Adsorption and activation of copper ions on chalcopyrite surfaces:A new viewpoint of self-activation

The adsorption behaviors of copper ions on chalcopyrite surfaces were investigated based on zeta potential measurements, X-ray photoelectron spectroscopy, copper ion adsorption experiments, first-principles calculations, and Hallimond tube cell flotation experiments. The results show that copper ions activate the chalcopyrite as a result of the interactions between copper ions and sulfur on the chalcopyrite surface. This adsorption increases the flotation rate under certain conditions, and this is beneficial for the flotation of chalcopyrite. The copper ions in the flotation pulp are mainly derived from surface oxidation dissolution and the release of fluid inclusions, and these effects enable chalcopyrite to be activated.

Preparation of UV-visible light responsive photocatalyst from titania-bearing blast furnace slag modified with(NH_4)_2SO_4

Sulfate-modified titanium dioxide-bearing blast furnace slag（STBBFS） photocatalysts were prepared by the high energy ball milling method with（NH4）2SO4 and titanium dioxide-bearing blast furnace slag（TBBFS） as raw materials.X-ray photoelectron spectroscopy（XPS）,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,thermogravimetric analysis（TGA）,UV-visible diffuse reflectance absorption spectra（UV-Vis）,adsorption experiment and photocatalytic degradation measurement were conducted to characterize the structure,surface status,light absorption capacity,adsorption capacity and photocatalytic activity of the obtained photocatalysts.The adsorption equilibrium was described by the Langmuir isotherm model with a maximum adsorption capacity of 8.25 mg/g of Cr（VI） ions onto the STBBFS photocatalysts.As a result,sulfation of TBBFS improved the photocatalytic activities of STBBFSx photocatalysts.At a low calcination temperature,the photocatalytic activity of STBBFS300 photocatalyst was markedly higher compared with TBBFSx prepared at high calcination temperature,indicating that the photocatalytic activity of STBBFSx photocatalyst was determined by the balanced result between adsorption capacity and perovskite content.

Adsorption behavior and mechanism of Bi(Ⅲ) ions on rutile-water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.

Temperature Effect on Boron Adsorption-Desorption Kinetics in Soils

The effect of temperature on the properties of boron adsorption-desorption in brown-red soil, yellowbrown soil and calcareous alluvial soil of Hubei Province was investigated with the mobile displacement technique. The experimental data of B adsorption-desorption amounts and reaction t line at 25 and 40℃ were fitted by the zero-order, first-order and parabolic diffusion kinetic equations. The adsorption process was in conformity with the parabolic diffusion law at both the temperatures, and the values of rate constant of the parabolic diffusion equation in B adsorption were 0.138, 0.124 and 0.105 mg kg-1 min-1/2 at 25℃, and 0.147, 0.146 and 0.135 mg kg-1 min-1/2 at 40℃ for the brown-red soil, yellow-brown soil, and calcareous alluvial soil, respectively. The relationship between amount of B desorption and reaction time could be well described by the first-order kinetic equation, and the corresponding values of rate constant were 0.0422, 0.0563 and 0.0384 min-1 at 25℃, and 0.0408, 0.042 3 and 0.0401 min-1 at 40℃ for the brown-red soil, the yellow-brown soil and the calcareous alluvial soil, respectively. Therefore, the desorption process of B might be related to the amount of B adsorbed in soil. The higher the temperature, the lower the amount of B adsorption for the same soil in the same reaction time. The values of the apparent activation energy of B adsorption in the three soils calculated with the rate constants of parabolic diffusion equation were 3.27, 8.44 and 12.99 kJ mol-1, respectively, based on the experimental data of B adsorption amounts and reaction time at 25 and 40℃.

