Lingyan Wu

Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals

A novel nanoadsorbent for the removal of heavy metal ions is reported. Cotton was first hydrolyzed to obtain cellulose nanocrystals (CNCs). CNCs were then chemically modified with succinic anhydride to obtain SCNCs. The sodic nanoadsorbent (NaSCNCs) was further prepared by treatment of SCNCs with saturated NaHCO3 aqueous solution. Batch experiments were carried out with SCNCs and NaSCNCs for the removal of Pb2+ and Cd2+. The effects of contact time, pH, initial adsorption concentration, coexisting ions and the regeneration performance were investigated. Kinetic studies showed that the adsorption equilibrium time of Pb2+ and Cd2+ was reached within 150 min on SCNCs and 5 min on NaSCNCs. The adsorption capacities of Pb2+ and Cd2+ on SCNCs and NaSCNCs increased with increasing pH. The adsorption isotherm was well fitted by the Langmuir model. The maximum adsorption capacities of SCNCs and NaSCNCs for Pb2+ and Cd2+ were 367.6 mg/g, 259.7 mg/g and 465.1 mg/g, 344.8 mg/g, respectively. SCNCs and NaSCNCs showed high selectivity and interference resistance from coexisting ions for the adsorption of Pb2+. NaSCNCs could be efficiently regenerated with a mild saturated NaCl solution with no loss of capacity after two recycles. The adsorption mechanisms of SCNCs and NaSCNCs were discussed.

Superb fluoride and arsenic removal performance of highly ordered mesoporous aluminas.

Highly ordered mesoporous aluminas and calcium-doped aluminas were synthesized through a facile and reproducible method. Their fluoride adsorption characteristics, including adsorption isotherms, adsorption kinetics, the effect of pH and co-existing anions were investigated. These materials exhibited strong affinity to fluoride ions and extremely high defluoridation capacities. The highest defluoridation capacity value reached 450 mg/g. These materials also showed superb arsenic removal ability. 1g of mesoporous alumina was able to treat 200 kg of arsenic contaminated water with a pH value of 7, reducing the concentration of arsenate from 100 ppb to 1 ppb.

Synthesis and characterization of multi-amino-functionalized cellulose for arsenic adsorption

A multi-amino adsorbent for arsenic adsorption was reported in this paper. Glycidyl methacrylate (GMA) was first grafted onto the surface of cotton cellulose using ceric ammonium nitrate (CAN) as the initiator, and then the introduced epoxy groups reacted with tetraethylenepentamine (TEPA) to obtain a multi-amino adsorbent. The adsorbent was characterized by FTIR, elemental analysis, (13)C NMR and SEM. Then, the adsorption of arsenic for this adsorbent was investigated. The results showed that the GMA and TEPA were successfully grafted onto the surface of cellulose, and the modification improved the arsenic adsorption performances. Kinetic study suggested that the chemisorptions were the rate-limiting step. Among the three adsorption isotherm models used, Langmuir model fitted the experimental data best. The adsorption capacities of arsenic were less affected by coexisting ions. The adsorbent could be effectively regenerated for four cycles with 0.1 mol/L NaOH solution.

Heterogeneous reaction of NO2 on Al2O3: the effect of temperature on the nitrite and nitrate formation.

Although recent evidence suggests that the heterogeneous reaction of NO2 on the surface of mineral aerosol plays an important role in the atmospheric chemistry, a fundamental understanding of how temperature influences the rate and extent of nitrate formation processes remains unclear. This work presents the first laboratory study of the effect of temperature on heterogeneous reaction of NO2 on the surface of γ-Al2O3 in the temperature range of 250-318 K at ambient pressure. From the analysis of IR spectra, nitrite was found to be an intermediate product at temperatures between 250 and 318 K. It is proved by our experiments that nitrite would convert to the bidentate nitrate as the reaction proceeded. In addition, it is interesting to find that the rate of conversion increased with decreasing temperature. Along with nitrite decrease, the initial rate of nitrate formation increased while the rate of nitrate formation in the steady region decreased with decreasing temperature. The uptake coefficients at seasonal temperatures were determined for the first time and were found to be sensitive to temperature. Finally, atmospheric implications of the role of temperature on the heterogeneous reaction of NO2 with mineral aerosol are discussed.

Fe3+ and amino functioned mesoporous silica: preparation, structural analysis and arsenic adsorption.

Two novel adsorbents to remove excess arsenate and arsenite in the drinking water were prepared for the first time by grafting monoamine and diamine, respectively, and then coordinating Fe(3+) on silica gel that was obtained using sol-gel method with two-step acid-base catalysis. It was found that both adsorbents had mesoporous structure, large specific surface, and high amino and iron content according to N(2) adsorption isotherms, FTIR, XPS, and NMR analysis. The removal ability and adsorption rate of the adsorbents were very high for both As(V) and As(III). Langmuir and Freundlich models were used to fit the adsorption isotherm and investigate the adsorption mechanism. The effects of chloride and sulfate anion on the removal of arsenate and arsenite for the two adsorbents were also studied.

