Layered Double Hydroxides Derived from MIL-88A(Fe) as an Efficient Adsorbent for Enhanced Removal of Lead (II) from Water.

The efficient removal of lead (II) from aqueous solution remains a big problem and the development of novel nanomaterials as adsorbents by various technologies to solve this problem is promising. This study contributed a novel nanostructure of MIL-88A-layered double hydroxides (LDHs) as the adsorbent for Pb2+, which was synthesized by a two-step solvothermal method with MIL-88A(Fe) as the precursor. The as-prepared material featured a chestnut-like core-shell structure, and exhibited excellent removal performance towards Pb2+ from water in comparison to MIL-88A(Fe) and LDHs (directly synthesized). The adsorption of Pb2+ by the MIL-88A-LDHs conformed to the pseudo-second-order kinetic model and the Langmuir and Freundlich isotherm models. The maximal adsorption capacity was 526.32, 625.00, and 909.09 mg g-1 at 278, 298, and 318 K, respectively. The thermodynamic parameters suggested that the adsorption was an endothermic, entropy-increasing, and spontaneous reaction. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface complexation was mostly responsible for Pb2+ elimination. The MIL-88A-LDHs can be readily regenerated and showed good cyclic performance towards Pb2+. Thus, the as-prepared MIL-88A-LDHs may hold promise for the elimination of aqueous heavy metals.

Treatment of tributyl phosphate by fenton oxidation: Optimization of parameter, degradation kinetics and pathway.

In nuclear industry, tributyl phosphate (TBP) is used as organic extracting solvent to separate uranium and plutonium. The spent TBP is finally discarded as the radioactive organic waste, which should be treated due to its potential risk. In this study, TBP degradation by Fenton oxidation was investigated in detail, including the optimization of operational conditions, degradation kinetics and degradation products. The optimal conditions for TBP degradation (per 10 ml) by Fenton oxidation was: 95 °C, pH 2, 150 ml 30% H2O2, and 105 ml 0.2 M Fe(II). H2O2 was continuously added with the flow rate of 0.5 ml/min, Fe(II) was intermittently added with the flow rate of 3 ml/10 min. The oil phase volume decreased with time and completely disappeared at the third hour. In contrast, the COD in water phase increased firstly and then decreased. At the end of the experiments, the COD achieved 23.8 g/L. The detection of phosphorus in water phase further confirmed the decomposition of TBP. Mono-butyl phosphate and di-butyl phosphate were identified as the intermediate products of TBP degradation. In addition, other four degradation products with the same m/z of 154 were identified, which may be derived from the hydroxylation of mono-butyl phosphate and di-butyl phosphate. Based on the degradation products, the degradation pathway of TBP was proposed. This study could provide an insight into the TBP degradation by Fenton oxidation, and an potential strategy for treating the spent radioactive organic solvent.

Degradation of the mixed organic solvents of tributyl phosphate and n-dodecane by heterogeneous Fenton-like oxidation using nanoscale zero-valent iron as the catalyst.

The treatment and disposal of spent radioactive organic solvents, i.e., tributyl phosphate (TBP) and diluent (such as kerosene, n-dodecane, etc.), produced in the reprocessing of spent fuel in the closed cycle are crucial for the sustainable development of the nuclear industry. In this study, the synthesized nanoscale zero-valent iron (nZVI) was used as the heterogeneous Fenton-like catalyst to promote the generation of hydroxyl radicals (•OH) by reacting with H2O2 to degrade the mixed organic solvents of TBP and n-dodecane. nZVI was characterized by scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, and X-ray photoelectron spectroscopy (XPS) to investigate the micro-morphology, nano-particle size, and surface valence state. The change of Fe2+/Fe3+ concentration ratio during the reaction was measured to clarify the performance of nZVI. The effects of temperature, catalyst dosage, H2O2 dosage, and acidifier concentration on the degradation of TBP and n-dodecane were studied, and the results were complemented by the COD of the aqueous solution and the volume reduction rate of the organic phase. The mixed organic solvents of TBP and n-dodecane containing Co2+ were used to simulate the spent radioactive organic solvents and to study the distribution of nuclides after the reaction. The results showed that most of the radioactivity was in the residual solution, and the condensate contained almost no radioactivity. The degradation of TBP and n-dodecane was carried out separately, which showed that n-dodecane was more difficult to degrade. Density functional theory (DFT) calculations were applied to determine the adsorption energy of organic solvents and nZVI. According to the Fourier transform infrared spectra (FTIR) and their corresponding DFT calculations, liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) of the sample after the reaction, the possible intermediates were analyzed, and the degradation mechanism was speculated.

