Adsorption Mechanisms of Mesoporous Adsorbents in Solutions

Sieve effect, complexation, ionic exchange, electrostatic interaction, hydrogen bonding, hydrophobic interaction, and molecular recognition based on molecular imprinting are comprehensively discussed.

A new liquid membrane diffusion model for characterizing the adsorption kinetics of europium by using a continuous measurement of adsorption platform

To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.

Characterization of adsorptive capacity and mechanisms on adsorption of copper, lead and zinc by modified orange peel

A novel adsorbent was prepared by modifying orange peel with sodium hydroxide and calcium chloride. The morphological and characteristics of the adsorbent were evaluated by infrared spectroscopy （IR）, scanning electron microscopy （SEM） and N2-adsorption techniques. The adsorption behavior of Cu^2＋, Pb^2＋ and Zn^2＋ on modified orange peel （SCOP） was studied by varying parameters like pH, initial concentration of metal ions. Equilibrium was well described by Langmuir equation with the maximum adsorption capacities for Cu^2＋, Pb^2＋ and Zn^2＋ of 70.73, 209.8 and 56.18 mg/g, respectively. Based on the results obtained in batch experiments, breakthrough profiles were examined using a column packed with SCOP for the separation of small concentration of Pb^2＋ from an excess of Zn^2＋ followed by elution tests. Ion exchange with Ca^2＋ neutralizing the carboxyl groups of the pectin was found to be the predominant mechanism.

Adsorption mechanisms of PFOA onto activated carbon anchored with quaternary ammonium/epoxide-forming compounds: A combination of experiment and model studies

When wood-based activated carbon was tailored with quaternary ammonium/epoxide(QAE) forming compounds(QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid(PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before halfbreakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.

Flotation and adsorption of novel Gemini decyl-bishydroxamic acid on bastnaesite:Experiments and density functional theory calculations

Rare earth element is an important strategic metal,but the supply of high purity rare earth ores is growing slowly,which is in sharp contradiction with the rapidly growing demand.Froth flotation has been confirmed to be an effective method to separate bastnaesite from its gangue minerls.However,the traditional collectors are facing serious problems in flotation separation of minerals,requiring the addition of excess depressant and regulator in the flotation process.Herein,we proposed and synthesized novel Gemini hydroxamic acids Octyl-bishydroxamic acid(OTBHA),Decyl-bishydroxamic acid(DCBHA)and Dodecyl-bishydroxamic acid(DDBHA)as the collectors in bastnaesite-barite flotation system.The effect of different carbon chain lengths on the molecular properties were explored by density functional theory(DFT)calculations.DCBHA possessed a stronger reactivity compared with OCBHA and DDBHA.The flotation results verified the consistency of the computational calculation about the performance prediction of Gemini hydroxamic acids.Compared with OCBHA and DDBHA,DCBHA displayed superior collecting affinity toward bastnaesite,and did not float barite.Zeta potential results showed that the presence of DCBHA increased the potential of bastnaesite,while it had almost no effect on barite,indicating DCBHA had a stronger affinity for bastnaesite.Then,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analyses indicated that the adsorption mechanism was due to two hydroxamate groups of DCBHA co-anchored on bastnaesite surface by forming five-membered hydroxamic―(O―O)―Ce complexes.In addition,atomic force microscopy(AFM)clearly observed that DCBHA uniformly aggregated on bastnaesite surface,which increased surface contact angle and improved the hydrophobicity of bastnaesite.

