The interaction of CO with an attapulgite-supported Cu(ii)Cl2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(ii)Cl2 sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ∼370 °C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu+ and a small amount of Cu2+. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu+/Cu2+ catalyst is required to support CO chemisorption.

In this study, a novel ionic liquid-type surfactant modified attapulgite named as 1-dodecyl-3-methylimidazolium bromide-attapulgite (C12MIM-ATP) is successfully prepared and applied in dispersive solid phase extraction (dSPE) for the fast determination of pyrethroid residues in tea drinks. The primary factors that influenced the extraction efficiency, including sorbent type, amount of sorbent, extraction time, desorption conditions, pH and ionic strength, are investigated. The optimized results reveal that the extraction and desorption equilibria are rapidly obtained within 1 min. Under the optimized conditions, good linearity (2-500 μg/L) is observed for four pyrethroids in tea drinks with determination coefficients (r2) ranged from 0.9992 to 1.0000. The limits of detection (LODs) are 0.6 μg/L for all pesticides. Acceptable extraction recoveries of target analytes are found from 90.28 to 107.56% with relative standard deviations (RSDs) less than 8.30% in real tea drink samples. The batch-to-bath repeatability is evaluated by recovery test on five independent synthesized C12MIM-ATP sorbents. Satisfactory batch-to-batch repeatability is obtained with the recovery factors varied in 15%. A small matrix effect is observed using C12MIM-ATP as the sorbent for detection pyrethroids in tea drinks.

Recently, reductant and carbon source were frequently used in groundwater nitrate remediation worldwide. Agricultural waste as a promising organic carbon source, has been paid much attention but the problem of sustainability, bioavailability and secondary pollution remained unsolved. This study was conducted to depict the characteristic and performance of developed sustainable-releasing compound carbon source material (SCCM) applied on the in-situ remediation of nitrate in shallow groundwater. Results showed the SCCM based on agricultural waste and zero valent-iron (ZVI) has a stable carbon releasing rate, which is suitable for stimulating the low microbial active environment in groundwater continuously, and capable of avoiding rapid TOC releasing in the early stage. The released carbon sources in SCCM leachate were mainly small molecular alcohols and acids with high microbial availability. As in-situ permeable reactive barrier (PRB) filling material, SCCM can form an optimal carbon source radiation range of 20 cm, with a maximum efficient carbon source radius of 1 m, which can reach an extended active zone. A positive correlation between the ZVI content and nitrate removal rate was found. The chemical and microbiological evidence both indicated that the expected chemical reduction and biological denitrification was gradually established. Additionally, the absorption of ammonia and chroma by attapulgite effectively avoided the secondary pollution. In conclusion, the application of SCCM in groundwater nitrate in-situ remediation optimized the nitrate removal efficiency and provided theoretical basis for engineer carbon sources development from straw-type agricultural waste.

Nitrogen (N) and phosphorus (P) pollution from aquaculture has increased dramatically in recent years, and it is urgent to develop a cost-effective method to clean these polluted waters. The objective of this study is to investigate N and P removal using a two-stage infiltration system based on NaCl modified clinoptilolite (NCLP) and thermally-treated calcium-rich attapulgite (TCAP). Results from a batch study indicated that the maximum ammonium sorption capacity of NCLPs was in the range of 6.64 to 7.27 mg. N/g and decreased slightly among the three particle sizes studied (0.2-0.5 mm, 0.5 mm-1.0 mm and 1-2 mm). A 150-day column experiment indicated that the two-stage infiltration system achieved an average removal efficiency of 99.4% N and 99.0% P, and a removal rate of 50.3 g N/m3/d and 8.83 g P/m3/d for an influent concentration of 50 mg N/L and 10 mg P/L with a hydraulic retention time (HRT) of 16 h. When the influent concentration increased to 100 mg N/L and 20 mg P/L, the average ammonium removal efficiency decreased to 65.3%, while the system can still keep a high average P removal efficiency of 97.9% for 72 days of the experiment. Longer HRT favored N and P removal efficiency, but short HRTs can oxygenate ammonium sorbed in the NCLP filter and thereby refresh its sorption capacity. The results also indicated that longer wet and dry cycles can enhance the N removal efficiency of the system, but had minor influence on P removal. The sorbed clays contained high N and P content and might have use as a slow-release fertilizer. The results of this study indicate that a reactive clay-based treatment system can be used for dual removal of N and P from aquaculture wastewaters, making possible the development of a sustainable aquaculture model.

In this study, chemo-enzymatic synthesis of furfuralcohol from biomass-derived xylose was successfully demonstrated by a sequential acid-catalyzed dehydration under microwave and whole-cells reduction. After dry dewaxed chestnut shells (CNS, 75 g/L) was acid-hydrolyzed with dilute oxalic acid (0.5 wt%) at 140 °C for 40 min, the obtained CNS-derived xylose (17.9 g/L xylose) could be converted to furfural at 78.8% yield with solid acid SO42-/SnO2-Attapulgite (2.0 wt% catalyst loading) in the dibutyl phthalate-water (1:1, v:v) under microwave (600 W) at 180 °C for 10 min. In the dibutyl phthalate-water (1:1, v/v) media at 30 °C and pH 6.5, the furfural liquor (47.0 mM furfural) was biologically converted to furfuralcohol by recombinant Escherichia coli CCZU-Y10 whole-cells harboring an NADH-dependent reductase (PgCR) without extra addition of NAD+ and glucose, and furfural was completely converted to furfuralcohol after 2.5 h. Clearly, this one-pot synthesis strategy can be effectively used for furfuralcohol production.