Ethanol production from xylo-oligosaccharides by xylose-fermenting Saccharomyces cerevisiae expressing ß-xylosidase.

Construction of xylose- and xylo-oligosaccharide-fermenting Saccharomyces cerevisiae strains is important, because hydrolysates derived from lignocellulosic biomass contain significant amounts of these sugars. We have obtained recombinant S. cerevisiae strain MA-D4 (D-XKXDHXR), expressing xylose reductase, xylitol dehydrogenase and xylulokinase. In the present study, we generated recombinant strain D-XSD/XKXDHXR by transforming MA-D4 with a ß-xylosidase gene cloned from the filamentous fungus Trichoderma reesei. The intracellular ß-xylosidase-specific activity of D-XSD/XKXDHXR was high, while that of the control strain was under the limit of detection. D-XSD/XKXDHXR produced ethanol, and xylose accumulated in the culture supernatant under fermentation in a medium containing xylo-oligosaccharides as sole carbon source. ß-Xylosidase-specific activity in D-XSD/XKXDHXR declined due to xylose both in vivo and in vitro. D-XSD/XKXDHXR converted xylo-oligosaccharides in an enzymatic hydrolysate of eucalyptus to ethanol. These results indicate that D-XSD/XKXDHXR efficiently converted xylo-oligosaccharides to xylose and subsequently to ethanol.

Mesoporous cerium oxide-anchored magnetic polyhedrons derived from MIL-100(Fe) for enhanced removal of arsenite from aqueous solution.

Efficient elimination of As(III) from drinking water and wastewater has been a challenge because of its neutral molecular form. To address this problem, a novel nanocomposite, mesoporous cerium oxide-anchored magnetic polyhedrons derived from MIL-100(Fe) was fabricated via a strategy combining impregnation and calcination. The resultant products (denoted as Fe2O3/CeO2-t) exhibited a unique octahedral nanostructure decorated by mesoporous cerium oxide. Surface modification of CeO2 enhanced As(III) removal in comparison to unmodified Fe2O3. Particularly, Fe2O3/CeO2-4 h can reduce As(III) concentration from 180 to 10 µg/L within 20 min, which was almost 9 times faster than unmodified Fe2O3. The adsorption behavior conformed to the pseudo-second-order kinetic model (R2 = 0.9908) and the Freundlich isotherm model (R2 = 0.9943). The maximum adsorption capacity of As(III) by Fe2O3/CeO2-4 h was 68.25 mg/g, higher than those reported for similar adsorbents. Its enhanced removal mechanism can be attributed mainly to the mesoporous characteristics and oxidization ability of surface ceria. The composite can be separated from water by external magnets and easily regenerated. This study may offer a clue to the design of metal-organic framework-based composites as an alternative adsorbent for arsenite cleanup.

Degradation of norfloxacin by hydroxylamine enhanced fenton system: Kinetics, mechanism and degradation pathway.

