Demulsification with simultaneous water purification by coupling filtration and enhanced oil droplet coalescence at anode interface in an electrochemical reactor.

With the increasing demand of recycling disposal of industrial wastewater, oil-in-water (O/W) emulsion has been paid much attention in recent years owing to its high oil content. However, due to the presence of surfactant and salt, the emulsion was usually stable with complex physicochemical interfacial properties leading to increased processing difficulty. Herein, a novel flow-through electrode-based demulsification reactor (FEDR) was well designed for the treatment of saline O/W emulsion. In contrast to 53.7% for electrical demulsification only and 80.3% for filtration only, the COD removal efficiency increased to 92.8% under FEDR system. Moreover, the pore size of electrode and the applied voltage were two key factors that governed the FEDR demulsification performance. By observing the morphology of oil droplets deposited layer after different operation conditions and the behavior of oil droplets at the electrode surface under different voltage conditions, the mechanism was proposed that the oil droplets first accumulated on the surface of flow-through electrode by sieving effect, subsequently the gathered oil droplets could further coalesce with the promoting effect of the anode, leading to a high-performing demulsification. This study offers an attractive option of using flow-through electrode to accomplish the oil recovery with simultaneous water purification.

Sequential Demulsification through the Hydrophobic-Hydrophilic-Hydrophobic Filtration Layer toward High-Performing Oil Recovery.

Demulsification using membranes is a promising method to coalesce highly stable emulsified oil droplets for oil recovery. Nevertheless, a structure of the current filtration medium that is not efficient for oil droplet coalescence impedes rapid permeability, thereby inevitably restricting their practical applications. Herein, we report a hydrophobic-hydrophilic-hydrophobic (3H) demulsification medium that exhibits a benchmark permeability of ∼2.1 × 104 L m-2 h-1 with a demulsification efficiency of >98.0%. Remarkably, this 3H demulsification medium maintains over 90% demulsification efficiency in the oil-in-water (O/W) emulsions with a wide range of surfactant concentrations, which shows excellent applicability. Based on the combined results of quasi situ microscope images and molecular dynamics simulations, we show that the polydimethylsiloxane-modified hydrophobic layer facilitates the capture and coalescence of oil droplets, the hydrophilic inner layer assists in squeezing the coalescence of enlarged droplets, and the third hydrophobic layer accelerates the discharge of demulsified oil to sustain permeability. The sequential demulsification mechanism between this 3H filtration layer provides a general guide for designing a demulsifying membrane with high demulsification efficiency and high flux toward oil recovery.

Synergetic Oxidation of the Hydroxyl Radical and Superoxide Anion Lowers the Benzoquinone Intermediate Conversion Barrier and Potentiates Effective Aromatic Pollutant Mineralization.

Regulation of the free radical types is crucial but challenging in the ubiquitous heterogeneous catalytic oxidation for chemosynthesis, biotherapy, and environmental remediation. Here, using aromatic pollutant (AP) removal as a prototype, we identify the massive accumulation of the benzoquinone (BQ) intermediate in the hydroxyl radical (•OH)-mediated AP degradation process. Theoretical prediction and experiments demonstrate that BQ is both a Lewis acid and base because of its unique molecular and electronic structure caused by the existence of symmetrical carbonyl groups; therefore, it is hard to be electrophilically added by oxidizing •OH as a result of the high reaction energy barrier (ΔG = 1.74 eV). Fortunately, the introduction of the superoxide anion (•O2-) significantly lowers the conversion barrier (ΔG = 0.91 eV) of BQ because •O2- can act as the electron donor and acceptor simultaneously, electrophilically and nucleophilically add to BQ synchronously, and break it down. Subsequently, the breakdown products can then be further oxidized by •OH until completely mineralized. Such synergistic oxidation based on •OH and •O2- timely eliminates BQ, potentiates AP mineralization, and inhibits electrode fouling caused by high-resistance polymeric BQ; more importantly, it effectively reduces toxicity, saves energy and costs, and decreases the environmental footprint, evidenced by the life cycle assessment.