Synergistic Effects between SO2 and HCOOH on α-Fe2O3

Heterogeneous reactions on mineral aerosols remain an important subject in atmospheric chemistry because of their role in altering the properties of particles and the budget of trace gases. Yet, the role of coadsorption of trace gases onto mineral aerosols and potential synergistic effects are largely uncertain, especially synergistic effects between inorganic and organic gas-phase pollutants. In this study, synergistic effects between HCOOH and SO2 were investigated for the first time using in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). It was found that the heterogeneous reaction of HCOOH is hindered significantly by coexisting SO2. The total amount of formate decreased, whereas the total amount of sulfate was not affected during coadsorption on the surface of α-Fe2O3. Futhermore, part of the formate on the surface was catalytically decomposed to CO2 by α-Fe2O3 with the help of SO2. These results suggest a possible mechanism for the observed correlations between sulfate and carboxylate in the atmosphere.

Influence of Temperature on the Heterogeneous Reaction of Formic Acid on α-Al2O3

Despite increased awareness of the role played by heterogeneous reactions of formic acid on mineral aerosol, the experimental determination of how these atmospheric reaction rates vary with temperature remain a crucially important part of atmosphere science. Here we report the first measurement of heterogeneous uptake of formic acid on α-Al(2)O(3) as a function of temperature (T = 240-298 K) at ambient pressure using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). From the analysis of the spectral features, crystalline HCOOH was identified at low temperature besides common product (formate ions) on the surface. It was also interesting to find that crystalline HCOOH can continue to react with α-Al(2)O(3). The reaction mechanisms at both room and low temperature were discussed. Furthermore, the reactive uptake coefficients were acquired and found to increase with decreasing temperature. Finally, the atmospheric lifetime of formic acid because of heterogeneous loss on mineral aerosol was estimated at temperatures related to the upper troposphere.

The influence of relative humidity on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate particles

Heterogeneous reactions of SO2 and O3 with CaCO3 particles were investigated at a series of relative humidity (RH, 1% to 90%) and 298K using a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The uptake coefficients of SO2 on CaCO3 at different RHs were obtained for the first time. Our results proved that high RH could substantially promote the formation of sulfate, for which the highest concentration (80% RH and reaction time of 200min) and highest formation rate in stable stage (85% RH) were 14 times and 43 times that at 1% RH, respectively. The surface products, increment of concentration and formation rate of sulfate changed with RH which were due to the surface adsorbed water (SAW) on the particles. SAW could increase the reactive sites on the particles and thus accelerate the conversion of SO2 into sulfite, and sulfite could be oxidized rapidly. Liquid-like water layers formed on the particle surface could enhance the ion mobility and promote the aggregation of CaSO4 hydrates, which could expose more reactive sites and result in additional adsorption of SO2. Piecewise equations of uptake coefficient with RH were given and could be referred by model simulation. The results are of importance in understanding the explosive growth of sulfate during severe haze episodes accompanied with high RH.

Temperature dependence of the heterogeneous uptake of acrylic acid on Arizona test dust

In this study, the temperature dependence of the heterogeneous uptake of acrylic acid on Arizona test dust (ATD) has been investigated within a temperature range of 255-315K using a Knudsen cell reactor. Combined with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiment, it was found that acrylic acid could adsorb on ATD via surface OH groups and convert to carboxylate on the particle surface. The kinetics study suggests that the initial true uptake coefficient (γt) of acrylic acid on ATD decreases from (4.02±0.12)×10-5 to (1.73±0.05)×10-5 with a temperature increase from 255 to 315K. According to the temperature dependence of uptake coefficients, the enthalpy (ΔHobs) and entropy (ΔSobs) of uptake processes were determined to be -(9.60±0.38) KJ/mol and -(121.55±1.33) J·K/mol, respectively. The activation energy for desorption (Edes) was calculated to be (14.57±0.60) KJ/mol. These results indicated that the heterogeneous uptake of acrylic acid on ATD surface was sensitive to temperature. The heterogeneous uptake on ATD could affect the concentration of acrylic acid in the atmosphere, especially at low temperature.

The formation and growth of calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved calcium carbonate

Calcium sulfate is a major constituent of atmospheric sulfate, with a typical rod-like morphology ranging from several hundred nanometers to approximately two micrometers observed in field studies. However, the chemical formation mechanism is still not well known. In this study, the kinetics and mechanism for the formation and growth of rod-like calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved CaCO3 at different relative humidity (RH) were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and scanning electron microscopy (SEM). We found that the concentration and formation rate of sulfate decreased with the increasing diameter of CaCO3 particles, and thus smaller particles could enhance the formation of sulfate due to more reactive sites on smaller particles. The rod-like calcium sulfate crystals were formed only at RH above 60% and in the presence of reactant gases through the heterogeneous pathway. The liquid-like water layer formed by promotion of high RH in the presence of reactant gases could facilitate the formation and aggregation of calcium sulfate hydrates and thus promote the formation and growth of rod-like calcium sulfate crystals. This study provides a possible mechanism for the formation and growth of rod-like calcium sulfate crystals existing in the atmosphere.