•The heterogeneous reaction of multicomponent particles is poorly understood.•Ca(NO3)2 formed on CaCO3 particles could further interact with Na2SO4 during the reaction.•The coexisting Na2SO4 alter the heterogeneous reactivity of CaCO3 with NO2.Atmospheric particles can undergo nucleation, coagulation, chemical-aging, dissolution-precipitation or other atmospheric processes, resulting in complex multicomponent aerosols. The coexisting species have potentially important consequences in the heterogeneous reactions of multicomponent aerosol particles with polluted gases, which are still poorly understood. The effect of coexisting Na2SO4 on heterogeneous uptake of NO2 on CaCO3 particles is investigated in a broad RH range. The combination of DRIFTS, Raman, SEM and IC provides qualitative and quantitative information about the formation of nitrate and other surface species. Ca(NO3)2 and NaNO3 are generated on mixed CaCO3-Na2SO4 particles under dry condition. Both the amount of NO3− formed and the NO3− formation rates for the mixtures can be predicted based on the linear addition of those for pure CaCO3 and Na2SO4 particles under dry condition. The further reaction of Ca(NO3)2 with Na2SO4 could lead to the formation of crystal NaNO3 and CaSO4·0.5H2O at 30% RH. Coagulation between Ca2 + and SO42 − in surface adsorbed water is observed after part conversion of CaCO3 to Ca(NO3)2, resulting in the formation of CaSO4·2H2O at 80% RH. The amount of NO3− formed on the mixtures is dramatically enhanced relative to the predictions at 30% and 80% RH. The findings presented here highlight the role of coexisting species in the heterogeneous reactions of trace gases with multicomponent aerosols due to the complexity of atmospheric particles.The reaction mechanism for the reactions of the Na2SO4-CaCO3 mixtures with NO2.Download high-res image (73KB)Download full-size image

To study the HONO formation mechanisms during a pollution period, a continuous measurement was performed in both urban and suburban aeras of Beijing. During this period, the PM2.5 concentrations increased to 201 and 137 μg/m3 in urban and suburban areas, respectively. The concentrations of HONO, CO, SO2, O3, NO, NO2, NOx were 1.45 ppbv, 0.61 ppmv, 8.7 ppbv, 4.3 ppbv, 44.4 ppbv, 37.4 ppbv, 79.4 ppbv and 0.72 ppbv, 1.00 ppmv, 1.2 ppbv, 7.9 ppbv, 3.7 ppbv, 8.2 ppbv, 11.9 ppbv, in urban and suburban areas, respectively. To compare possible pathways of HONO formation in both sites, the contributions of direct emissions, heterogeneous formations, and homogeneous productions were studied. HONO/NO2 ratios in the two sites indicated that heterogeneous reactions of NO2 were more efficient in suburban areas. And in both urban and suburban areas, the increase of PM2.5 concentrations and RH would promote the conversion efficiency in RH that ranged from 0% to 85%. However, when RH was above 85%, the HONO formation slowed down. Moreover, the study of direct emissions and homogeneous reactions showed that they contributed to a majority of HONO increase in urban areas than the 20% contributions in suburban areas. It implied that the high NOx concentrations and NO concentrations in urban areas or in pollution periods would make direct emissions and homogeneous reactions become dominant in HONO formations.

Porous magnetic cellulose beads have been successfully prepared via a facile one-pot wet extrusion by in situ depositing CoFe2O4 nanoparticles on cellulose beads. Cellulose beads serve as a template to prevent CoFe2O4 particles from aggregating. The deposited CoFe2O4 nanoparticles are tightly entrapped within cellulose beads because of the strong attractive interactions between the cellulose beads and CoFe2O4 particles. The functionalized cellulose beads can be easily separated from aqueous solution by the external magnetic field. The encapsulated CoFe2O4 nanoparticles act as the magnetic substrate and the active sites to adsorb metal ions. An attractive feature of this preparation method is that it is versatile to prepare a variety of cellulose-based functional nanocomposites in the form of macroscopic beads by incorporating functional particles into the pores of cellulose beads.

