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1.

Water pollution and the unsustainable use of fossil fuel derivatives require advanced catalytic methods to clean waters and to produce fine chemicals from modern biomass. Classical homogeneous catalysts such as sulfuric, phosphoric, and hydrochloric acid are highly corrosive and non-recyclable, whereas heterogeneous catalysts appear promising for lignocellulosic waste depolymerization, pollutant degradation, and membrane antifouling. Here, we review the use of sulfonated graphene and sulfonated graphene oxide nanomaterials for improving membranes, pollutant adsorption and degradation, depolymerization of lignocellulosic waste, liquefaction of biomass, and production of fine chemicals. We also discuss the economy of oil production from biomass. Sulfonated graphene and sulfonated graphene oxide display an unusual large theoretical specific surface area of 2630 m2/g, allowing the reactants to easily enter the internal surface of graphene nanosheets and to reach active acid sites. Sulfonated graphene oxide is hydrophobic and has hydrophilic groups, such as hydroxyl, carboxyl, and epoxy, thus creating cavities on the graphene nanosheet’s surface. The adsorption capacity approached 2.3–2.4 mmol per gram for naphthalene and 1-naphthol. Concerning membranes, we observe an improvement of hydrophilicity, salt rejection, water flux, antifouling properties, and pollutant removal. The nanomaterials can be reused several times without losing catalytic activity due to the high stability originating from the stable carbon–sulfur bond between graphene and the sulfonic group.

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2.
This study investigated the effects of surface functional groups, cation exchange capacity (CEC), surface charge, sesquioxides and specific surface area (SSA) of three soil clay fractions (SCFs) (kaolinite–illite, smectite and allophane) on the retention of dissolved organic carbon (DOC) in soils. Physico-chemical properties of the SCFs before and after removing native carbon and/or sesquioxides were characterised, and the DOC adsorption–desorption tests were conducted by a batch method. Native organic carbon (OC)/sesquioxide removal treatments led to a small change in the CEC values of kaolinite–illite, but significant changes in those of smectite and allophane. The net negative surface charge increased in all samples with an increase in pH indicating their variable charge characteristics. The removal of native OC resulted in a slight increase in the net positive charge on soil clay surfaces, while sesquioxide removal increased the negative charge. Changes in the functional groups on the SCF surfaces contributed to the changes in CEC and zeta potential values. There was a strong relationship (R 2 = 0.93, p < 0.05) between the Langmuir maximum DOC adsorption capacity (Q max) and SSA. The Q max value also showed a moderately strong relationship (R 2 = 0.55, p < 0.05) with zeta potential (at pH 7). Q max was only poorly correlated with CEC and native OC content. Therefore, along with SSA, the surface charge and functional groups of SCFs played the key role in determining the adsorption affinity and hence retention of DOC in soils.  相似文献   

3.
A new type of Au/TiO2/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO2 on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO2 and RGO. Au/TiO2/RGO had a better photocatalytic activity than Au/ TiO2 for the degradation of phenol. Electrochemical measurements indicated that Au/TiO2/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO2/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO2/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO2 to effectively reduce photogenerated charge recombination.
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4.
ABSTRACT

Pharmaceutical compounds are considered emerging environmental pollutants that have a potential harmful impact on environment and human health. In this study, the spiky green horse-chestnut shell was used for the biosorption and removal of acetaminophen from aqueous solution. It was analysed how the parameters, like contact time, pH, mass of biosorbent and temperature, influence the effectiveness of acetaminophen removal from aqueous solutions. The equilibrium was quickly achieved after 10?min (~60%). The amount of acetaminophen adsorption slightly increased with the increase of the mass of biosorbent, and for example for an aqueous solution containing 10?mg/L of acetaminophen adsorption was increased from 62% to 81%. The promising results obtained at pH ranged between 2 and 9, which shows that the adsorption of acetaminophen did not depend on the pH and it may be a consequence of the predominant microporous sorbent and its surface charge. The result is better correlated to a pseudo-second-order kinetic model of type 2 (r 2?=?0.9992) than pseudo-first-order. A sorption mechanism of acetaminophen on biosorbent was also proposed. The sorption of acetaminophen over biosorbent is mainly preceded by hydrophilic interactions between hydroxyl and carbonyl groups in pharmaceutical molecules and hydroxyl and carboxyl groups on the surface of biosorbent.  相似文献   

