Selective capture of ammonium ions from municipal wastewater treatment plant effluent with a nickel hexacyanoferrate electrode.

Currently, intercalation materials such as Prussian blue analogs have attracted considerable attention in water treatment applications due to their excellent size-based selectivity toward cations. This study aimed to explore the feasibility of using a nickel hexacyanoferrate (NiHCF) electrode for selective NH4+ capture from effluent from a municipal wastewater treatment plant. To assess the competitive intercalation between NH4+ and other common cations (Na+, Ca2+), a NiHCF//activated carbon (AC) hybrid capacitive deionization (CDI) cell was established to treat mixed-salt solutions. The results of cyclic voltammetry (CV) analysis showed a higher current response of the NiHCF electrode toward NH4+ ions than toward Na+ and Ca2+ ions. In a single-salt solution with NH4+, the optimized operating voltage of the hybrid CDI cell was 0.8 V, with a higher salt adsorption capacity (51.2 mg/g) than those obtained at other voltages (0.1, 0.4, 1.2 V). In a multisalt solution containing NH4+, Na+, and Ca2+ ions, the selectivity coefficients of NH4+/Ca2+ and NH4+/Na+ were 9.5 and 4.9, respectively. The feasibility of selective NH4+ capture using the NiHCF electrode in a hybrid CDI cell was demonstrated by treating the effluent from a municipal wastewater treatment plant (WWTP). The intercalation preference of the NiHCF electrode with the WWTP effluent was NH4+>K+>Na+>Ca2+>Mg2+, and NH4+ showed the highest salt adsorption capacity among the cations during consecutive cycles. Our results revealed that cations with smaller hydrated radii and lower (de)hydration energies were more favorably intercalated by the NiHCF electrode. The results provide important knowledge regarding the use of intercalation-type electrodes for selective nutrient removal and recovery from wastewater.

Cation selectivity of activated carbon and nickel hexacyanoferrate electrode materials in capacitive deionization: A comparison study.

In this study, the electrosorption selectivity of porous activated carbon (AC) and nickel hexacyanoferrate (NiHCF), which represent two working mechanisms of capacitive electrosorption and redox intercalation, was investigated to separate cations in capacitive deionization (CDI). The cyclic voltammetry diagrams of AC showed the rectangular shape of double-layer charging, while that of NiHCF showed separated peaks associated with redox reactions. The specific capacitance of NiHCF was 143.6 F/g in 1 M NaCl, which was almost two times higher than that of AC. Cation selectivity experiments were conducted in single-pass CDI for a multi-cation solution. The electrosorption preference of the AC cathode was determined by a counterbalance between the ionic charge and hydrated size, reflecting the selectivity coefficient of different cations over Na+ in the range of 0.86-2.63. For the NiHCF cathode, the cation selectivity was mainly dominated by the hydrated radius and redox activity. Notably, high selectivities of K+/Na+ ≈ 3.57, Na+/Ca2+ ≈ 9.97, and Na+/Mg2+ ≈ 18.92 were obtained. A significant improvement in the electrosorption capacity and monovalent ion selectivity can be achieved by utilizing the NiHCF electrode. The study demonstrates the fundamental aspects and promising opportunities of CDI in regard to ion selectivity.

An integrated active biochar filter and capacitive deionization system for high-performance removal of arsenic from groundwater.

An integrated process of filtration and electrosorption was first applied to enable high-performance arsenic removal for groundwater remediation. An active manganese dioxide-rice husk biochar composite (active BC) filter was utilized for oxidization of As(III) to As(V) and initial removal of As(III, V). Subsequently, electrosorption by capacitive deionization (CDI) was applied as a posttreatment to improve arsenic removal. The active BC approach exhibited fast removal rates of 0.75 and 0.63 g mg-1 h-1 and high maximum removal capacities of 40.76 and 48.15 mg g-1 for As(III) and As(V), respectively. Importantly, column experiments demonstrated that the arsenic removal capacity in the active BC filter was 2.88 mg g-1, which was 72 times higher than that of BC. The results were due to the high efficiency (94%) of redox transformation of As(III) to As(V). The electrosorptive removal of arsenic was further controlled by changing the voltage in CDI. With a charging step of 1.2 V, the total arsenic concentration can be reduced to 0.001 mg L-1 with a low energy consumption of 0.0066 kW h m-3. Furthermore, the integrated system can remove As from real groundwater to achieve the World Health Organization guideline value for drinking water quality.

Active MnO2/biochar composite for efficient As(III) removal: Insight into the mechanisms of redox transformation and adsorption.

In the present work, an active MnO2/rice husk biochar (BC) composite (MBC) was prepared to enhance As(III) removal for groundwater remediation. The MBC material obtained an improved porous structure (i.e., specific surface area, pore volume and mesoporosity) with MnO2, providing abundant reaction or interaction sites for surface or interface-related processes such as redox transformation and adsorption of arsenic. As a result, a significant enhancement in arsenic removal can be achieved by using MBC. More specifically, MBC showed a high removal capacity for As(III), which was tenfold higher than that of BC. This improvement can be ascribed to the redox transformation of As(III) via MnO2, resulting in the more effective removal of As(V) species. In addition, pH was an important factor that could influence the As(III) removal capacity. Under alkaline conditions, the As(III, V) removal capacity of MBC was clearly lower than those under acidic and neutral conditions due to the negative effects of electrostatic repulsion. Importantly, a powerful transformation capability of As(III) via MBC was presented; namely, only 5.9% As(III) remained in solution under neutral conditions. Both MnO2 and the BC substrate contributed to the removal of arsenic by MBC. MnO2 delivered Mn-OH functional groups to generate surface complexes with As(V) produced by As(III) oxidation, while the reduced Mn(II) and As(V) could precipitate on the MBC surface. The BC substrate also provided COOH and OH functional groups for As(III, V) removal by a surface complexation mechanism. Note that the application of MBC in the treatment of simulated groundwater demonstrated an efficient arsenic removal of 94.6% and a concentration of arsenic as low as the 10 µg L-1 WHO guideline.

Meso/micropore-controlled hierarchical porous carbon derived from activated biochar as a high-performance adsorbent for copper removal.

High-quality meso/micropore-controlled hierarchical porous carbon (HPC) was synthesized by a hard template method utilizing rice husk biochar and then used to adsorb copper ions from an aqueous solution. The preparation procedure included two main steps: base leaching and physicochemical activation. During the activation process, the porosity characteristics (i.e., specific surface area and meso/micropore ratio) were controlled by altering the KOH impregnation ratio, activation time, and temperature under the CO2 atmosphere. In addition, a copper adsorption study was performed using three HPC samples with different pore structures and characteristics. The results of this study indicate that the adsorption capacity of HPC material derived from rice husk biochar is strongly influenced by its meso/micropore ratio. As evidenced, HPC 3-0.5-800, which was impregnated by a KOH:biochar ratio of 3 and activated at 800°C for 0.5h under a CO2 atmosphere, has a very high specific surface area of 2330 m2g-1 with an 81% mesopore to total specific surface area. Importantly, it exhibited a superior adsorption capacity of 265mgg-1 and rapid adsorption kinetics for copper ions. The improvement is ascribed to the high specific surface area and favorable hierarchical structure. The findings demonstrate the feasibility of controlling the hierarchical pore structure of rice husk biochar-derived carbons as high-performance adsorbents for copper ion removal from water.