Biomass Carbon Improves the Adsorption Performance of Gangue-Based Ceramsites:Adsorption Kinetics and Mechanism Analysis

The large accumulation of coal gangue,a common industrial solid waste,causes severe environmental problems,and green development strategies are required to transform this waste into high-value-added products.In this study,low-cost ceramsites adsorbents were prepared from waste gangue,silt coal,and peanut shells and applied to remove the organic dye methylene blue from wastewater.We investigated the microstructure of ceramsites and the effects of the sintering atmosphere,sintering temperature,and solution pH on their adsorption performance.The ceramsites sintered at 800℃under a nitrogen atmosphere exhibited the largest three-dimensional-interconnected hierarchical porous structure among the prepared ceramsites;further,it exhibited the highest methylene blue adsorption performance,with an adsorption capacity of 0.954 mg·g^(−1),adsorption efficiency of over 95%,and adsorption equilibrium time of 1 h at a solution pH of 9.The removal efficiency remained greater than 75%after five adsorption cycles.The adsorption kinetics data were analyzed using various models,including the pseudosecond-order kinetic model and Langmuir equation,and the adsorption was attributed to electrostatic interactions between the dyes and ceramsites,n-interactions,and hydrogen bonds.The prepared coal gangue ceramsites exhibited excellent adsorption capacities,removal rates,and cyclic stabilities,demonstrating their promising application prospects for the comprehensive utilization of solid waste and for wastewater treatment.

Adsorption mechanism of 2-mercaptobenzothiazole on chalcopyrite and sphalerite surfaces:Ab initio and spectroscopy studies

Interaction mechanism of the collector,2-mercaptobenzothiazole（MBT）,with chalcopyrite and sphalerite surfaces were investigated by Fourier transform infrared（FTIR） and density functional theory,Results of FTIR showed that some characteristic peaks of MBT were observed on the chalcopyrite surface,including C=N,C=N-S and C-S stretching vibration peaks,and the adsorption product was CuMBT.But there were no characteristic peaks of MBT on the sphalerite surface.The thione molecular form of MBT was the most efficient and stable,N and exocyclic S were the more favourable reactive sites for nucleophilic attacked by metal atoms.Compared with ZnS（110）,MBT is more readily adsorbed on CuFeS2（112）.Attachment of MBT occurs due to strong bonding through exocyclic S p and s orbits with Cu d orbit on CuFeS2（112） and electron transfer from Cu atom to S atom.Under the vacuum condition,MBT in the form of thione molecular cannot be adsorbed on ZnS（110） spontaneously.

Efficient removal of Cr(VI) by polydopamine-modified lignin from aqueous solution: Batch and XAFS studies

Lignocellulose has the potential to become a bio-based adsorbent due to its biodegradability and renewability.In this study,a novel polydopamine functionalized-lignin(lignin@PDA),prepared via self-polymerization of dopamine(PDA)on lignin,was used as a bio-based adsorbent for rapid scavenging of hexavalent chromium(Cr(VI)).The morphology,functional groups,crystalline structure,and chemical composition of lignin@PDA were characterized with a scanning electron microscope-energy dispersive spectrometer,Fourier transform infrared spectroscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.The Cr(VI)adsorption process of lignin@PDA was studied using batch experiments as a function of pH,ionic strength,adsorbent dose,and contact time at room temperature.The adsorption rate of lignin@PDA was five times greater than that of the unmodified lignin,with a maximum adsorption capacity of 102.6 mg/g in an acidic medium.The adsorption of Cr(VI)on lignin@PDA fit the pseudo-secondorder equation and the Freundlich model,indicating that the adsorption process was mainly dominated by chemisorption and surface complexation.The thermodynamic parameters showed that adsorption of Cr(VI)on lignin@PDA was an endothermic and spontaneous process.The X-ray absorption fine structure results showed that sorption and reduction of Cr(VI)into Cr(II)occurred simultaneously on lignin.Moreover,PDA coating not only improved the reactivity of lignin but also promoted the complete reduction of Cr(VI)by lignin.According to these results,polydopamine functionalized-lignin is a promising bio-based adsorbent for immobilization of Cr(VI)from wastewater.

Collecting performances of N-dodecylethylene-diamine and its adsorption mechanism on mineral surface

The collecting performances of N-dodecylethylene-diamine （ND） to quartz and hematite were studied via single mineral flotation. Experimental results show that ND has stronger collecting ability to quartz than hematite. Different floatability of quartz and hematite was presented in the existence of depressant. Compared with lauryl amine, ND has stronger collecting performances to quartz. Satisfied separation result of artificially mixed sample was acquired with iron grade of concentrate of 59.92% and iron recovery of 88.85% when pulp pH value was 7.27 with 41.7 mg/L collector and 3.33 mg/L starch. Polar group properties calculation results indicated that ND has stronger collecting capability and better selectivity than lauryl amine. Measurement results of zeta-potentials and infrared spectrum showed that hydrogen bonding adsorption and electrostatic adsorption occur between the surface of ND and quartz.