5.
V2O5-WO3/TiO2 catalyst was poisoned by impregnation with NH4Cl, KOH and KCl solution, respectively. The catalysts were characterized by X-ray diffraction (XRD), inductively coupled plasma (ICP), N2 physisorption, Raman, UV-vis, NH3 adsorption, temperature-programmed reduction of hydrogen (H2-TPR), temperature-programmed oxidation of ammonia (NH3-TPO) and selective catalytic reduction of NO x with ammonia (NH3-SCR). The deactivation effects of poisoning agents follow the sequence of KCl>KOH?NH4Cl. The addition of ammonia chloride enlarges the pore size of the titania support, and promotes the formation of highly dispersed V = O vanadyl which improves the oxidation of ammonia and the high-temperature SCR activity. K+ ions are suggested to interact with vanadium and tungsten species chemically, resulting in a poor redox property of catalyst. More importantly, potassium can reduce the Brønsted acidity of catalysts and decrease the stability of Brønsted acid sites significantly. The more severe deactivation of the KCl-treated catalyst can be mainly ascribed to the higher amount of potassium resided on catalyst.  相似文献   

6.
A simple solvothermal method was used to prepare monodisperse magnetite (Fe3O4) nanoparticles attached onto graphene oxide (GO) sheets as adsorbents to remove tetrabromobisphenol A (TBBPA) from an aqueous solution. These Fe3O4/GO (MGO) nanocomposites were characterized by transmission electron microscopy. The adsorption capacity at different initial pH, contact duration, and temperature were evaluated. The kinetics of adsorption was found to fit the pseudo-second-order model perfectly. The adsorption isotherm well fitted the Langmuir model, and the theoretical maximum of adsorption capacity calculated by the Langmuir model was 27.26 mg?g-1. The adsorption thermodynamics of TBBPA on the MGO nanocomposites was determined at 303 K, 313 K, and 323 K, respectively. The results indicated that the adsorption was spontaneous and endothermic. The MGO nanocomposites were conveniently separated from the media by an external magnetic field within several seconds, and then regenerated in 0.2 M NaOH solution. Thus, the MGO nanocomposites are a promising candidate for TBBPA removal from wastewater.  相似文献   

7.
GO or RGO promotes bromate formation during ozonation of bromide-containing water. CeO2/RGO significantly inhibits bromate formation compared to RGO during ozonation. CeO2/RGO shows an enhancement on DEET degradation efficiency during ozonation. Ozone (O3) is widely used in drinking water disinfection and wastewater treatment. However, when applied to bromide-containing water, ozone induces the formation of bromate, which is carcinogenic. Our previous study found that graphene oxide (GO) can enhance the degradation efficiency of micropollutants during ozonation. However, in this study, GO was found to promote bromate formation during ozonation of bromide-containing waters, with bromate yields from the O3/GO process more than twice those obtained using ozone alone. The promoted bromate formation was attributed to increased hydroxyl radical production, as confirmed by the significant reduction (almost 75%) in bromate yield after adding t-butanol (TBA). Cerium oxide (less than 5 mg/L) supported on reduced GO (xCeO2/RGO) significantly inhibited bromate formation during ozonation compared with reduced GO alone, and the optimal Ce atomic percentage (x) was determined to be 0.36%, achieving an inhibition rate of approximately 73%. Fourier transform infrared (FT-IR) spectra indicated the transformation of GO into RGO after hydrothermal treatment, and transmission electron microscope (TEM) results showed that CeO2 nanoparticles were well dispersed on the RGO surface. The X-ray photoelectron spectroscopy (XPS) spectra results demonstrated that the Ce3+/Ce4+ ratio in xCeO2/RGO was almost 3‒4 times higher than that in pure CeO2, which might be attributed to the charge transfer effect from GO to CeO2. Furthermore, Ce3+ on the xCeO2/RGO surface could quench Br⋅ and BrO⋅ to further inhibit bromate formation. Meanwhile, 0.36CeO2/RGO could also enhance the degradation efficiency of N,N-diethyl-m-toluamide (DEET) in synthetic and reclaimed water during ozonation.  相似文献   

