Study on the performance and mechanism of cobaltous ion removal from water by a high-efficiency strontium-doped hydroxyapatite adsorbent.

In this study, a high-efficiency strontium-doped hydroxyapatite (Sr-HAP) adsorbent was synthesized by a sol-gel method for removing cobaltous ions (Co(II)) from water. The effects of adsorbent dose, initial solution pH, initial Co(II) concentration and temperature on the removal performance of Co(II) were investigated. Experimental results indicated that the optimum Sr-HAP dose was 0.30 g/50 mL solution, the Sr-HAP adsorbent could effectively remove Co(II) in a wide pH range of 3-8. Increasing temperature was conducive to the adsorption, and the maximum Co(II) adsorption capacity by Sr-HAP reached 48.467 mg/g at 45 °C. The adsorption of Co(II) followed the pseudo-second-order kinetic model, indicating that the Co(II) adsorption by Sr-HAP was attributed mainly to chemisorption. The isothermal adsorption results showed that at lower Co(II) equilibrium concentration, the Langmuir model fitted the data better than the Freundlich model but opposite at higher Co(II) equilibrium concentration. Therefore, the adsorption of Co(II) was a process from monolayer adsorption to multilayer adsorption with the increase of the Co(II) equilibrium concentration. The diffusion analysis of Co(II) to Sr-HAP indicated that the internal diffusion and surface adsorption were the rate-controlled steps of Co(II) adsorption. Thermodynamic study demonstrated that the Co(II) adsorption process was spontaneous and endothermic. The mechanism study revealed that in addition to chemisorption, Sr-HAP also removed Co(II) ions from water via ion exchange and surface complexation.

Performance and mechanism analysis of sludge-based biochar loaded with Co and Mn as photothermal catalysts for simultaneous removal of acetone and NO at low temperature.

Replacing NH3 in NH3-SCR with VOCs provides a new idea for the simultaneous removal of VOCs and NOx, but the technology still has urgent problems such as high cost of catalyst preparation and unsatisfactory catalytic effect in the low-temperature region. In this study, biochar obtained from sewage sludge calcined at different temperatures was used as a carrier, and different Co and Mn injection ratios were selected. Then, a series of sludge-based biochar (SBC) catalysts were prepared by a one-step hydrothermal synthesis method for the simultaneous removal of acetone and NO in a low-temperature photothermal co-catalytic system with acetone replacing NH3. The characterization results show that heat is the main driving force of the reaction system, and the abundance of Co and Mn atoms in high valence states, surface-adsorbed oxygen, and oxygen lattice defects in the catalyst are the most important factors affecting the performance of the catalyst. The performance test results showed that the optimal pyrolysis temperature of sludge was 400 °C, the optimal dosing ratio of Co and Mn was 4:1, and the catalyst achieved 42.98% and 52.41% conversion of acetone and NO, respectively, at 240 °C with UV irradiation. Compared with the pure SBC without catalytic effect, the SBC loaded with Co and Mn gained the ability of simultaneous removal of acetone and NO through the combined effect of multiple factors. The key reaction steps for the catalytic conversion of acetone and NO on the catalyst surface were investigated according to the Mars-van Krevelen (MvK) mechanism, and a possible mechanism was proposed. This study provides a new strategy for the resource utilization of sewage sludge and the preparation of photothermal catalysts for the simultaneous removal of acetone and NO at low cost.

Novel amino-modified bamboo-derived biochar-supported nano-zero-valent iron (AMBBC-nZVI) composite for efficient Cr(VI) removal from aqueous solution.

Biochar-supported nano-zero-valent iron (BC-nZVI) composites have been extensively investigated for the treatment of Cr(VI)-containing wastewater. However, the inherent oxygen-containing groups with negative charges on BC exhibit electrostatic repulsion of the electronegative Cr(VI) species, limiting Cr(VI) removal. To overcome this limitation, this study prepared and used amino-modified bamboo-derived BC (AMBBC) as a supporting matrix to synthesize a novel AMBBC-nZVI composite. The amino groups (-NH2) on AMBBC were easily protonated and transformed into positively charged ions (-NH3+), which favored the attraction of Cr(VI) to AMBBC-nZVI, enhancing Cr(VI) removal. The experimental results demonstrated that the Cr(VI) removal efficiency of AMBBC-nZVI was 95.3%, and that of BBC-nZVI was 83.8% under the same conditions. The removal of Cr(VI) by AMBBC-nZVI followed the pseudo-second-order kinetic model and Langmuir isotherm model and was found to be a monolayer chemisorption process. Thermodynamic analysis revealed that the Cr(VI) removal process was spontaneous and endothermic. The mechanism analysis of Cr(VI) removal indicated that under an acidic condition, the -NH3+ groups on AMBBC adsorbed the electronegative Cr(VI) species via electrostatic interaction, promoting the attachment of Cr(VI) on AMBBC-nZVI; the adsorbed Cr(VI) was then reduced to Cr(III) by Fe0 and Fe(II), accompanied by the formation of Fe(III); moreover, AMBBC allowed the electron shuttle of nZVI to reduce Cr(VI); finally, the Cr(III) and Fe(III) species deposited on the surface of AMBBC-nZVI as Cr(III)-Fe(III) hydroxide coprecipitates.