Attapulgite (or palygorskite) is a magnesium aluminium phyllosilicate. Modified attapulgite-supported nanoscale zero-valent iron (NZVI) was created by a liquid-phase reduction method and then applied for nitrate-nitrogen (NO3-N) removal (transformation) in simulated groundwater. Nanoscale zero-valent iron was sufficiently dispersed on the surface of thermally modified attapulgite. The NO3-N removal efficiency reached up to approximately 83.8% with an initial pH values of 7.0. The corresponding thermally modified attapulgite-supported nanoscale zero-valent iron (TATP-NZVI) and NO3-N concentrations were 2.0 g/L and 20 mg/L respectively. Moreover, 72.1% of the water column NO3-N was converted to ammonium-nitrogen (NH4-N) within 6 h. The influence of environmental boundary conditions including dissolved oxygen (DO) concentration, light illumination and water temperature on NO3-N removal was also investigated with batch experiments. The results indicated that the DO concentration greatly impacted on NO3-N removal in the TATP-NZVI-contained solution, and the NO3-N removal efficiencies were 58.5% and 83.3% with the corresponding DO concentrations of 9.0 and 0.3 mg/L after 6 h of treatment, respectively. Compared to DO concentrations, no significant (p > 0.05) effect of light illumination on NO3-N removal and NH4-N generation was detected. The water temperature also has great importance concerning NO3-N reduction, and the removal efficiency of NO3-N at 25 °C was 1.25 times than that at 15 °C. For groundwater, therefore, environmental factors such as water temperature, anaerobic conditions and darkness could influence the NO3-N removal efficiency when TATP-NZVI is present. This study also demonstrated that TATP-NZVI has the potential to be developed as a suitable material for direct remediation of NO3-N-contaminated groundwater.

Recently, polyaniline (PANI) has received widespread attention for the free volume, optical transmittance and electrical conductivity. In this study, a chemical vapor deposition method was developed to synthesize the conductive PANI-clay composite catalyzed by Fe(III)-saturated attapulgite (Fe(III)-ATTP). The reaction is initiated by the electron transfer from aniline (ANI) to Fe(III), subsequently generating ANI radical cation. The radical could further polymerize and form PANI in the constrained micropore structure of ATTP. The Raman, Fourier transform infrared and X-ray photoelectron spectra confirmed the formation of PANI on Fe(III)-ATTP surface by comparison with the PANI standard. The newly synthesized Fe(III)-ATTP-PANI composite exhibited superior reactivity as indicated by the efficient dissipation of atrazine in the presence of hydrogen peroxide (H2O2), and the degradation rate increased up to almost 150 times compared to Fe(III)-ATTP. The higher reactivity of Fe(III)-ATTP-PANI/H2O2 system was attributed to the accelerated electron transfer, the formation of ferrous ions, and the enhanced adsorption of atrazine onto attapulgite. Furthermore, our experimental results demonstrated that Fe(III)-ATTP-PANI showed good stability and it could be reused for several reaction cycles with high reactivity. This new material could act as an environmental-friendly catalyst in Fenton-like reaction system and show promising potential to effectively eliminate many persistent organic contaminants.

An excellent ternary composite photocatalyst consisting of silver orthophosphate (Ag3PO4), attapulgite (ATP), and TiO2 was synthesized, in which heterojunction was formed between dissimilar semiconductors to promote the separation of photo-generated charges. The ATP/TiO2/Ag3PO4 composite was characterized by SEM, XRD, and UV-vis diffuse reflectance spectroscopy. The co-deposition of Ag3PO4 and TiO2 nanoparticles onto the surface of ATP forms a lath-particle structure. Compared with composite photocatalysts consisting of two phases, ATP/TiO2/Ag3PO4 ternary composite exhibits greatly improved photocatalytic activity for degradation of rhodamine B under simulated solar irradiation. Such ternary composite not only improves the stability of Ag3PO4, but also lowers the cost by reducing application amount of Ag3PO4, which provides guidance for the design of Ag3PO4- and Ag-based composites for photocatalytic applications.

Polydopamine-modified granule organo-attapulgite adsorbent (PDA-GOAT) was facilely prepared via a dip-coating approach. The samples were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Surface area and pore size were calculated from the Brunauer-Emmett-Teller method by N2 adsorption-desorption isotherm. The adsorption behaviour of methylene blue (MB) onto PDA-GOAT was systematically investigated. The experimental data revealed that the adsorption process fitted well with the pseudo-second-order kinetics equation and the adsorption isotherm fitted better with the Langmuir model. Thermodynamic analyses illustrated that MB adsorption onto PDA-GOAT was a physisorption endothermic process. Importantly, PDA-GOAT can be regenerated by NaBH4 aqueous solution. The obtained results prove that PDA-GOAT can be a superior reusable adsorbent for the removal of MB from effluent.

In current study, a new polyethyleneimine (PEI)-modified attapulgite material was prepared serving as a solid support in matrix solid-phase dispersion for the extraction and determination (by atomic absorption spectrometry) of cadmium in seafood products. The major factors affecting PEI grafting were optimized using various PEI amounts and molecular weights. Parameters pivotal to MSPD extraction efficiency, like: pH, volume of eluting solvent, and the sorbent mass-to-sample ratio were investigated. Quantitative recoveries were achieved with 0.21g of fish sample, 0.13g of PEI-modified attapulgite dispersing agent, and 50% HNO3 eluting solution. The limit of detection and the limit of quantification were found to be 2.5 and 8.3μgkg-1 for cadmium in surimi samples, respectively. The recoveries were in the range of 89.2-100.1%, with RSDs ranged from 3.0% to 7.9% (n = 5). When compared to the method stipulated by the Chinese National Standard GB 5009.15-2014, the newly developed MSPD provides comparable accuracy and even better repeatability for the analysis of the cadmium in real seafood samples.