Modelling and Fixed Bed Column Adsorption of Cr(Ⅵ) onto Orthophosphoric Acid-activated Lignin

The advantage of using an available and abundant residual biomass, such as lignin, as a raw material for activated carbons is that it provides additional economical interest to the technical studies. In the current investigation, a more complete understanding of adsorption of Cr（VI） from aqueous systems onto HaPO4-acid activated lignin has been achieved via microcolumns, which were operated under various process conditions. The practice of using microcolumn is appropriate for defining the adsorption parameters and for screening a large number of poten- tial adsorbents. The effects of solution pH （2-8）, initial metal ion concentration （0.483-1.981 mmol.L-1）, flow rate （1.0-3.1 cm3-min-1）, ionic strength （0.01-0.30 mmol-L-1） and adsorbent mass （0.11 0.465 g） on Cr（VI） adsorption were studied by assessing the microcolmnn breakthrough curve. The microcolumn data were fitted by the Thomas model, the modified Dose model and the BDST model. As expected, the adsorption capacity increased with initial Cr（VI） concentration. High linear flow rates, pH values and ionic strength led to early breakthrough of Cr（VI）. The model constants obtained in this study can be used for the design of pilot scale adsorption process.

Removal of Cu(Ⅱ) from Aqueous Solution Using a Novel Crosslinked Alumina-Chitosan Hybrid Adsorbent

A novel biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to activated alumina based on oil shale ash via crosslinking. The adsorbent was characterized by various techniques, such as Fourier transform infrared spectroscopy, scarming＇ elec.tron micros cop.y, the rmogravimetric-differentialthermal analysis, and X-ray photoelectron spectroscope. Batch isothermal equilibrium adsorption experiments were condcted to evaluate the adsorbent for the removal of Cu（Ⅱ） from wastewater. The effect of pH and agitation time on the adsorption capacity was also investigated, indicating that the optimum pH was 6.0. The equilibrium adsorp-tion data were correlated with Langmuir and Freundlich models. The maximum monolayer adsorption capacity of chitosan coated alumina sorbent as obtained from Langmuir adsorption isotherm was fotmd to be 315.46 mg.g-1 for Cu（Ⅱ）. The adsorbent loaded with Cu（Ⅱ） was readily regenerated using 0.1 mol.L-1 sodium hydroxide solution. All these indicated that chitosan coated alumina adsorbent not only have high adsorption activity, but also had good stability in the wastewater treatment process.

Selective adsorption of thiocyanate anions on Ag-modified g-C_3N_4 for enhanced photocatalytic hydrogen evolution

Silver‐modified semiconductor photocatalysts typically exhibit enhanced photocatalytic activitytoward the degradation of organic substances.In comparison,their hydrogen‐evolution rates arerelatively low owing to poor interfacial catalytic reactions to producing hydrogen.In the presentstudy,thiocyanate anions(SCN–)as interfacial catalytic active sites were selectively adsorbed ontothe Ag surface of g‐C3N4/Ag photocatalyst to promote interfacial H2‐evolution reactions.The thiocyanate‐modified g‐C3N4/Ag(g‐C3N4/Ag‐SCN)photocatalysts were synthesized via photodepositionof metallic Ag on g‐C3N4and subsequent selective adsorption of SCN– ions on the Ag surface by animpregnation method.The resulting g‐C3N4/Ag‐SCN photocatalysts exhibited considerably higherphotocatalytic H2‐evolution activity than the g‐C3N4,g‐C3N4/Ag,and g‐C3N4/SCN photocatalysts.Furthermore,the g‐C3N4/Ag‐SCN photocatalyst displayed the highest H2‐evolution rate(3.9μmolh?1)when the concentration of the SCN– ions was adjusted to0.3mmol L?1.The H2‐evolution rateobtained was higher than those of g‐C3N4(0.15μmol h?1)and g‐C3N4/Ag(0.71μmol h?1).Consideringthe enhanced performance of g‐C3N4/Ag upon minimal addition of SCN– ions,a synergistic effectof metallic Ag and SCN– ions is proposed―the Ag nanoparticles act as an effective electron‐transfermediator for the steady capture and rapid transportation of photogenerated electrons,while theadsorbed SCN– ions serve as an interfacial active site to effectively absorb protons from solution andpromote rapid interfacial H2‐evolution reactions.Considering the present facile synthesis and itshigh efficacy,the present work may provide new insights into preparing high‐performance photocatalytic materials

Adsorption of dimethyl trisulfide from aqueous solution on a low-cost adsorbent:thermally activated pinecone