Selective Oxygen Activation to Reactive Oxygen Species on a Carbon Layer-Encapsulated CuxO Electrocatalyst for Water Purification.

In situ synthesis of reactive oxygen species (ROS) on demand via oxygen activation (OA) is significant in biological, chemical, and environmental fields. Thus, the design of OA catalysts with adequate reactivity, durability, and selectivity is critical but challenging. Here, we report a CuxO@C core@shell photoelectrode prepared by encapsulating Cu/Cu2O/CuO into a carbon layer through anodic electropolymerization (electrophoresis-coupled self-assembly of carbon quantum dots). Theoretical prediction and experiments indicate that the carbon layer can effectively facilitate optical trapping and charge transfer, thus promoting photoelectric conversion and anti-photocorrosion performance of CuxO@C. The inner CuxO core acts as an electron reservoir and continuously injects electrons into the outer carbon layer shell, and the carbon atoms adjacent to oxygen-enriched functional groups (C-O-C and -COOH) in the electron-rich carbon layer work as the reactive sites to adsorb O2 and donate electrons to the antibonding orbital [lowest unoccupied molecular orbital (π*)] of dioxygen. Optimized adsorption and hydrogenation of the critical intermediates (*O2, *OOH, and *H2O2) and thermodynamically tunable O-O bond cleavage enable O2 being selectively reduced to the superoxide anion and hydroxyl radical via the mixed multielectron processes consisting of one- and three-electron pathways. Sulfamethoxazole, an emerging refractory organic contaminant widely present in the environment, can be effectively degraded (∼100% removal) in such an electrochemical platform, benefiting from the abundant ROS generated in situ. Our findings demonstrate an innovative strategy to develop highly efficient and selective OA catalysts for practical water purification.

Electrically Controlled Adsorptive Membranes with Tunable Affinity for Selective Chromium (VI) Separation from Water.

Ionic contaminants such as Cr(VI) pose a challenge for water purification using membrane-based processes. However, existing membranes have low permeability and selectivity for Cr(VI). Therefore, in this study, we prepared an electrically controlled adsorptive membrane (ECAM-L) by coating a loose Cl--doped polypyrrole layer on a carbon nanotube substrate, and we evaluated the performance of ECAM-L for Cr(VI) separation from water. We also used electrochemical quartz crystal microbalance measurements and molecular dynamics and density functional theory calculations to investigate the separation mechanisms. The adsorption and desorption of Cr(VI) could be modulated by varying the electrostatic interactions between ECAM-L and Cr(VI) via potential control, enabling the cyclic use of the ECAM-L without additional additives. Consequently, the oxidized ECAM-L showed high Cr(VI) removal performance (<50 µg/L) and treatment capacity (>3500 L/m2) at a high water flux (283 L/m2/h), as well as reusability after the application of a potential. Our study demonstrates an efficient membrane design for water decontamination that can selectively separate Cr(VI) through a short electric stimulus.

Electrically Redox-Active Membrane with Switchable Selectivity to Contaminants for Water Purification.

Membrane technology provides an attractive approach for water purification but faces significant challenges in separating small molecules due to its lack of satisfactory permselectivity. In this study, a polypyrrole-based active membrane with a switchable multi-affinity that simultaneously separates small ionic and organic contaminants from water was created. Unlike conventional passive membranes, the designed membrane exhibits a good single-pass filtration efficiency (>99%, taking 1-naphthylamine and Pb2+ as examples) and high permeability (227 L/m2/h). Applying a reversible potential can release the captured substances from the membrane, thus enabling membrane regeneration and self-cleaning without the need for additives. Advanced characterizations reveal that potential switching alters the orientation of the doped amphipathic molecules with the self-alignment of the hydrophobic alkyl chains or the disordered sulfonate anions to capture the target organic molecules or ions via hydrophobic or electrostatic interactions, respectively. The designed smart membrane holds great promise for controllable molecular separation and water purification.

