Guangren Qian

A Heterostructure Coupling of Exfoliated Ni–Fe Hydroxide Nanosheet and Defective Graphene as a Bifunctional Electrocatalyst for Overall Water Splitting

Herein, the authors demonstrate a heterostructured NiFe LDH-NS@DG10 hybrid catalyst by coupling of exfoliated Ni-Fe layered double hydroxide (LDH) nanosheet (NS) and defective graphene (DG). The catalyst has exhibited extremely high electrocatalytic activity for oxygen evolution reaction (OER) in an alkaline solution with an overpotential of 0.21 V at a current density of 10 mA cm-2 , which is comparable to the current record (≈0.20 V in Fe-Co-Ni metal-oxide-film system) and superior to all other non-noble metal catalysts. Also, it possesses outstanding kinetics (Tafel slope of 52 mV dec-1 ) for the reaction. Interestingly, the NiFe LDH-NS@DG10 hybrid has also exhibited the high hydrogen evolution reaction (HER) performance in an alkaline solution (with an overpotential of 115 mV by 2 mg cm-2 loading at a current density of 20 mA cm-2 ) in contrast to barely HER activity for NiFe LDH-NS itself. As a result, the bifunctional catalyst the authors developed can achieve a current density of 20 mA cm-2 by a voltage of only 1.5 V, which is also a record for the overall water splitting. Density functional theory calculation reveals that the synergetic effects of highly exposed 3d transition metal atoms and carbon defects are essential for the bifunctional activity for OER and HER.

Removal efficiency of arsenate and phosphate from aqueous solution using layered double hydroxide materials: intercalation vs. precipitation

Adsorption behaviours of arsenate and phosphate over Mg-based and Ca-based layered double hydroxide (LDH) adsorbents have been examined in kinetics and thermodynamics. Removal of these anions from aqueous solution follows the Lagergren first-order and/or pseudo-second-order model, and the adsorption isotherm is well fitted with either the Langmuir or the Freundlich model. Structure analysis of used LDH adsorbents reveals that two processes, i.e. intercalation and precipitation, are responsible for the anion removal. Adsorption over the Mg-based LDH adsorbent occurs by way of intercalation into the interlayer spacing while that over the Ca-based adsorbent occurs by means of precipitation of dissolved Ca2+ with the anion. More particularly, we have found that As(V) at a concentration below 10 mg/L can be very efficiently removed through intercalation into the interlayer of reconstructed MgAl-LDHs, with less than 0.010 mg/L of As left in solution. We have also noted that phosphate at [P] up to 100 mg/L can be quickly and effectively removed through precipitation with CaAl-Cl-LDH, giving rise to ∼0.1 mg/L of P left in solution with the maximum adsorption amount up to 135 mg/g. Therefore, these two LDH materials (calcined Mg3Al-CO3-LDH and uncalcined Ca2Al-Cl-LDH) are potential cost-effective adsorbents for arsenate and phosphate, respectively.

Efficient removal of dyes by a novel magnetic Fe3O4/ZnCr-layered double hydroxide adsorbent from heavy metal wastewater

A novel magnetic Fe(3)O(4)/ZnCr-layered double hydroxide adsorbent was produced from electroplating wastewater and pickling waste liquor via a two-step microwave hydrothermal method. Adsorption of methyl orange (MO) from water was studied using this material. The effects of three variables have been investigated by a single-factor method. The response surface methodology (RSM) based on Box-Behnken design was successfully applied to the optimization of the preparation conditions. The maximum adsorption capacity of MO was found to be 240.16 mg/g, indicating that this material may be an effective adsorbent. It was shown that 99% of heavy metal ions (Fe(2+), Fe(3+), Cr(3+), and Zn(2+)) can be effectively removed into precipitates and released far less in the adsorption process. In addition, this material with adsorbed dye can be easily separated by a magnetic field and recycled after catalytic regeneration with advanced oxidation technology. Meanwhile, kinetic models, FTIR spectra and X-ray diffraction pattern were applied to the experimental data to examine uptake mechanism. The boundary layer and intra-particle diffusion played important roles in the adsorption mechanisms.

Effective removal and fixation of Cr(VI) from aqueous solution with Friedel's salt.