Thermally activated pinecone(TAP) was used for the adsorption of dimethyl trisulfide(DMTS)from aqueous solutions,which was proved to be the main odorous in algae-caused black bloom.The effects of adsorbent dosage,adsorbate concentration and contact time on DMTS biosorption were studied.The TAP produced at 600℃ exhibited a relatively high surface area(519.69 m^2/g) and excellent adsorption capacity.The results show that the adsorption of DMTS was initially fast and that the equilibrium time was6 h.Higher initial DMTS concentrations led to lower removal percentages but higher adsorption capacity.The removal percentage of DMTS increased and the adsorption capacity of TAP decreased with an increase in adsorbent dosage.The adsorption process conforms well to a pseudo-second-order kinetics model.The adsorption of DMTS is more appropriately described by the Freundlich isotherm(R^2=0.996 1) than by the Langmuir isotherm(R^2=0.916 9).The results demonstrate that TAP could be an attractive low-cost adsorbent for removing DMTS from water.

Electrochemical study on adsorption behavior of surfactants at β-2CaO·SiO2/NaAlO2 interface

β-2CaO＇SiO2 was obtained with analytical grade reagents. Polyethylene glycol （PEG）, sodium polyacrylate （PAAS） and their mixture were used to inhibit the decomposition of β-2CaO·SiO2 in sodium aluminate solution. The potential of solid-liquid interface and the adsorption mechanism were studied by the methods of Zeta potential measurement and XPS. The results indicate that PEG and PAAS have synergistic effect on the inhibition of secondary reaction. The inhibitory effect is the best when the volume ratio of PAAS to PEG is 1：1 and the total concentration is 12.5 mg/L. PAAS adsorbs on the surface of β-2CaO-SiO2 by the formation of --COOCa coordinate bond, and the negative charge enters into Stem layer, which results in the decrease of particle potential and the obvious change of binding energy of Ca 2p, Si 2p and O Is. PEG only physically adsorbs on the surface ofβ-2CaO·SiO2, and had little effect on particle potential and binding energy of Ca 2p, Si 2p and O Is.

Synergetic effects for p-nitrophenol abatement using a combinedactivated carbon adsorption-electrooxidation process

A novel fluidized electrochemical reactor that integrated advanced electrochemical oxidation with activated carbon (AC) fluidization in a single cell was developed to model pollutant p-nitrophenol (PNP) abatement. AC fluidization could enhance COD removal by 22%-30%. In such a combined process, synergetic effects on PNP and COD removal was found, with their removal rate being enhanced by 137.8% and 97.8%, respectively. AC could be electrochemically regenerated and reused, indicating the combined process would be promising for treatment of biorefractory organic pollutants.

Isotherm Equation Study of F Adsorbed from Water Solution by Fe2（SO4）3-modified Granular Activated Alumina

The adsorption equilibrium of a fluoride solution on 1-2 mm granular activated alumina modified by Fe2(SO4)3 solution was investigated.The experiments were conducted using a wide range of initial fluoride concentrations(0.5 to 180 mg·L-1 at pH～7.0) and an adsorbent dose of 1.0 g·L-1.The application of Langmuir and Freundlich adsorption isotherm models(linear and nonlinear forms) generally showed that a single Langmuir or Freundlich equation cannot fit the entire concentration gap.Experimental data on low equilibrium concentrations(0.1 to 5.0 mg·L-1) was in line with both Langmuir and Freundlich isotherm models,whereas that of high equilibrium concentrations(5.0 to 150 mg·L-1) was more in line with the Freundlich isotherm model.A new LangmuirFreundlich function was used for the entire concentration gap,as well as for low and high concentrations.

