Steam activation of porous concave polymer nanospheres for high-efficient chromium and cadmium removal.

The issue of heavy metal contamination in water is a global concern, and the development of highly efficient adsorbent materials is crucial for the removal and detoxification of heavy metals. Polymer-based materials have emerged as a promising class of adsorbents due to their ability to capture heavy metal pollutants and reduce them to less toxic forms. The limited surface area of conventional polymer adsorbents makes them less effective for high-capacity adsorption. Herein, we present a low-temperature steam activation approach to address this challenge. This activation approach leads to a remarkable increase of over 20 times in the surface area of concave aminophenol-formaldehyde (APF) polymer nanospheres (from 45 to 961 m2/g) while preserving their reductive functional groups. The activated concave APF nanospheres were evaluated for their adsorption capabilities towards two typical heavy metal ions (i.e., Cr(VI) and Cd(II)) in aqueous solutions. The maximum adsorption capacities achieved were 1054 mg g-1 for Cr(VI) and 342 mg g-1 for Cd(II), which are among the highest performances reported in the literature and are much higher than the capacities of the non-activated APF nanospheres. Additionally, approximately 71.5 % of Cr(VI) was simultaneously reduced to Cr(III) through the benzenoid amine pathway during adsorption, highlighting the crucial role of the steam activation strategy in enhancing the capability of polymer adsorbents.

Sulfhydryl-Functionalized Amino Group Polymer Microcomposites toward Efficient Adsorption of Aqueous Cr(VI), As(III), Cd(II), and Pb(II).

The development of efficient adsorbents for heavy metal pollution, especially five toxic heavy metals, has attracted great research interest. Polymer-based adsorbents have aroused research value for their abundant functional groups and high porosity to the ability to capture metal ions. We designed a sulfhydryl-functionalized polymer microcomposite to take up Cr(VI), As(III), Cd(II), and Pb(II). The adsorption capacity achieved was 64.2 mg g-1 for Cr(VI), 44.9 mg g-1 for As(III), 35.5 mg g-1 for Cd(II), and 18.2 mg g-1 for Pb(II). Langmuir and Sips isotherm model is dominant for As(III), Cd(II), and Pb(II) adsorption. Pseudo-second-order kinetic models can better describe the adsorption behavior of Cr(VI), implying that chemisorption is accompanied by Cr(VI) adsorption. Cr(VI) simultaneous reduction to Cr(III) through the benzenoid amine oxidate pathway was the dominant mechanism, precipitation for Cd(II) adsorption was convinced, and chelation between As(III)/Pb(II) and─SH group and complexation between Pb(II) and C═O or benzene hydroxyl were a plausible mechanism for As(III) and Pb(II) adsorption.

Phosphate recovery and simultaneous nitrogen removal from urine by electrochemically induced struvite precipitation.

The direct discharge of urine into water bodies leads to environmental pollution, and an increase in the water treatment cost, whereas recycling of the nutrients in urine is of significant economic value. A single-compartment reactor was investigated for the recycling of phosphate and simultaneous removal of nitrogen from urine wastewater by electrochemical magnesium induction, and electrochemical oxidation for the removal of residual nitrogen from the supernatant. The results demonstrated that phosphate recovery capacity was greater than 11 mg P cm-2 h-1 at a current density of 15 m A cm-2 and anodizing time of 20 min; the removal rates of ammonium and total nitrogen in the synchronous electrochemical oxidation were 80% and 75%, respectively, at a current density of 45 m A cm-2 and anodizing time of 60 min. The anodizing time and initial pH were determined to be critical control factors in the electrochemical struvite induction and nitrogen electrochemical oxidation. The on-site electrochemical nitrogen oxidation could rapidly utilize the alkaline supernatant following phosphate recovery. Thus, the integration of the single-compartment reactor, electrochemical magnesium dosage, and simultaneous nitrogen electrochemical oxidation demonstrates potential for application to decentralized reactors to treat source-separated urine.

Shaping Nanoparticles for Interface Catalysis: Concave Hollow Spheres via Deflation-Inflation Asymmetric Growth.

Hollow spheres are charming objects in nature. In this work, an unexpected deflation-inflation asymmetric growth (DIAG) strategy is reported, generating hollow nanoparticles with tailored concave geometry for interface catalysis. Starting from aminophenol-formaldehyde (APF) nanospheres where the interior crosslinking degree is low, fully deflated nanobowls are obtained after etching by acetone. Due to APF etching and repolymerization reactions occuring asymmetrically within a single particle, an autonomous inflation process is observed similar to a deflated basketball that inflates back to a "normal" ball, which is rare at the nanoscale. A nucleophilic addition reaction between acetone and APF is elucidated to explain the chemistry origin of the DIAG process. Interestingly, the deflated APF hollow spheres enable preferential immobilization of lipase in the concave domain, which facilitates the stabilization of Pickering emulsion droplets for enhanced enzymatic catalysis at the oil-water interface. The study provides new understandings in the designable synthesis of hollow nanoparticles and paves the way toward a wide range of applications of asymmetric architectures.

Formation of magnesium hydrosilicate nanomaterials and its applications for phosphate/ammonium removal.