8.
An integrated process-based model was used to study how the changing climate affects the availability of water and nitrogen, and consequently the dynamics of productivity of Norway spruce (Picea abies) on sites with different initial soil water conditions in southern Finland over a 100-year period. The sensitivity of the total stem volume growth in relation to short-term availability of water and nitrogen was also analyzed. We found that a high proportion (about 88–92%) of the total precipitation was lost in total evapotranspiration (incl. canopy evaporation (Ec), transpiration (Et) and ground surface evaporation (Eg)), under both current and changing climate. Furthermore, under the changing climate the cumulative amount of Ec and Eg were significantly higher, while Et was largely lower than under the current climate. Additionally, the elevated temperature and increased expansion of needle area index (L) enhanced Ec. Under the changing climate, the increasing soil water deficit (Wd) reduced the canopy stomatal conductance (gcs), the Et, humus yield (H, available nitrogen source) and nitrogen uptake (Nup) of the trees. During the latter phases of the simulation period, the canopy net photosynthesis (Pnc) was lower due to the reduced Nup and soil water availability. This also reduced the total stem volume production (Vs) on the site with the lower initial soil moisture content. The growth was slightly more sensitive to the change in precipitation than to the change in nitrogen content of the needles, when the elevated temperature was assumed. According to our findings, drought stress episodes may become more frequent under the changing climate. Thus, adaptive management strategies should be developed to sustain the productivity of Norway spruce in these conditions, and thus, to mitigate the adverse impacts of climate change.  相似文献   

9.
Selective catalytic reduction (SCR) of NO x with NH3 is an effective technique to remove NO x from stationary sources, such as coal-fired power plant and industrial boilers. Some of elements in the fly ash deactivate the catalyst due to strong chemisorptions on the active sites. The poisons may act by simply blocking active sites or alter the adsorption behaviors of reactants and products by an electronic interaction. This review is mainly focused on the chemical poisoning on V2O5-based catalysts, environmental-benign catalysts and low temperature catalysts. Several common poisons including alkali/alkaline earth metals, SO2 and heavy metals etc. are referred and their poisoning mechanisms on catalysts are discussed. The regeneration methods of poisoned catalysts and the development of poison-resistance catalysts are also compared and analyzed. Finally, future research directions in developing poisoning resistance catalysts and facile efficient regeneration methods for SCR catalysts are proposed.  相似文献   

10.
With extensive use of lithium ion batteries (LIBs), amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content (12%–21%) of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°C for 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
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11.
以乙二胺盐酸盐(EDH)为改性剂改性氧化石墨烯(GO),水热法制备氨基化氧化石墨烯(Amino-functionalized;graphene;oxide,AGO).SEM、XRD、FTIR和Zeta电位表征分析发现,AGO表面含有羟基、羧基及氨基基团,Zeta电位为pH=10.14.以水中低浓度六价铬Cr(Ⅵ)为污染物,探讨了乙二胺盐酸盐(EDH)用量、pH、AGO用量、Cr(Ⅵ)初始浓度以及常见干扰离子对AGO吸附Cr(Ⅵ)影响.结果表明,在pH=6.0、7-AGO用量为0.8;mg·L-1和Cr(Ⅵ)初始浓度为2.0;mg·L-1,7-AGO对Cr(Ⅵ)去除率可达95.1%;SO42-会明显抑制AGO对Cr(Ⅵ)的吸附.AGO对Cr(Ⅵ)的吸附过程符合二级动力学模型,吸附机制主要为静电作用.  相似文献   

12.

In this study, we investigated cadmium toxicity created by adsorption kinetics in several mixtures containing two types of multi-walled carbon nanotubes (COOH-MWCNT and NH2-MWCNT) and natural kaolinite. Characteristics of two types of MWCNTs were measured by zeta potential and ATR FT-IR graphs and TEM images. The solution of CNTs and kaolinite was tested to study Cd adsorption kinetics and mechanisms of differentiation-associated toxicity using Daphnia magna in a binary system (Cd–MWCNTs and Cd–kaolinite) and a ternary system (Cd–MWCNTs–kaolinite). In the binary system, Cd removal efficiency was nearly 100% and 40% for MWCNTs and kaolinite because of surface charge, respectively, with increasing sorbent concentration. In the ternary system, the trend of adsorption rate was similar to that of binary system. In comparison with percent mortality in the binary system, the solution in the ternary system showed higher toxicity due to the interaction of MWCNTs–kaolinite coagulated particles, thereby decreasing Cd adsorption onto CNTs and kaolinites. Overall, kaolinite can affect the adsorption process of Cd on MWCNTs in negative ways, depending on adsorption state. In conclusion, our studies suggest that kaolinite differs with adsorption ability of Cd by MWCNTs, and toxicity is likely to be produced by multivariable regression in the adsorption state.