Effects of Microporous Structure of Activated Carbon on Adsorption Performance of N-butane

[Objective] The paper was to study the effect of microporous structure of ac- tivated carbon on adsorption performance of n-butane. [Method] Using 8 activated car- bons prepared from different materials and technologies, the effects of physical prop- erties of activated carbon on butane adsorption performance were investigated. [Result] Specific surface area, pore volume and pore size distribution of activated carbon exert- ed remarkable effects on butane adsorption. The activated carbon with high percent- age of micropore volume within the range of 1.2-2 nm possessed high butane activity. The level of butane retentivity rose with the increase of the volume of pore within the range of 0.5-0,9 nm, which led to smaller butan working capacity （BWC）. [Conclusion] The study provided reference for the adsorption research for activated carbon.

Efficient Sequestration of Congo Red Dye from Aqueous Solutions Using Pamam Dendrimer-Silica Composite

This study investigates the removal of Congo Red dye from aqueous solution using functionalized generation 3.0 and 5.0 polyamidoamine dendrimer-silica gel composite (G-3PS, G-5PS). Fourier Transform-Infra Red spectroscopy, Brunauer Emmett and Teller, Thermo Gravimetric Analysis, pH at point of zero charge, and scanning electron microscopy measurements have been applied to characterize the synthetic nanohybrid composite, these techniques revealed the successful functionalization of both dendrimer molecules and subsequent immobilization onto silica gel. The implications of varying adsorption parameters such as contact time, initial concentration of adsorbate, temperature and pH on both composites were studied. Experimental data obtained from batch adsorption processes were fitted into two equilibrium isotherms (Langmuir and Freundlich) and 3 kinetic models (Pseudo-First-Order, Pseudo-Second-Order, Intra Particle Diffusion). Adsorption mechanism was mainly governed by film diffusion due to electrostatic interactions between the functionalized dendrimer surface and Congo Red molecules. Thermodynamic parameters illustrate that the adsorption is endothermic and spontaneous. Findings suggest the Nanocomposites (G-3PS and G-5PS) are good adsorbents for the removal of Congo Red dye from aqueous solutions.

Flotation performance and adsorption mechanism of novel 1-(2-hydroxyphenyl)hex-2-en-1-one oxime flotation collector to malachite

A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotation test,zeta potential,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis techniques.Compared with benzohydroxamic acid(BA),1-(2-hydroxyphenyl)ethan-1-one oxime(HPEO)and sodium isobutyl xanthate(SIBX),HPHO exhibited excellent collecting power to malachite without additional reagents,such as Na2S regulator and methyl isobutyl carbinol(MIBC)frother.Results of zeta potential indicated that HPHO was coated on malachite surfaces through a chemisorption process.FTIR and XPS data gave clear evidence for the formation of Cu−oxime complex on malachite surfaces after HPHO adsorption through the linkage between C=C,—OH,N—OH group and Cu species.

Highly Efficient Adsorption of Copper Ions by a PVP-Reduced Graphene Oxide Based On a New Adsorptions Mechanism

Polyvinylpyrrolidone-reduced graphene oxide was prepared by modified hummers method and was used as adsorbent for removing Cu ions from wastewater. The effects of contact time and ions concentration on adsorption capacity were examined. The maximum adsorption capacity of 1689 mg/g was observed at an initial p H value of 3.5 after agitating for 10 min. It was demonstrated that polyvinylpyrrolidone-reduced graphene oxide had a huge adsorption capacity for Cu ions, which was 10 times higher than maximal value reported in previous works. The adsorption mechanism was also discussed by density functional theory. It demonstrates that Cu ions are attracted to surface of reduced graphene oxide by C atoms in reduced graphene oxide modified by polyvinylpyrrolidone through physisorption processes, which may be responsible for the higher adsorption capacity. Our results suggest that polyvinylpyrrolidone-reduced graphene oxide is an effective adsorbent for removing Cu ions in wastewater. It also provides a new way to improve the adsorption capacity of reduced graphene oxide for dealing with the heavy metal ion in wastewater.

