mg/L. TiO2 had certain adsorption ability of DEP. TiO2 could adsorb the most DEP at the approximately neutral pH of 6.91. Degradation of DEP was not affected obviously by additives OP-10 and DBS. Degradation rate of DEP was not enhanced greatly in the presence of surfactants, but degradation of DBS was sped up. Degradation rate of DEP was depressed in the presence of additive CTAB. The more CTAB was added, the less DEP was degraded. Degradation rate of CTAB became slow with the increase of initial CTAB concentration. The possible adsorption models among TiO2, DEP and surfactants were given.
基金supported by the National Natural Science Foundation of China (Nos.51274104,50874052)the National Basic Research Program of China (No.2011CB933700)。
文摘A continuous online in situ attenuated total reflection Fourier-transform infrared(ATR-FTIR)spectroscopic technique was used to investigate the adsorption and desorption kinetics of heptyl xanthate(KHX)on the surface of ZnO and Cu(Ⅱ)activated ZnO.The results showed that Cu(Ⅱ)facilitated the xanthate adsorption process on the surface,and led to the formation of cuprous xanthate(CuX),dixanthogen(X_(2))and xanthate aggregates.The adsorption of xanthate on the surface of ZnO and Cu(Ⅱ)activated ZnO was found to both follow the pseudo-first-order kinetic model.When the NaOH solution was used as a desorption agent,the adsorbed xanthate can largely be removed due to the competition between OH^(−)and HX−.However,for Cu(Ⅱ)activated ZnO,the peak intensities at 1197 and 1082 cm^(−1) had no obvious weakening,and the absorption intensities at 1261 and 1026 cm^(−1) increased in the first 5 min,indicating an ion-exchange reaction between OH^(−)and surface zinc bonded xanthate HX−and the reorganization of adsorbed xanthate.
基金supported by Beijing Elitist Foundation (Grant no. 2005IA05016012) Beijing New Century Talent Foundation (Grant no. 011 005400601)
文摘The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by mathematical models. Chemical modification experiments and Fourier transform infrared spectra indicated that carboxyl and amine groups were the important functional groups for adsorption of Cd. The maximum contribution of physical adsorption in the overall adsorption process was evaluated as 5.5%. These results indicated that chemisorption was the dominating mechanism of Cd biosorption by C.reinhardtii.
文摘Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis indicated that the AIGHS were hetero-porous.Boehm titrations and Fourier-transform infrared spectra demonstrated the chemical heterogeneity of the AIGHS surface.Batch biosorption studies were used to examine the effects of process parameters in the following range:pH 2-12,temperature 293-313 K,contact time 1-5 h and initial concentration 200-600 mg·L^(-1).The matching of equilibrium data with the Langmuir-Freundlich form of isotherms indicated that the BV10 was adsorbed via chemisorption and pore diffusion.Kinetic investigation indicated multiple order chemisorption through an Avrami kinetic model.Film diffusion controlled the rate of BV10 biosorption onto AIGHS.The spontaneous and endothermic nature of sorption was corroborated by thermodynamic study.Continuous biosorption experiments were performed using a fixed-bed column and the influence of operating parameters was explored for different ranges of initial concentration 100-300 mg·L^(-1),bed height 5-10 cm,and flow rate 2.5-4.5 ml·min^(-1).A dose response model accurately described the fixed-bed biosorption data.An external mass transfer correlation was formulated explaining BV10-AIGHS sorption.
基金supported by the National Natural Science Foundation of China(21377020)the Fundamental Research Funds for the Central Universities(DUT15QY17)
文摘Quantum-sized CdS-coated TiO2 nanotube array (Q-CdS-TiO2 NTA) was fabricated by the modified successive ionic layer absorption and reaction method. Scanning electron microscope and transmission electron microscope images showed the regular structure of TiO2 NTA, where quantum-sized CdS (diameter 〈10nm) deposited on both the inside and outside of TiO2 nanotube wall. Fabrication conditions including immersing cycles, calcination temperature and drying process were well optimized, and the Q-CdS-TiO2 NTA and its photoelectrochemical (PEC) properties were characterized by X-ray fluorescence spectrometer, UV-Vis diffuse reflectance spectra and photovoltage. Distinct increases in visible light absorption and photocurrent were observed as the immersing cycle was increased from 5 to 20 times. The additional drying process accelerated the CdS crystal growth rate, and thus, the fabrication time could be shortened accordingly. Calcination temperature influenced the PEC property of Q-CdS-TiO2 NTA deeply, and the optimized calcination temperature was found as 500 ℃. As the Q-CdS-TiO2 NTA was fabricated under such condition, the visible photocurrent density increased to 2.8 mA/cm and the photovoltage between 350 and 480 nm was enhanced by 2.33 times than that without calcination. This study is expected to optimize Q-CdS-TiO2 NTA fabrication conditions for the purpose of improving its PEC performance.