This study demonstrated a fast and efficient degradation of a typical antibiotic norfloxacin (NOR) in a hydroxylamine enhanced Fenton (HA-Fenton) system, which showed a higher catalytic activity over a wider pH range (3.0-9.0). The removal efficiency of NOR was 96% at following conditions: 10 mg/L NOR, 10 µM Fe2+, 1.0 mM H2O2, 0.4 mM HA and pH 5.0. The degradation rate of NOR in the HA-Fenton system (0.23 min-1) was 10.9 times of that (0.021 min-1) in Fenton system. The addition of HA to Fenton system accelerated the conversion of Fe3+ to Fe2+, leading to the high concentration of ·OH in the HA-Fenton system. Ten degradation transformation products were detected by ultra-performance liquid chromatography tandem quadrupole time of flight mass spectrometer (UPLC-QTOF-MS), consequently, three main degradation steps were proposed, including defluorination, quinolone group transformation, and defluorination and piperazinyl ring opening. Further analyses of NO3-, NO2- and F- after the reaction indicated that defluorination process was the crucial degradation step. The HA-Fenton system might offer an efficient alternative for degradation of antibiotics in wastewater.

Efficient removal of Co(II) and Sr(II) from aqueous solution using polyvinyl alcohol/graphene oxide/MnO2 composite as a novel adsorbent.

In this study, a novel adsorbent, polyvinyl alcohol/graphene oxide/MnO2 composite was prepared, characterized and used for efficient removal of Co2+ and Sr2+ from aqueous solution. Polyvinyl alcohol (PVA) and Mn2+ played a synergistic role in the gelation of PVA/GO/Mn2+, while Mn2+ can be further converted into oxide to achieve functionalized aerogel (PVA/GO/MnO2). The spectroscopy analysis manifested that hydrogen bonds and electrostatic attraction were responsible for the formation of PVA/GO/MnO2. The functionalization of MnO2 enhanced the adsorption capacity for Co2+ (2.1 folds) and Sr2+ (1.3 folds) by PVA/GO/MnO2. The composite showed high adsorption capacity at broad pH range of 4.0-9.0. For competitive adsorption test, Ni2+/Zn2+ exerted the most interfering effect on Co2+ adsorption, while Mg2+/Ca2+ showed severe interfering effect on Sr2+ adsorption. Both electrostatic attraction and oxygen-containing groups contributed to the adsorption mechanism. This study may provide a new adsorbent for separation of Co2+ and Sr2+ from aqueous solution.

Adsorptive removal of Sr(II) from aqueous solution by polyvinyl alcohol/graphene oxide aerogel.

In this study, a new adsorbent, polyvinyl alcohol (PVA) and graphene oxide (GO), was prepared, characterized and used for the removal of Sr2+ from aqueous solution. In PVA/GO composite, the inter-lamellar spacing of adjacent GO layers was dramatically enlarged due to the intercalation of PVA molecules, such a unique architecture significantly mitigated the aggregation of GO layers, which facilitated the accessible exposure of active sites and the mass transfer of strontium ions (Sr2+), thus enhancing the adsorption capacity toward Sr2+. The adsorption of Sr2+ by PVA/GO composite conformed to the pseudo second-order kinetic model (R2 = 0.9994), the Langmuir model (R2 = 0.9042), and the Freundlich model (R2 = 0.9598). The complexation interaction between Sr2+ and oxygen atoms/π-electron domain of PVA/GO composite was primarily responsible for the adsorption mechanism, based on the characterization results of X-ray photoelectron spectroscopy (XPS), scanning electron microscope equipped with energy dispersion spectroscopy (SEM-EDS) and powder X-ray diffraction (PXRD).

Magnetic zeolitic imidazolate frameworks composite as an efficient adsorbent for arsenic removal from aqueous solution.

In this study, magnetic zeolitic imidazolate frameworks (ZIF-8) was prepared by a one-step method, where its evolution involved the coprecipitation reactions concomitant with the self-assembly reactions. Structural characterizations indicated that magnetic ZIF-8 showed irregular polyhedral morphology with a large specific surface area (696.5 m2/g) and saturation magnetization (4.31 emu/g). The as-prepared magnetic ZIF-8 enhanced the adsorption performance of As(III) and As(V), compared with bare Fe3O4. The pseudo second-order kinetic model (R2 = 0.9627 and 0.9893 for As(III) and As(V), respectively) and the Langmuir model (R2 = 0.9441 for As(III) and 0.9851 for As(V)) can fit the adsorption process well, confirming the nature of single-layer homogeneous chemisorption. The adsorption capacity was 30.87 and 17.51 mg/g, and their corresponding values of PC were 2.664 and 1.286 L/g, for As(III) and As(V), respectively. Solution pH showed an adverse effect on As(V) adsorption whereas no obvious effect on As(III). The ionic strength and coexisting ions had not obvious influence on adsorption of As(III) and As(V). The adsorption mechanism was explored and discussed based on the detailed spectroscopy analysis. This adsorbent can be recovered magnetically after use, which is promising for the practical application.