Friedels salt (3CaO x Al2O3 x CaCl2 x 10 H2O or Ca4Al2(OH)12Cl2(H2O)4) is a calcium aluminate hydrate formed by hydrating cement or concrete in seawater at a low cost. In the current study, we carefully examined the adsorption behaviors of Friedels salt for Cr(VI) from aqueous solution at different concentrations and various initial pHs. The adsorption kinetic data are well fitted with the pseudo-first-order Lageren equation at the initial Cr(VI) concentration from 0.10 to 8.00 mM. Both the experimental and modeled data indicate that Friedels salt can adsorb a large amount of Cr(VI) (up to 1.4 mmol Cr(VI)/g) very quickly (t1/2 = 2-3 min) with a very high efficiency (>99% Cr(VI) removal at [Cr] < 4.00 mM with 4.00 g/L of adsorbent) in the pH range of 4-10. In particular, the competitive adsorption tests show that the Cr(VI) removal efficiency is only slightly affected by the co-existence of Cl(-) and HCO3(-). The Cr(VI)-fixation stability tests show that only less than 0.2% adsorbed Cr(VI) is leaching out in water at pH 4-10 for 24 h because the adsorption/exchange of Cr(VI) with Friedels salt leads to the formation of a new stable phase (3CaO x Al2O3 x CaCrO4 x 10 H2O). This research thus suggests that Friedels salt is a potential cost-effective adsorbent for Cr(VI) removal in wastewater treatment.

Chemical characteristics and risk assessment of typical municipal solid waste incineration (MSWI) fly ash in China.

The release of heavy metals in municipal solid waste incineration (MSWI) fly ash has become a worrying issue while fly ash is utilized or landfilled. This work investigated the potential mobility of heavy metals in the fly ashes from 15 typical MSWI plants in Chinese mainland by the characterization of distribution, chemical speciation and leaching behavior of heavy metals. The results showed that total content of heavy metals decreased in the order Zn>Pb>Cu>Cr>Ni>Cd in samples. The toxicity characteristics leaching procedure (TCLP) of fly ash indicated that the amount of leached Cd in 67% of samples exceeded the regulated limit. Also, the excess amount of leached Zn and Pb was observed in 40% and 53% of samples, respectively. The chemical speciation analysis revealed that this excess of heavy metal leached in TCLP was contributed to the high content of acid soluble fraction (F1) and reducible fraction (F2) of heavy metal. Moreover, the great positive relevance between leaching behavior of heavy metals and F1 fraction was supported by principal component analysis (PCA). Risk assessment code (RAC) results suggested that Cd and Pb showed a very high risk class to the environment.

Enhanced removal of triphosphate by MgCaFe-Cl-LDH: Synergism of precipitation with intercalation and surface uptake

Triphosphate (TPP) is an important form of phosphate pollutants while its removal investigation has been just started now. This research examined the removal of triphosphate using Mg(2-x)Ca(x)FeCl-LDH (x = 0-2) as absorbents. We found that the removal of triphosphate over Mg(2)FeCl-LDH mainly underwent the surface adsorption and the near-edge intercalation, with the practical removal amount (9-11 mg(P)/g) corresponding to 10-15% of the theoretical one. In contrast, Ca(2)FeCl-LDH removed a higher amount of triphosphate (56.4 mg(P)/g). The comprehensive analysis of the triphosphate-uptake products with XRD/XPS/FTIR reveals that Ca(2)FeCl-LDH dissolves first and then released Ca(2+) ions react with triphosphate (TPP) to form insoluble Ca-TPP precipitate. Combination of these two different removal mechanisms enables Mg(0.5)Ca(1.5)FeCl-LDH to take up 84.2mg(P)/g from aqueous solution under similar conditions.