Non-Interacting Ni and Fe Dual-Atom Pair Sites in N-Doped Carbon Catalysts for Efficient Concentrating Solar-Driven Photothermal CO2 Reduction.

Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni-N4 and Fe-N4 pair sites is designed for boosting gas-solid CO2 reduction with H2 O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)-N-C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 µmol g-1 h-1 ), CH4 (135.35 µmol g-1 h-1 ) and CH3 OH (59.81 µmol g-1 h-1 ), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe-N-C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)-N-C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni-N-N-Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar-driven photothermal CO2 reduction to initial CO production.

Effects of Pretreatment and Polarization Shielding on EK-PRB of Fe/Mn/C-LDH for Remediation of Arsenic Contaminated Soils.

In this study, coupling electrokinetic (EK) with the permeable reactive barriers (PRB) of Fe/Mn/C-LDH composite was applied for the remediation of arsenic-contaminated soils. By using self-made Fe/Mn/C-LDH materials as PRB filler, the effects of pretreatment and polarization shielding on EK-PRB of Fe/Mn/C-LDH for remediation of arsenic contaminated soils were investigated. For the pretreatment, phosphoric acid, phosphoric acid and water washing, and phosphate were adopted to reduce the influence of iron in soil. The addition of phosphate could effectively reduce the soil leaching toxicity concentration. The removal rate of the soil pretreated with phosphoric acid or phosphoric acid and water washing was better than with phosphate pretreatment. For the polarization shielding, circulating electrolyte, electrolyte type, anion and cation membranes, and the exchange of cathode and anode were investigated. The electrolyte circulates from the cathode chamber to the anode chamber through the peristaltic pump to control the pH value of the electrolyte, and the highest arsenic toxicity removal rate in the soil reaches 97.36%. The variation of total arsenic residue in soil using anion and cation membranes is the most regular. The total arsenic residue gradually decreases from cathode to anode. Electrode exchange can neutralize H+ and OH- produced by electrolyte, reduce the accumulation of soil cathode area, shield the reduction of repair efficiency caused by resistance polarization, enhance current, and improve the removal rate of arsenic in soil.

Strontium-doped hydroxyapatite as adsorbent effectively to remove lead ions from water.

In this study, a strontium-doped hydroxyapatite (Sr-HAP) was synthesized by the solgel method, which was used as adsorbent to remove lead ions (Pb2+) from water. The results showed that the adsorption capacities of the Sr-HAP were obviously higher than those of the HAP, the adsorption capacities of which for Pb2+ reached 651.175 mg/g. The proper increasement in the dosage of adsorbent was beneficial to the removal of Pb2+ by Sr-HAP. Meanwhile Sr-HAP had a wide applicable pH range for Pb2+. And the increasement in temperature could increase the adsorption capacity of Sr-HAP for Pb2+ to a certain extent. The Langmuir model was used to fit the isotherm adsorption process of Sr-HAP to Pb2+ in water. Compared with HAP, the specific surface area of Sr-HAP has increased by 11.1%, and the pore size distribution of Sr-HAP tended to be smaller and more uniform. Hence, Sr-HAP could be used as an ideal adsorbent to remove Pb2+ in wastewater.

Effective Remediation of Arsenic-Contaminated Soils by EK-PRB of Fe/Mn/C-LDH: Performance, Characteristics, and Mechanism.