Selective adsorption of cesium (I) from water by Prussian blue analogues anchored on 3D reduced graphene oxide aerogel.

In this paper, Prussian blue analogues (PBAs) anchored on 3D reduced graphene aerogel (denoted as 3D rGO/PBAs) was prepared, characterized and applied for adsorption of Cs(I) from aqueous solution. The results showed that 3D rGO/PBAs had high specific surface and good hydrophilic property, which was beneficial to the exposure of adsorptive sites and the transfer of adsorbates. The composite exhibited excellent adsorption performance towards Cs(I), and the maximum adsorption capacity was up to 204.9 mg/g, higher than most of reported values. The pseudo second-order kinetic model (R2 = 0.999) and the Langmuir isotherm model (R2 = 0.997) could fit the adsorption process well, suggesting the nature of homogeneous monolayer chemisorption. High distribution coefficients (kd) (2.8 × 104 to 5.8 × 104 mL/g), revealed that the composite had good selectivity. Ion-exchange, ion trapping and the complexation interaction might be involved in the process of cesium adsorption, in which ion-exchange may be dominant by characterization results.

Porous walnut-like La2O2CO3 derived from metal-organic frameworks for arsenate removal: A study of kinetics, isotherms, and mechanism.

Exploration of renewable materials for efficient elimination of arsenic from water is highly imperative. Herein, one kind of novel porous walnut-like La2O2CO3 composite is reported for the first time, fabricated via direct pyrolysis of La-MOFs at 550 °C under the air atmosphere. The as-synthesized material predominantly consists of La2O2CO3, featuring micrometer-scale walnut-like morphology and an abundant mesoporous structure. Adsorption experiments demonstrated that a pseudo-second-order model with a high correlation coefficient (0.9976-0.9988) can depict this adsorption process in a good manner and indicates chemical adsorption. Analysis of the isotherms further revealed that this adsorption is a monolayer and homogeneous process, with an excellent adsorption capacity (210.1 As mg/g), as calculated from the Langmuir model. Thermodynamic parameters indicated this adsorption process to be a spontaneous and endothermic, with a positive change in entropy. By characterization results, it can be deduced that the anion-exchange interaction (i.e. carbonate is prone to being replaced by arsenate) and inner-sphere complexation were both responsible for arsenate removal. A broad working pH range (3.0-9.0) and a good cyclic performance (removal rate is above 90% for the fourth cycle) as well as an excellent adsorption capacity make this adsorbent a promising arsenic scavenger.

Formation of anaerobic granules and microbial community structure analysis in anaerobic hydrolysis denitrification reactor.

An anaerobic hydrolysis denitrification (AnHD) process was developed to pretreat municipal wastewater for integrating partial nitration/anammox process. The results indicated that the carbon to nitrogen (C/N) ratio of municipal wastewater changed from 4.4 ± 0.3 to 2.2 ± 0.2 after pretreatment by AnHD process, which was favorable to the partial nitration/anammox process. The influent C/N ratio had influence on the formation of anaerobic granules. Two intrinsic factors, cyclic diguanylic acid (c-di-GMP) concentration and core bacterial community, were mainly responsible for the anaerobic granular formation. The higher c-di-GMP content increased the extracellular polymeric substances and decreased the motility of the bacteria, which was beneficial for the formation of anaerobic granules. The microbial community analysis showed that the lactic acid bacteria (Lactococcus) was the core bacteria during anaerobic hydrolysis process, while the denitrifying bacteria (Denitratisoma and unclassified Comamonadaceae) were the core bacterial community during AnHD process, which were responsible for nitrogen removal and anaerobic granular formation.