Understanding the Effect of the Exchange-Correlation Functionals on Methane and Ethane Formation over Ruthenium Catalysts

Density functional theory(DFT)has been established as a powerful research tool for heterogeneous catalysis research in obtaining key thermodynamic and/or kinetic parameters like adsorption energies,enthalpies of reaction,activation barriers,and rate constants.Understanding of density functional exchangecorrelation approximations is essential to reveal the mechanism and performance of a catalyst.In the present work,we reported the influence of six exchange-correlation density functionals,including PBE,RPBE,BEEF+vdW,optB86b+vdW,SCAN,and SCAN+rVV10,on the adsorption energies,reaction energies and activation barriers of carbon hydrogenation and carbon-carbon couplings during the formation of methane and ethane over Ru(0001)and Ru(1011)surfaces.We found the calculated reaction energies are strongly dependent on exchange-correlation density functionals due to the difference in coordination number between reactants and products on surfaces.The deviation of the calculated elementary reaction energies can be accumulated to a large value for chemical reaction involving multiple steps and vary considerably with different exchange-correlation density functionals calculations.The different exchange-correlation density functionals are found to influence considerably the selectivity of Ru(0001)surface for methane,ethylene,and ethane formation determined by the adsorption energies of intermediates involved.However,the influence on the barriers of the elementary surface reactions and the structural sensitivity of Ru(0001)and Ru(1011)are modest.Our work highlights the limitation of exchange-correlation density functionals on computational catalysis and the importance of choosing a proper exchange-correlation density functional in correctly evaluating the activity and selectivity of a catalyst.

Enhanced degradation of carbon tetrachloride by surfactant-modified zero-valent iron

Sorption of carbon tetrachloride （CT） by zero-valent iron （ZVI） is the rate-limiting step in the degradation of CT, so the sorption capacity of ZVl is of great importance. This experiment was aimed at enhancing the sorption of CT by ZVI and the degradation rate of CT by modification of surfactants. This study showed that ZVI modified by cationic surfactants has favorable synergistic effect on the degradation of CT. The CT degradation rate of ZVI modified by cetyl pyridinium bromide （CPB） was higher than that of the unmodified ZVI by 130%, and the CT degradation rate of ZVI modified by cetyl trimethyl ammonium bromide （CTAB） was higher than that of the unmodified ZVI by 81%. This study also showed that the best degradation effect is obtained at the near critical micelle concentrations （CMC） and that high loaded cationic surfactant does not have good synergistic effect on the degradation due to its hydrophilicity and the block in surface reduction sites. Furthermore degradation of CT by ZVI modified by nonionic surfactant has not positive effect on the degradation as the ionic surfactant and the ZVI modified by anionic surfactant has hardly any obvious effects on the degradation.

CO_2 Capture by Vacuum Swing Adsorption Using F200 and Sorbead WS as Protective Pre-layers

In order to solve the water issues when 13X zeolite was applied to capture CO 2 from wet flue gas by vacuum swing adsorption process, multi-layered adsorption system was considered regarding activated alumina F200 and silica gel based Sorbead WS as pre-layer materials. LBET (extended Largmuir-BET) model and extended CMMS (cooperative multimolecular sorption) equation were simulated respectively to describe water loading on F200 and Sorbead WS. The two equations can be well added into our in-house simulator to simulate double-layered CO 2 -VSA (vacuum swing adsorption) process. Results indicated that water can be successfully stopped in pre-layers with a good CO 2 capture performance.

Adsorption Studies of Chlorpropham and 3-Chloroaniline on Chemically Activated Halloysite

Chemically modified halloysite proved to be an effective adsorbent for the pesticide chlorpropham and 3-chloroaniline from an aqueous solution. Adsorption experiments were conducted using such procedures as the time-dependent （kinetic） procedure and the concentration dependent （isotherm） procedure. Results indicate that the adsorption process is related to the kind of the studied compound. The equilibrium data are well suited to a Freundlich isotherm in the case of both investigated compounds. Adsorption kinetics of chlorpropham and 3-chloroaniline on acid-treated halloysite was successfully described by pseudo-second order kinetic model and the model of Weber and Morris. From the present study, we suggest that the adsorption of chlorpropham and 3-chloroaniline on the modified halloysite is a rather complex process involving two steps： external mass transfer and intra-particle diffusion.