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13.
The aim of this work was to test a process-based model (hydrological model combined with forest growth model) on the simulation of seasonal variability of evapotranspiration (ET) in an even-aged boreal Scots pine (Pinus sylvestris L.) stand over a 10 year period (1999-2008). The water flux components (including canopy transpiration (Et) and evaporation from canopy (Ec) and ground surface (Eg) were estimated in order to output the long-term stand water budget considering the interaction between climate variations and stand development. For validation, half-hourly data on eddy water vapor fluxes were measured during the 10 growing seasons (May-September). The model predicted well the seasonal course of ET compared to the measured values, but slightly underestimated the water fluxes both in non-drought and drought (2000, 2003 and 2006) years. The prediction accuracy was, on average, higher in drought years. The simulated ET over the 10 years explained, on average, 58% of the daily variations and 84% of the monthly amount of ET. Water amount from Et contributed most to the ET, with the fractions of Et, Ec and Eg being, on average, 67, 11 and 23% over the 10-year period, respectively. Regardless of weather conditions, the daily ET was strongly dependent on air temperature (Ta) and vapor pressure deficit (Da), but less dependent on soil moisture (Ws). On cloudy and rainy days, there was a non-linear relationship between the ET and solar radiation (Ro). During drought years, the model predicted lower daily canopy stomatal conductance (gcs) compared with non-drought years, leading to a lower level of Et. The modeled daily gcs responded well to Da and Ws. In the model simulation, the annual LAI increased by 35% between 1999 and 2008. The ratio of Ec: ET correlated strongly with LAI. Furthermore, LAI reduced the proportion of Eg as a result of the increased share of Ec and Et and radiation interception. Although the increase of LAI affected positively Et, the contribution of Et in ET was not significantly correlated with LAI. To conclude, although the model predicted reasonably well the seasonal course of ET, the calculation time steps of different processes in the model should be homogenized in the future to increase the prediction accuracy.  相似文献   

14.
There is a demand for the development of environmental friendly methods for the synthesis of graphene composites. Reduced graphene oxide/silver (RGO/Ag) nanocomposites are very good catalysts. Here, we propose a simple, green method for the synthesis of RGO/Ag nanocomposite using the amino acid tyrosine as bioreductant and stabilizing agent. RGO/Ag nanocomposite was characterized by using various analytical techniques and studied for its catalytic degradation of 4-nitrophenol. Results of attenuated total reflectance Fourier transform infrared spectroscopy and Zeta potential at ?55 mV reveal the surface capping of tyrosine onto the reduced graphene oxide nanosheets. RGO/Ag nanocomposites show excellent catalytic reduction of 4-nitrophenol with NaBH4, when compared to actual individual silver nanoparticles.  相似文献   

15.
When pieces of the staghorn coral Acropora acuminata are incubated with 14C-urea, the label is incorporated into skeletal carbonate. Incorporation of this label differs from that of H14CO 3 - , suggesting urea is not immediately hydrolysed to provide a further source of HCO 3 - . The effects of certain organic substrates upon calcification suggest the ornithine cycle is involved. Citrulline, an ornithine cycle intermediate, is found in high concentrations in the tissues of hermatypic corals. Urea, allantoins, NH3 and arginine are also present. These compounds are barely detectable in zooxanthellae or an ahermatypic coral. The allantoins may be present as calcium salts. It is suggested that allantoins are the medium by which Ca2+ and CO2 are transported to sites of calcification. Hydrolysis of urea, formed by breakdown of allantoins, yields CO2 and NH3. The NH3 may neutralise protons formed during precipitation of CaCO3 and bring about their removal from sites of calcification. As well as providing urea, the ornithine cycle may also be involved in the removal of NH3 from sites of calcification.  相似文献   