Preparation of Clay/Biochar Composite Adsorption Particle and Performance for Ammonia Nitrogen Removal from Aqueous Solution

This study aimed to present a novel clay/biochar composite adsorption particle, which made from abandoned reed straw and clay to remove ammonia nitrogen(NH4^+-N) from micro-contaminated water. The removal performance of NH4^+-N by composite adsorption particle was monitored under different raw material proportions and initial NH4^+-N concentration. Besides, adsorption kinetics and adsorption isotherms were investigated to reveal the adsorption mechanisms. The results showed that NH4^+-N was effectively removed under optimal proportion of biochar, foaming agent and crosslinker with 20%, 3%, and 3%, respectively. The optimal contact time was 150 min and the best removal efficiency was 88.6% at initial NH4^+-N concentration of 20 mg L^-1. The adsorption performance was well described by the second order kinetic model and Freundlich model. The novel clay/biochar composite adsorption particle in this study demonstrated a high potential for NH4^+-N removal from surface water.

CO_2 adsorption performance of different amine-based siliceous MCM-41 materials

A series of amine-based adsorbents were synthesized using siliceous MCM-41 individually impregnated with four different amines（ethylenediamine（EDA）,diethylenetriamine（DETA）,tetraethylenepentamine（TEPA） and pentaethylenehexamine（PEHA）） to study the effect of amine chain length and loading weight on their CO2 adsorption performances in detail.The adsorbents were characterized by FT-IR,elemental analysis,and thermo-gravimetric analysis to confirm their structure properties.Thermo-gravimetric analysis was also used to evaluate the CO2 adsorption performance of adsorbents.Longer chain amine-based materials can achieve higher amine loadings and show better thermal stability.The CO2 adsorption capacities at different temperatures indicate that the CO2 adsorption is thermodynamically controlled over EDAMCM41 and DETA-MCM41,while the adsorption over TEPA-MCM41 and PEHA-MCM41 is under kinetic control at low temperature.The chain length of amines affects the CO2 adsorption performance and the adsorption mechanism significantly.The results also indicate that CO2 adsorption capacity can be enhanced despite of high operation temperatures,if appropriate amines（TEPA and PEHA） are applied.However,adsorbents with short chain amine exhibit higher adsorption and desorption rates due to the collaborative effect of rapid reaction mechanisms of primary amines and less diffusion resistance of shorter chain length amines.

Adsorption of platinum(Ⅳ)onto D301R resin

Pt（Ⅳ） was quantitatively adsorbed by D301R resin in the medium of pH = 3.47. The statically saturated adsorption capacity is 410 mg/g. Pt（Ⅳ） adsorbed on D301R resin can be eluted by 1.0-2.0 mol/L NaOH. The rate constant is k298 = 5.43 × 10^-5 s^-1. The adsorption of Pt（Ⅳ） on D301R resin obeys the Freundlich isotherm. The adsorption parameters of thermodynamics are as follows： enthalpy change AH = 4.37 kJ/mol, Gibbs free energy change AG = -5.39 kJ/mol, and entropy change AS = 32.76 J/（mol.K）. The apparent activation energy is Ea = 22.5 kJ/mol. The coordination molar ratio of the functional group of D301R resin to Pt（Ⅳ） is 2：1.