PREPARATION OF ACTIVATED CARBON FIBER AND THEIR XENON ADSORPTION PROPERTIES (III)-ADSORPTION ON MODIFIED ACTIVATED CARBON FIBER

Structures of a series of activated carbon fibers were modified by impregnating them with organic and inorganic materials such as Methylene blue(Mb)、p-nitrophenol (PNP)、NaCl or by oxidizing with KMnO4 or HNO3. The influence of pore filling or chemical treatment on their xenon adsorption properties was studied. The experimental results show that Mb and PNP filling of activated carbon fibers result in the decrease of xenon adsorption capacities of these treated ACFs, which is due to the decrease of their surface area and micro-pore volume. However, the adsorption capacity increases greatly with oxidizing treatment of activated carbon fibers by 7mol/L HNO3.

Biosorption of basic violet 10 onto activated Gossypium hirsutum seeds:Batch and fixed-bed column studies

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.

金属元素修饰碳基材料光/电还原CO_(2)研究进展

推进“碳达峰碳中和”目标,缓解能源危机和实现CO_(2)减排,光/电催化技术可将CO_(2)还原为可再生碳氢燃料和高附加值化学品,被认为是经济有效的双赢策略。其中,高效光/电催化剂研制作为关键核心问题。碳基材料凭借其良好的物理化学稳定性、表面性质、独特导电性和优异吸附性能引起了广泛关注。更重要的是,对其引入金属活性组分,不但可以影响金属的表面形貌、粒径大小、分散性以及存在形式,而且与金属组分间的相互作用能控制金属与载体之间的电荷转移,增强催化剂对CO_(2)的吸附能力和催化转化效率。基于此,综述了碳基材料负载不同种类金属(Fe,Co,Ni,Cu和双金属)的制备方法,探讨了碳基材料与不同种类金属之间的结合方式对催化性能的影响规律,最后对碳基金属复合材料存在的问题以及未来的应用前景进行了总结与展望。

Effects of Iron and Aluminum Oxides and Kaolinite on Adsorption and Activities of Invertase *1

Experiments were conducted to study the influences of synthetic bayerite, non crystalline aluminum oxide (N AlOH), goethite, non crystalline iron oxide (N FeOH) and kaolinite on the adsorption, activity, kinetics and thermal stability of invertase. Adsorption of invertase on iron, aluminum oxides fitted Langmuir equation. The amount of invertase held on the minerals followed the sequence kaolinite > goethite > N AlOH > bayerite > N FeOH. No correlation was found between enzyme adsorption and the specific surface area of minerals examined. The differences in the surface structure of minerals and the arrangement of enzymatic molecules on mineral surfaces led to the different capacities of minerals for enzyme adsorption. The adsorption of invertase on bayerite, N AlOH, goethite, N FeOH and kaolinite was differently affected by pH. The order for the activity of invertase adsorbed on minerals was N FeOH > N AlOH > bayerite > reak goethite > kaolinite. The inhibition effect of minerals on enzyme activity was kaolinite > crystalline oxides > non crystalline oxides. The pH optimum of iron oxide and aluminum oxide invertase complexes was similar to that of free enzyme (pH 4.0), whereas the pH optimum of kaolinite inv ertase complex was one pH unit higher than that of free enzyme. The affinity to substrate and the maximum reaction velocity as well as the thermal stability of combined invertase were lower than those of the free enzyme.

Synergy of adsorption and visible light photocatalysis to decolor methyl orange by activated carbon/nanosized CdS/chitosan composite

Activated carbon/nanosized CdS/chitosan(AC/n-CdS/CS) composites as adsorbent and photoactive catalyst were prepared under low temperature(≤60 ℃) and ambient pressure.Methyl orange(MO) was chosen as a model pollutant to evaluate synergistic effect of adsorption and photocatalytic decolorization by this innovative photocatalyst under visible light irradiation.Effects of various parameters such as catalyst amount,initial MO concentration,solution pH and reuse of catalyst on the decolorization of MO were investigated to optimize operational conditions.The decolorization of MO catalyzed by AC/n-CdS/CS fits the Langmuir-Hinshelwood kinetics model,and a surface reaction,where the dyes are absorbed,is the controlling step of the process.Decolorization efficiency of MO is improved with the increase in catalyst amount within a certain range.The photodecolorization of MO is more efficient in acidic media than alkaline media.The decolorization efficiency of MO is still higher than 84% after five cycles and 60 min under visible light irradiation,which confirms the reusability of AC/n-CdS/CS composite catalyst.