Nanomaterials of magnesium hydrosilicate Mg3Si2O5(OH)4 were developed for phosphate and ammonium recovery from wastewater in virgin, which had the structure of diffuse interlamellar order, and synthesized under hydrothermal conditions at temperatures of 200°C for 36-72 h from mixtures of magnesite and zeolite as mineralizers. The amount of magnesium released has gone up to 48 mg/g by magnesium hydrosilicate, which was increased with the increase in the weight ratio of magnesite:zeolite. When magnesium hydrosilicate was used to adsorb phosphate and ammonium, electrostatic adsorption was not a dominant mechanism, the adsorbing capacity of phosphate was about 19 mg/g, and the simultaneous adsorbing capacity of ammonium was 7.8 mg/g.

A novel treatment processes of struvite with pretreated magnesite as a source of low-cost magnesium.

By crystallization process, phosphorus can be recycled from wastewater. However, the reagent cost limits the application of struvite precipitation. Magnesite, as a low-cost magnesium source, can result in a cost savings, while the poor dissolution offset of low-cost reagent. In this study, most of the pyrolysate of magnesite was dissolved by changing the process of reagent addition; the solubility of the pyrolysate was increased at acid wastewater. The removal rate of phosphate by the pyrolysate was higher than that of magnesite, the phosphate removal rate was from 70.2 to 88.2% at 600 °C, 0.5 h to 1200 °C, 3 h. Phosphate removal rate was achieved optimal when calcination temperature was 700 °C at 2 h. By adding the pyrolysate to acid wastewater (pH ≤ 2) before NH4Cl, phosphate removal rate was closed to that of MgCl2 as magnesium source, while magnesite was priced at similar levels to lime.

Ammonium removal from wastewater via struvite pyrolysate recycling with Mg(OH)2 addition.

Magnesium ammonium phosphate (MAP) pyrolysate recycling technology was investigated with Mg(OH)2-mediated pyrolysis. The results revealed that the removal ratio of ammonium was stable at about 75%, and could be increased to 79% after additional acidolysis. The phosphate concentration in the supernate was low at 2 mg/L. The optimum conditions for ammonia release were a 1:1 molar ratio of Mg(OH)2:NH4(+), a heating temperature of 110 °C and a heating time of 3 h. With continual additions of Mg(OH)2 to release ammonia, magnesium phosphate (Mg3(PO4)2) was suggested as a possible derivative. However, with Mg(OH)2-mediated pyrolysis, the growth and nucleation of MAP was inhibited during MAP pyrolysate recycling.

A kinetic study of struvite precipitation recycling technology with NaOH/Mg(OH)2 addition.

Struvite precipitation recycling technology is received wide attention in removal ammonium and phosphate out of wastewater. While past study focused on process efficiency, and less on kinetics. The kinetic study is essential for the design and optimization in the application of struvite precipitation recycling technology. The kinetics of struvite with NaOH/Mg(OH)2 addition were studied by thermogravimetry analysis with three rates (5, 10, 20 °C/min), using Friedman method and Ozawa-Flynn-Wall method, respectively. Degradation process of struvite with NaOH/Mg(OH)2 addition was three steps. The stripping of ammonia from struvite was mainly occurred at the first step. In the first step, the activation energy was about 70 kJ/mol, which has gradually declined as the reaction progress. By model fitting studies, the proper mechanism function for struvite decomposition process with NaOH/Mg(OH)2 addition was revealed. The mechanism function was f(α)=α(α)-(1-α)(n), a Prout-Tompkins nth order (Bna) model.

Struvite pyrolysate recycling combined with dry pyrolysis for ammonium removal from wastewater.

The dry pyrolysis of magnesium ammonium phosphate (MAP) with NaOH powder for ammonium release was investigated, as well as the utility of MAP pyrolysate recycling. The identities of the MAP pyrolysate and its derivatives were experimentally validated. The results showed that the pyrolysate was amorphous magnesium hydrogen phosphate (MgHPO4) and magnesium pyrophosphate (Mg2P2O7). The best molar ratio of sodium hydroxide (NaOH) powder to ammonium was 1:1, at 110°C for 3h. The optimum pH for pyrolysate recycling was 9.5. The ammonia removal ratio could be maintained above 80% with MAP pyrolysate recycling. Seed crystal inoculation increased the rate of MAP crystallization by 20.86%, as well as the MAP grain size (2.08nm with seeding versus 1.72nm without). MAP particle size with NaOH treatment decreased: d(0.5)=19.34µm versus d(0.5)=30.35µm for direct pyrolysis. The results demonstrated that crystal growth was controlled by adding NaOH during MAP pyrolysis.

Combination of struvite pyrolysate recycling with mixed-base technology for removing ammonium from fertilizer wastewater.

Removal of ammonium from wastewater via struvite (MAP) pyrolysate recycling combined with a mixed-base NaOH/Mg(OH)(2) technology was investigated, and the phosphate and magnesium concentration in the supernatant were measured. The optimal parameters for acidolysis were a pH of 1; temperature of 120°C and time of 2h. The presence of derivatives of amorphous magnesium hydrogen phosphate (MgHPO(4)), namely magnesium phosphate (Mg(3)(PO(4))(2)) and magnesium pyrophosphate (Mg(2)P(2)O(7)) were verified by experiment. The ammonium removal ratio in this combined mixed-base technology was 96.8% in the first cycle, 80.6% in the second, and 81.0% after acidolysis. The phosphate and magnesium ions concentration in the supernatant were about 1mg/L and 40 mg/L, respectively. The grain size of MAP was 1.52 nm without seeding and 1.79 nm with seeding, and the growth rate of MAP was 17.6%.