16.
This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO2(s) (δMnO2), and investigated the feasibility of employing δMnO2 for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO2 than that with lower molecular mass. Ca2+ facilitated more humic acid adsorption than Mg2+; UV-Vis spectra analysis indicated higher capabilities of Ca2+ coordinating with acidic functional groups of humic acid than that of Mg2+. Additionally, ζ potential characterization indicated that Ca2+ showed higher potential of increasing gz potential of δMnO2 than Mg2+. Ca2+ of 1.0 mmol/L increased ζ potential of δMnO2 from ?37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg2+ increased to lower value as ?9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO2, showing the important roles of-COO? functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO2.  相似文献   

17.
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NO x with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperatureprogrammed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NO x conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NO x .
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18.
Mn-CeO x /Ti-pillared clay (PILC) is an attractive catalyst for selective catalytic reduction of NO x at low temperature because of its low cost. The poisoning of K and Ca on the catalyst of Mn-CeO x /Ti-PILC is an important problem because K and Ca are always in presence in flue gas. To investigate the effect of K and Ca on the physicochemical characters of the catalysts, the techniques of NH3-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) were used to analyze the fresh and deactivated catalysts of Mn-CeO x /Ti-PILC. (Ca)Mn-CeO x /Ti-PILC and (K)Mn-CeO x /Ti-PILC are denoted for the dopes of the catalyst of Mn-CeO x /Ti-PILC with Ca and K, respectively. The activities of Mn-CeO x /Ti-PILC, (Ca)Mn-CeO x /Ti-PILC and (K)Mn-CeO x / Ti-PILC for NH3-selective catalytic reduction (SCR) reaction at low temperature were investigated. The results showed that with the dopes of K and Ca on the catalysts, the SCR activities of the catalysts decreased greatly, and K exhibited more poisoning effect than Ca. With the dopes of K and Ca, the acidity, the redox property and chemisorbed oxygen on the surfaces of the catalysts were decreased, which resulted in a decreasing in SCR activity.  相似文献   

19.
H. Fechter 《Marine Biology》1973,19(4):285-289
The perivisceral fluid of Paracentrotus lividus (Lamarck) contains, as main end-products of the nitrogenous metabolism, ammonia, urea, creatine, creatinine and traces of uric acid. In the organs analysed, the distribution and abundance of ammonia and urea fluctuate considerably. the intestine was found to have the highest NH4 +?N and the lowest urea-N contents. The axial organ contained the highest amount of urea-N and the lowest quantity of NH4 +?N; the perivisceral fluid, including the coelomocytes, contained intermediate amounts. The special relations to hemal system and coelothel, the presence of excretory material, and the analogous conditions to other invertebrates, suggest that the coelomocytes and parts of the intestine and axial organ are excretophoric and able to synthesize urea. From the known distribution of ammonia and urea in echinoid species, it is concluded that the ability to synthesize urea must have developed and improved in efficiency during echinoid evolution. P. lividus is predominantly ureotelic. It excretes approximately 91% of the nitrogenous wastes released into the surrounding sea water as urea-N, and only 9% as ammonia-N. Ammonia, and most of the urea, are excreted via the body surface — probably through respiratory surfaces; however, one third of the urea is excreted through the intestine, since urea excretion decreases by this amount when the anus is sealed artificially.  相似文献   

20.
The effects of two carbon-based nanomaterials, nano-sized carbon black (nCB), and single-layer graphene oxide (GO) on settlement of Amphibalanus amphitrite (Cirripedia, Crustacea) cypris larvae (cyprids) were assessed after 24, 48, and 72 h of exposure. Additionally, the effects of these nanomaterials on the mortality and swimming behaviour of the nauplius larvae (nauplii) of the same organism were determined after 24 and 48 h. The data indicate that nCB is more effective as a potential antisettlement agent than single-layer GO; moreover, nCB did not show any adverse effects on the larvae. The swimming behaviour of II stage nauplii of A. amphitrite exposed to a suspension of nCB was inhibited only at very high nCB concentrations (≥0.5 mg/mL). Single-layer GO, on the contrary, showed lower antisettlement effects and was more active in altering the survival and inhibiting the swimming behaviour of the nauplii. An indication of the toxic or non-toxic mechanisms of the antisettlement properties of both of these nanomaterials is provided by the reversibility of the antisettlement activity. In conclusion, we propose nCB as an innovative antifouling nanomaterial that shows low toxicity towards the model organism (crustaceans) used in this study.  相似文献   

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