Revealing the Pore Size-Dependent Sorption Mechanism of Toluene and Cetane in Porous Carbon by Nuclear Magnetic Resonance.

The adsorption of contaminants by porous carbon has been extensively studied by conventional isotherm and kinetic methods. However, the co-adsorption behavior and sorption sites of multiple contaminants in different-sized pores remain unclear. Herein, the nuclear magnetic resonance (NMR) approach is performed to investigate the adsorption mechanism of toluene and cetane in the confined space of carbon at the molecular level. The ring current effect induces the variation in the NMR chemical shifts of in-pore adsorbed toluene and cetane, realizing the identification of pore-dependent adsorption sites for contaminant removal. Cetane has a slower adsorption kinetic but a higher binding energy than toluene, which could squeeze toluene from micropores to larger pores with increasing adsorption quantity. This leads to a stronger competitive adsorption effect in small micropores than in mesopores. Accordingly, hierarchical porous carbons are determined to be the most effective adsorbents for the adsorption of coexisting contaminants. This study not only provides an effective NMR method to reveal the adsorption mechanism in the confined space of porous carbon at the molecular level but also offers new insights into the pore size-dependent adsorption of activated carbon for petroleum contaminant treatment.

Visualization of Electrochemically Accessible Sites in Flow-through Mode for Maximizing Available Active Area toward Superior Electrocatalytic Ammonia Oxidation.

Active chlorine species-mediated electrocatalytic oxidation is a promising strategy for ammonia removal in decentralized wastewater treatment. Flow-through electrodes (FTEs) provide an ideal platform for this strategy because of enhanced mass transport and sufficient electrochemically accessible sites. However, limited insight into spatial distribution of electrochemically accessible sites within FTEs inhibits the improvement of reactor efficiency and the reduction of FTE costs. Herein, a microfluidic-based electrochemical system is developed for the operando observation of microspatial reactions within pore channels, which reveals that reactions occur only in the surface layer of the electrode thickness. To further quantify the spatial distribution, finite element simulations demonstrate that over 75.0% of the current is accumulated in the 20.0% thickness of the electrode surface. Based on these findings, a gradient-coated method for the active layer was proposed and applied to a Ti/RuO2 porous electrode with an optimized pore diameter of ∼25 µm, whose electrochemically accessible surface area was 381.7 times that of the planar electrode while alleviating bubble entrapment. The optimized reactor enables complete ammonia removal with an energy consumption of 60.4 kWh kg-1 N, which was 24.2% and 39.9% less than those with pore diameters of ∼3 µm and ∼90 µm, respectively.

Insight into the Key Role of Cr Intermediates in the Efficient and Simultaneous Degradation of Organic Contaminants and Cr(VI) Reduction via g-C3N4-Assisted Photocatalysis.

Photocatalysis provides an impetus for the synergetic removal of Cr(VI) and organic contaminants, but the generation of Cr intermediates and their potential oxidizability may be overlooked in pollutant conversion. Herein, the Cr intermediates in the Cr(VI) reduction process were emphasized in Cr(VI)/bisphenol A (BPA) by using graphitic carbon nitride as a photocatalyst. The active species for BPA photodegradation in the BPA system and Cr(VI)/BPA system suggested that the Cr(VI) reduction process indeed promotes BPA photodegradation. Electron paramagnetic resonance (EPR) of Cr complexes and in situ variable-temperature EPR analysis demonstrated Cr(V) intermediate (g = 1.978) generation in Cr(VI) reduction and its oxidization for BPA degradation in photocatalysis. By adding the electron donor Na2SO3, BPA degradation was induced in Cr(VI)/BPA solution, further confirming the positive effect of Cr(V). Moreover, the difference in BPA degradation products in the BPA/air, Cr(VI)/BPA/air, and Cr(VI)/BPA/Ar systems indirectly explained why the Cr(V) intermediate was involved in BPA degradation. Density functional theory calculations revealed that photogenerated electrons can reduce the free energy (0.98 eV) of converting Cr(VI) into Cr(V), which can facilitate the subsequent Cr(V) oxidation step for BPA degradation. This work contributes to the exploration of the Cr(VI) reduction process and the synergistic removal of organic pollutants in Cr(VI)/organics systems.