Adsorption of Acetanilide Herbicides on Soil and Its Components: Ⅳ. Sorption of Acetanilide Herbicides on Soils and its Correlation with Soil Properties

Sorption of acetanilide herbicides, metolachlor, acetochlor, pretilachlor and butachlor on eight soils with various physical and chemical properties was studied. The adsorption isotherms could fit Freundich equation well (r 2 ≥0.91) and the adsorption extents increased in the order: metolachlor < acetochlor < pratilachlor < butachlor. The product of Freundlich adsorption constants, Kf (1/n), showed to have a good correlation with organic matter content (OM) of soils for each of these herbicides, suggesting that OM is the primary factor dominating in the adsorption process of these asetanilide herbicides. Multivariant correlation regression between Kf (1/n) and two factors, water solubility (S.) of herbicides and OM, was also performed. Kf(1/n) correlated with 1/S. and OM/S. well, showing that high S. corresponds to a weak tendency to adsorb on soils. Infrared (IR) spectra and electron spin resonance (ESR) parameters confirmed that multifunctional H-bonds and charge-transfer bonds were the main adsorption mechanisms of these acetanilide herbicides. The abilities of herbicides to form these adsorption bonds with HA increased in the same order as the extent of adsorption.

Adsorption of cadmium ions from aqueous solutions by activated carbon with oxygen-containing functional groups

The adsorption of aqueous cadmium ions(Cd(Ⅱ)) have been investigated for modified activated carbon(AC-T)with oxygen-containing functional groups.The oxygen-containing groups of AC-T play an important role in Cd(Ⅱ) ion adsorption onto AC-T.The modified activated carbon is characterized by scanning electron microscopy,Fourier transform infrared spectroscopy(FT-IR) and X-ray photoelectron spectroscopy(XPS).The results of batch experiments indicate that the maximal adsorption could be achieved over the broad pH range of 4.5 to 6.5.Adsorption isotherms and kinetic study suggest that the sorption of Cd(Ⅱ) onto AC-T produces monolayer coverage and that adsorption is controlled by chemical adsorption.And the adsorbent has a good reusability.According to the FT-IR and XPS analyses,electrostatic attraction and cation exchange between Cd(Ⅱ) and oxygen-containing functional groups on AC-T are dominant mechanisms for Cd(Ⅱ) adsorption.

Adsorption mechanism of sodium oleate and styryl phosphonic acid on rutile and amphibole surfaces

A reagent combination of sodium oleate(NaOl)and salicyl hydroximic acid was employed as the roughing and scavenging collectors,whereas styryl phosphoric acid(SPA)and octanol were employed as the cleaning collectors.Results of bench-scale flotation demonstrate that the dosage of SPA can be reduced by about 80%,and that a better flotation index can be obtained using the proposed reagent system.The results of adsorption amount and contact angle measurements indicate that the rutile surface adsorbed not only a large amount of residual NaOl but also SPA and a small amount of NaOl remained on the amphibole surface in strong acidic solution.The hydrophobic difference between rutile and amphibole surfaces was therefore amplified in cleaning,and their further separation became much easier consequently.

Simulation of methane adsorption in diverse organic pores in shale reservoirs with multi-period geological evolution

In shale reservoirs,the organic pores with various structures formed during the thermal evolution of organic matter are the main storage site for adsorbed methane.However,in the process of thermal evolution,the adsorption characteristics of methane in multi type and multi-scale organic matter pores have not been sufficiently studied.In this study,the molecular simulation method was used to study the adsorption characteristics of methane based on the geological conditions of Longmaxi Formation shale reservoir in Sichuan Basin,China.The results show that the characteristics of pore structure will affect the methane adsorption characteristics.The adsorption capacity of slit-pores for methane is much higher than that of cylindrical pores.The groove space inside the pore will change the density distribution of methane molecules in the pore,greatly improve the adsorption capacity of the pore,and increase the pressure sensitivity of the adsorption process.Although the variation of methane adsorption characteristics of different shapes is not consistent with pore size,all pores have the strongest methane adsorption capacity when the pore size is about 2 nm.In addition,the changes of temperature and pressure during the thermal evolution are also important factors to control the methane adsorption characteristics.The pore adsorption capacity first increases and then decreases with the increase of pressure,and increases with the increase of temperature.In the early stage of thermal evolution,pore adsorption capacity is strong and pressure sensitivity is weak;while in the late stage,it is on the contrary.