Arsenic is highly toxic and carcinogenic. The aim of the present work is to develop a good remediation technique for arsenic-contaminated soils. Here, a novel remediation technique by coupling electrokinetics (EK) with the permeable reactive barriers (PRB) of Fe/Mn/C-LDH composite was applied for the remediation of arsenic-contaminated soils. The influences of electric field strength, PRB position, moisture content and PRB filler type on the removal rate of arsenic from the contaminated soils were studied. The Fe/Mn/C-LDH filler synthesized by using bamboo as a template retained the porous characteristics of the original bamboo, and the mass percentage of Fe and Mn elements was 37.85%. The setting of PRB of Fe/Mn/C-LDH placed in the middle was a feasible option, with the maximum and average soil leaching toxicity removal rates of 95.71% and 88.03%, respectively. When the electric field strength was 2 V/cm, both the arsenic removal rate and economic aspects were optimal. The maximum and average soil leaching toxicity removal rates were similar to 98.40% and 84.49% of 3 V/cm, respectively. Besides, the soil moisture content had negligible effect on the removal of arsenic but slight effect on leaching toxicity. The best leaching toxicity removal rate was achieved when the soil moisture content was 35%, neither higher nor lower moisture content in the range of 25-45% was conducive to the improvement of leaching toxicity removal rate. The results showed that the EK-PRB technique could effectively remove arsenic from the contaminated soils. Characterizations of Fe/Mn/C-LDH indicated that the electrostatic adsorption, ion exchange, and surface functional group complexation were the primary ways to remove arsenic.

Controllable synthesis various morphologies of 3D hierarchical MnOx-TiO2 nanocatalysts for photothermocatalysis toluene and NO with free-ammonia.

Via various hydrothermal synthetic conditions, controllable synthesis various morphologies of MnOx-TiO2 catalysts for simultaneous removal toluene and NO with free-ammonia under the photothermocatalysis system based on UV light irradiation. The morphologies obtained included 3D hierarchical sheet structure (C sample), 3D hierarchical sheet stacked MnOx-TiO2 microspheres (P sample), and 3D hierarchical sticks stacked MnOx-TiO2 microspheres (N sample). Compared with other samples, N sample exhibited the excellent catalytic activity for the toluene and NO, with the conversion rates of toluene and NO achieved 72% and 91% at 240 °C, respectively. Using a variety of characterization and analysis methods, it was confirmed that the morphology of the catalysts would affect its catalytic performance by affecting the specific surface area, surface-adsorbed oxygen species, oxygen vacancies, the high-valence atomic species and reducibility. This was the reason why the N sample could show remarkable performance. Moreover, this work demonstrated a new strategy for simultaneously removing toluene and NO with free-ammonia under the photothermocatalysis system based on UV light irradiation.

Multi-templates surface molecularly imprinted polymer for simultaneous and rapid determination of sulfonamides and quinolones in water: effect of carbon-carbon double bond.

In this work, the effect of a carrier modified with a carbon-carbon double bond (C=C) on preparing multi-templates surface molecularly imprinted polymer MIP (C=C@MIP) for simultaneous detection of sulfonamides and quinolones was investigated. The results showed that the adsorption capacities of the C=C@MIP were obviously higher than those of MIP, which is the carrier without modified C=C, suggesting that C=C played a key role in preparing MIP with higher adsorption capacities. Then, C=C@MIP was used as adsorbents for solid-phase extraction (SPE) and coupled with high-performance liquid chromatography (HPLC) for the simultaneous determination of sulfonamides and quinolones in water. The method showed excellent applicability, with the adsorption capacities of 19.92, 16.38, 12.92, 18.37, 14.49, 12.01, 16.98, 23.33, and 14.29 mg/g for SDZ, STZ, SMZ, SMX, SDM, ENRO, OFL, LOME, and GATI, respectively. The spiked recoveries and relative standard deviations (RSDs) of sulfonamides and quinolones using C=C@MIP were 81.59-100.7 % and 3.75-7.37 %, respectively. The limits of detection (LODs) for SDZ, STZ, SMZ, SMX, SDM, ENRO, OFL, LOME, and GATI were 0.013, 0.012, 0.012, 0.013, 0.014, 0.012, 0.013, 0.015, and 0.015 µg/L, respectively.

Novel Nonaqueous Liquid-Liquid Biphasic Solvent for Energy-Efficient Carbon Dioxide Capture with Low Corrosivity.

To address the problems of the relatively high energy penalty and corrosivity of aqueous biphasic solvents, a novel nonaqueous biphasic solvent composed of 2-((2-aminoethyl)amino)ethanol (AEEA), dimethyl sulfoxide (DMSO), and N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) was proposed for CO2 capture. With optimization, this novel AEEA-DMSO-PMDETA (A-D-P) biphasic solvent could achieve a high CO2 loading of 1.75 mol·mol-1, of which 96.8% of the absorbed CO2 was enriched in the lower phase with only 49.6% of the total volume. 13C NMR analysis and quantum calculations revealed that A-D-P could absorb CO2 to form not only carbamate but also carbamic acid species, which were stabilized by DMSO via hydrogen-bonding interactions. Most products were highly polar and preferred to dissolve in polar DMSO rather than the less polar PMDETA, thus leading to the phase change. The thermodynamics results showed that the heat duty of A-D-P was only 1.66 GJ·ton-1 CO2 (393.15 K), which was significantly lower than that of the benchmark MEA (3.59 GJ·ton-1 CO2) and the reported aqueous biphasic solvents. Moreover, A-D-P presented a noncorrosive behavior to steel after CO2 saturation, clearly showing its superiority over MEA and the aqueous biphasic solvents. Therefore, with superior properties of energy savings and noncorrosiveness, the A-D-P biphasic solvent could be a promising candidate for CO2 capture.