Composite materials, containing magnetic nanoparticles and cellulose, were synthesized by one-step co-precipitation using NaOH–thiourea–urea aqueous solution for cellulose dissolution. The NaOH in cellulose solution acted as the precipitant of iron oxide nanoparticles, and low-cost cellulose was used as the template to promote the growing of nanoparticles in the cellulose matrix. The method provided a facile, “green” pathway for the fabrication of magnetic nanomaterials. The synthesized cellulose@iron oxide nanoparticles were characterized by FTIR, XRD, SEM, TEM, XPS, TG and VSM. The FTIR, XRD and XPS results demonstrated the formation of Fe2O3 nanoparticles in the composite materials after the co-precipitation. SEM and TEM characterization showed that the Fe2O3 nanoparticles were dispersed in the cellulose matrix due to the synergistic effect. Magnetometric measurements revealed that the resultant composites of cellulose@Fe2O3 nanoparticles exhibited a sensitive magnetic-induced behavior and could be easily separated from aqueous solution through the external magnetic field. The composite materials were applied to remove arsenic from aqueous solution. The results showed that the magnetic nanoparticle composites displayed excellent adsorption efficiency of arsenic compared with other magnetic materials reported, and the Langmuir adsorption capacities of the composites for the removal of arsenite and arsenate were 23.16 and 32.11 mg g−1, respectively.

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, 13C 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.Highlights► A multi-amino-functionalized cellulose was synthesized for the removal of arsenic. ► The aminated cellulose has relative high nitrogen content. ► The adsorbent has a high adsorption capacity for As(V). ► The adsorption capacities of arsenic were less affected by coexisting ions. ► The adsorbent can be efficiently regenerated with NaOH solution.

Cellulose@hydroxyapatite (HA) nanocomposites were prepared in NaOH/thiourea/urea/H2O solution via situ hybridization. The composite materials combine the advantage of cellulose and HA with the high specific surface area and the strong affinity toward fluoride. The composite materials were characterized by FTIR, SEM, XRD, TG and XPS, and the adsorption of fluoride was investigated. Adsorption kinetics indicated the adsorption equilibrium of fluoride was within 360 min and the adsorption process was well described by the pseudo-second-order kinetic model. The Langmuir and Freundlich isotherm models could fit the experimental data well. At the initial fluoride concentration of 10 mg/L, the residual concentration using above 3 g/L adsorbent dose could meet the drinking water standard of WHO norms. Furthermore, the coexisting anions had no significant effect on fluoride adsorption.Highlights► The nano-size HA was uniformly dispersed in the cellulose template matrix. ► The fluoride concentration could meet the drinking water standard after adsorption. ► The coexisting anions had no significant effect on fluoride adsorption.

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.

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.

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-Al2O3 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-Al2O3. 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.

Acetyl acrylic anhydride (CH3C(O)OC(O)CHCH2) and its halogen-substituted derivatives (CF3C(O)OC(O)CHCH2 and CCl3C(O)OC(O)CHCH2) were prepared by the heterogeneous reaction of gaseous CH2═CHC(O)Cl with CX3C(O)OAg (X = H, F, or Cl). The molecular conformations and electronic structure of these three compounds were investigated by HeI photoelectron spectroscopy, photoionization mass spectroscopy, FT-IR, and theoretical calculations. They were theoretically predicted to prefer the [ss-c] conformation, with each C═O bond syn with respect to the opposite O–C bond and the C═C bond in cis orientation to the adjacent C═O bond. The experimental first vertical ionization potential for CH3C(O)OC(O)CHCH2, CF3C(O)OC(O)CHCH2, and CCl3C(O)OC(O)CHCH2 was determined to be 10.91, 11.42, and 11.07 eV, respectively. In this study, the rule of the conformation properties of anhydride XC(O)OC(O)Y was improved by analyzing the different conformations of anhydrides with various substitutes.

Composite materials, containing magnetic nanoparticles and cellulose, were synthesized by one-step co-precipitation using NaOH–thiourea–urea aqueous solution for cellulose dissolution. The NaOH in cellulose solution acted as the precipitant of iron oxide nanoparticles, and low-cost cellulose was used as the template to promote the growing of nanoparticles in the cellulose matrix. The method provided a facile, “green” pathway for the fabrication of magnetic nanomaterials. The synthesized cellulose@iron oxide nanoparticles were characterized by FTIR, XRD, SEM, TEM, XPS, TG and VSM. The FTIR, XRD and XPS results demonstrated the formation of Fe2O3 nanoparticles in the composite materials after the co-precipitation. SEM and TEM characterization showed that the Fe2O3 nanoparticles were dispersed in the cellulose matrix due to the synergistic effect. Magnetometric measurements revealed that the resultant composites of cellulose@Fe2O3 nanoparticles exhibited a sensitive magnetic-induced behavior and could be easily separated from aqueous solution through the external magnetic field. The composite materials were applied to remove arsenic from aqueous solution. The results showed that the magnetic nanoparticle composites displayed excellent adsorption efficiency of arsenic compared with other magnetic materials reported, and the Langmuir adsorption capacities of the composites for the removal of arsenite and arsenate were 23.16 and 32.11 mg g−1, respectively.