Effect and aftereffect of gamma radiation pretreatment on enzymatic hydrolysis of wheat straw.

Irradiation pretreatment of wheat straw was carried out at different doses by using Co-60 gamma radiation. The weight loss and fragility of wheat straw after irradiation, the combination effect of irradiation and mechanical crushing on enzymatic hydrolysis of wheat straw as well as the aftereffect of irradiation were examined. It is shown that irradiation can cause significant breakdown of the structure of wheat straw. The weight loss of wheat straw increased and the size distribution after crushing moved to fine particles at elevated irradiation doses. The glucose yield of enzymatic hydrolysis of wheat straw increased with increasing doses and achieved the maximum (13.40%) at 500 kGy. A synergistic effect between irradiation and crushing was observed, with a glucose yield of 10.24% at a dose of 500 kGy with powder of 140 mesh. The aftereffect of irradiation had important impact on enzymatic hydrolysis of wheat straw. The aftereffect (at 22nd day) of 400 kGy irradiation accounted for 20.0% of the initial effect for glucose production, and the aftereffects of 50, 100, 200 (at 9th day) and 300 kGy (at 20th day) accounted for 12.9%, 14.9%, 8.9% and 9.1%, respectively, for reducing sugar production.

Structural insights into rice straw pretreated by hot-compressed water in relation to enzymatic hydrolysis.

Pretreatment-induced structural alteration is critical in influencing the rate and extent of enzymatic saccharification of lignocellulosic biomass. The present work has investigated structural features of rice straw pretreated by hot-compressed water (HCW) from 140 to 240 °C for 10 or 30 min and enzymatic hydrolysis profiles of pretreated rice straw. Compositional profiles of pretreated rice straw were examined to offer the basis for structural changes. The wide-angle X-ray diffraction analysis revealed possible modification in crystalline microstructure of cellulose and the severity-dependent variation of crystallinity. The specific surface area (SSA) of pretreated samples was able to achieve more than 10-fold of that of the raw material and was in linear relationship with the removal of acetyl groups and xylan. The glucose yield by enzymatic hydrolysis of pretreated materials correlated linearly with the SSA increase and the dissolution of acetyl and xylan. A quantitatively intrinsic relationship was suggested to exist between enzymatic hydrolysis and the extraction of hemicellulose components in hydrothermally treated rice straw, and SSA was considered one important structural parameter signaling the efficiency of enzymatic digestibility in HCW-treated materials in which hemicellulose removal and lignin redistribution happened.

Pretreatment of rice straw by a hot-compressed water process for enzymatic hydrolysis.

Hot-compressed water (HCW) is among several cost-effective pretreatment processes of lignocellulosic biomass for enzymatic hydrolysis. The present work investigated the characteristics of HCW pretreatment of rice straw including sugar production and inhibitor formation in the liquid fraction and enzymatic hydrolysis of pretreated material. Pretreatment was carried out at a temperature ranging from 140 to 240 degrees C for 10 or 30 min. Soluble oligosaccharides were found to constitute almost all the components of total sugars in the liquid fraction. The maximal production of total glucose at 180 degrees C and below accounted for 4.4-4.9% of glucan in raw material. Total xylose production peaked at 180 degrees C, accounting for 43.3% of xylan in raw material for 10-min pretreatment and 29.8% for 30-min pretreatment. The production of acetic acid increased at higher temperatures and longer treatment time, indicating more significant disruption of lignocellulosic structure, and furfural production achieved the maximum (2.8 mg/ml) at 200 degrees C for both 10-min and 30-min processes. The glucose yield by enzymatic hydrolysis of pretreated rice straw was no less than 85% at 180 degrees C and above for 30-min pretreatment and at 200 degrees C and above for 10-min pretreatment. Considering sugar recovery, inhibitor formation, and process severity, it is recommended that a temperature of 180 degrees C for a time of 30 min can be the most efficient process for HCW pretreatment of rice straw.