Effects of prepolymerization on surface molecularly imprinted polymer for rapid separation and analysis of sulfonamides in water.

This work systematically investigated the effects of prepolymerization on the property of multi-templates surface molecularly imprinted polymer (MIP), which was utilized to quickly and simultaneously separate and detect six sulfonamides (sulfadiazine, sulfathiazole, sulfamerazine, sulfamethazine, sulfamethoxazole and sulfadoxine) in real waters. The MIPs were prepared using the six sulfonamides as the templates, mesoporous silica supported onto the surface of magnetic graphene oxide as the carrier and 4-vinylbenzoic as the functional monomer, with and without prepolymerization of templates with functional monomer. The preparation and adsorption conditions were optimized. It was found that the adsorption capacities of the selected six sulfonamides on the MIP (pre) prepared with prepolymerization were apparently higher than those on the MIP (no pre) synthesized without prepolymerization. Subsequently, the MIPs were utilized as adsorbents for SPE of these sulfonamides, and coupled with high performance liquid chromatography (HPLC) for the determination of sulfonamides. The developed analytical method showed outstanding applicability for the detection of trace sulfonamides in real water samples. The spiked recoveries and relative standard deviations (RSDs) of the six sulfonamides using MIP (no pre) and MIP (pre) were 73.34-99.43% and 87.37-102.34%, 2.28-7.77% and 3.18-6.49%, respectively.

Multi-templates surface molecularly imprinted polymer for rapid separation and analysis of quinolones in water.

Rapid separation and analysis of trace quinolones (fleroxacin (FLRX), enoxacin (EN), norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENRO), and lomefloxacin hydrochloride (LOME)) in real water samples were achieved by using a multi-templates molecularly imprinted polymer (MIP) based solid phase extraction (SPE) coupled with dispersive liquid-liquid microextraction (DLLME) followed by high performance liquid chromatography (HPLC). The MIP was prepared via surface molecular imprinting, using the selected quinolones as the templates and mesoporous silica modified magnetic graphene oxide as the carrier. The preparation and adsorption conditions were optimized. The MIP presented high adsorption capacity and wonderful selective recognition for the quinolones, with the adsorption capacities of 20.15, 20.88, 18.01, 20.01, 16.98, and 17.09 mg/g for FLRX, EN, NOR, CIP, ENRO, and LOME, respectively. Meanwhile, a SPE-DLLME-HPLC method for trace detection of FLRX, EN, NOR, CIP, ENRO, and LOME in real water samples was developed and showed outstanding applicability. The spiked recoveries and relative standard deviations (RSDs) were 89.67-100.5%, and 3.59-7.12%, respectively.

Enhanced removal of As(â ¢) and As(â ¤) from aqueous solution using ionic liquid-modified magnetic graphene oxide.

In this study, ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6])-modified magnetic graphene oxide (MGO-IL) was prepared for the first time, and was used to adsorb and remove arsenic (As(Ⅲ) and As(V)) ions from aqueous solution. MGO-IL was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and magnetization curves. Effects of ionic liquid type, solution pH, initial arsenic concentration and contact time on the adsorption performance of MGO-IL for As(Ⅲ) and As(V) were studied. The experimental results showed that the adsorption equilibrium was achieved within 30 min, with maximum adsorption capacities of 160.65 mg g-1 for As(Ⅲ) and 104.13 mg g-1 for As(V), respectively, and MGO-IL could be rapidly isolated from solution by applying a magnetic field. MGO-IL was reused for 5 times, without marked decrease in its adsorption capacities. Moreover, common coexisting anions did not interfere with the absorption of As(Ⅲ) and As(V). Compared with MGO, the sorption quantities of MGO-IL for As(Ⅲ) and As(V) were greatly enhanced, and the equilibrium time was significantly reduced. Therefore, MGO-IL can potentially serve as an excellent adsorbent for the simultaneous separation and removal of As(Ⅲ) and As(V) from water.