Biofiltration treatment of odors from municipal solid waste treatment plants

An in situ compost biofilter was established for the treatment of odors from biostabilization processing of municipal solid waste. The concentrations of total volatile organic compounds (VOCs) in odors and their components were measured. Biofilter media was characterized in terms of total carbon (TC), total nitrogen (TN), total phosphorus (TP), organic matter (OM), pH value and determination of bacterial colony structure. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the main components of the produced gas were benzene, toluene, ethylbenzene and xylene (BTEX) along with other alkanes, alkenes, terpenes, and sulphur compounds. The compost biofilter had remarkable removal ability for alkylated benzenes (>80%), but poor removal for terpenes ( approximately 30%). Total VOC concentrations in odors during the biostabilization process period ranged from 0.7 to 87 ppmv, and the VOC removal efficiency of the biofilter varied from 20% to 95%. After about 140 days operation, TN, TC, TP and OM in compost were kept almost stable, but the dissolved N, NH(4)-N and NO(3)-N experienced an increase of 44.5%, 56.2% and 76.3%, respectively. Dissolved P decreased by 27.3%. The pH value experienced an increase in the early period and finally varied from 7.38 to 8.08. Results of bacterial colony in packing material indicated that bacteria and mold colony counts increased, but yeasts and actinomyces decreased along with biofilter operation, which were respectively, 3.7, 3.4, 0.04 and 0.07 times of their initial values.

In-situ stabilization of Pb, Zn, Cu, Cd and Ni in the multi-contaminated sediments with ferrihydrite and apatite composite additives.

Three additives were evaluated for their effectiveness in the attenuation of Pb2+, Zn2+, Cu2+, Cd2+, Ni2+ in contaminated sediments. Apatite, ferrihydrite and their composite were applied to the sediments. For the remediation, BCR, SEM/AVS and TCLP were adopted as the evaluating method and comparison of their results were used for the first time to test in-situ stabilization effect. The results showed that after 5 months composite treatment, more than 70% Pb2+, 40% Zn2+, 90% Cu2+, 50% Cd2+ and 80% Ni2+ was immobilized in oxidizable and residual phases, respectively. Compared to untreated sediment, Pb2+, Zn2+, Cu2+, Cd2+ in residual fraction increased 20%, 10%, 10%, 10% with composite treatment after 5 months, respectively. SigmaSEM/AVS ratio declined from 12.6 to 9.3, in addition, composite treatments reduced the leaching of Pb2+ and Zn2+ from 10.6 mg L(-1) and 42.5 mg L(-1) to 5.4 mg L(-1) and 24.1 mg L(-1) in the sediment by TCLP evaluation. Meanwhile, apatite and ferrihydrite composite additives lowered the bioavailability and toxicity of sediments as well. Ferrihydrite had a positive effect in controlling the bioavailability and toxicity of heavy metals because it effectively retarded the oxidation of AVS in sediment.

Characterization of mercury- and zinc-doped alkali-activated slag matrix. Part I. Mercury

The physical properties, pore structure, hydration process and hydration products of mercury-doped (Hg-doped) alkali-activated slag (AAS) matrixes have been evaluated by examination of physical properties, pore structure analysis and XRD, TG-DTG, FTIR and TCLP methods. Low concentrations of Hg2+ ions had little effect on the compressive strength, pore structure and degree of hydration of AAS matrixes. The addition of 2% Hg2+ ions into the AAS matrix brought out an evident retardation on early hydration and reduction of early compressive strength, but no negative effects were noticed after hydration for 28 days. The results also show that up to 2% of Hg2+ ions can be effectively immobilized in the AAS matrix, with the leaching meeting the TCLP mercury limit. Two mechanisms, physical encapsulation and chemical fixation, are assumed to be responsible for the immobilization of mercury in the AAS matrix.

Effective removal of selenate from aqueous solutions by the Friedel phase

This research has demonstrated that the Friedel phase, e.g. a chloride-containing hydrocalumite (Ca(2)Al(OH)(6)Cl(H(2)O)(2) x mH(2)O), can rapidly adsorb large amounts of SeO(4)(2-) (up to 1.37 mmol/g). SeO(4)(2-) is removed via anionic exchange, as evidenced by the expansion of the d-spacing from 0.78 nm of Cl-hydrocalumite to 0.97-0.98 nm of SeO(4)-hydrocalumite. The newly formed SeO(4)-adsorbed hydrocalumite is stable in water at pH 4-13, indicating the strong fixation of selenate within the phase. In contrast, intercalated selenate in the Freidel phase can be recovered by desorbing in the NaCl solution, which can also regenerate and recycle the used adsorbent. The findings in this research strongly suggest that the Friedel phase is a new, environmentally friendly and cost-effective adsorbent to adsorb selenate from wastewater streams and dilute solutions.