Systematic Design of a Flow-Through Titanium Electrode-Based Device with Strong Oil Droplet Rejection Property for Superior Oil-in-Water Emulsion Separation Performance.

Oily wastewater treatment has been restricted by the existence of stable oil-in-water (O/W) emulsions containing micrometer-sized oil droplets. However, the strong adhesion and stacking of emulsified oil droplets on the surface of current separation media cause serious fouling of the treatment unit and the rapid decline of treatment efficiency. Herein, a novel flow-through titanium (Ti) electrode-based filtration device with remarkable oil droplet rejection property was well designed for the continuously separating O/W emulsion. In contrast to the pristine Ti foam, the permeance of the TiO2 nanoarray-coated Ti foam (NATF) increased from 2538 to 4364 L m-2 h-1 bar-1 through gravity-driven flow. Further, more than ∼70% permeability can be maintained after 6 h of O/W emulsion filtration using the current device, the value of which was markedly higher than that of conventional oil/water separation filters (less than 5%). According to the results of wettability test, the super-oil-repellent surface endowed by this nanoarray structure primarily avoided the formation of a compact oil fouling layer. When the voltage was applied, accompanied by the electrophoresis effect, redistribution of surfactant molecules on the surface of oil droplets induced by an electric field made them readily captured by the microbubbles continuously generated from the electrode, thereby rapidly migrating these bubble-adhered oil droplets far from the filtration medium.

Facilitating Molecular Activation and Proton Feeding by Dual Active Sites on Polymeric Carbon Nitride for Efficient CO2 Photoreduction.

Photoreduction of CO2 provides an appealing way to alleviate the energy crisis and manage the global carbon balance but is limited by the high activation energy and the rate-limiting proton transfer. We now develop a dual-site strategy for high-efficiency CO2 conversion through polarizing CO2 molecules at pyridine N vacancies and accelerating the intermediate protonation by protonated pyridine N adjacent to nitrogen vacancies on polymeric carbon nitride. Our photocatalysts with atomic-level engineered active sites manifest a high CO production rate of 1835 µmol g-1 h-1 , 183 times higher than the pristine bulk carbon nitride. Theoretical prediction and experimental studies confirm that such excellent performance is attributed to the synergistic effect between vacant and protonated pyridine N in decreasing the formation energy of the key *COOH intermediates and the efficient electron transfer relay facilitated by the defect-induced shallow trap state and homogeneous charge mediators.

Synergetic Hydroxyl Radical Oxidation with Atomic Hydrogen Reduction Lowers the Organochlorine Conversion Barrier and Potentiates Effective Contaminant Mineralization.

For effective treatment and reuse of wastewater, removal of organochlorines is an important consideration. Oxidation or reduction of these compounds by one-component free radicals is difficult because of the high-energy barrier. Theoretical calculations predict that redox synergy can significantly lower the energy barriers. Hence, we developed an energy-efficient dual photoelectrode photoelectrochemical system wherein the oxidized and reduced radicals coexist. Taking p-chloroaniline as an example, the atomic hydrogen first initiates nucleophilic hydrodechlorination to form a critical intermediate followed by the electrophilic oxidation of the hydroxyl radical; the process shows stable free-energy changes. Compared to oxidation alone, the reaction rate and mineralization in the redox synergy system were ∼4.5 and ∼2.1 times higher, respectively. Nitrogen was also completely removed via this system. The full life cycle assessment with power consumption as the boundary showed that the proposed system was sustainable and highly energy efficient, ensuring its application in organochlorine wastewater treatment.

Optimization of a Hierarchical Porous-Structured Reactor to Mitigate Mass Transport Limitations for Efficient Electrocatalytic Ammonia Oxidation through a Three-Electron-Transfer Pathway.

Regulation of fast three-electron-transfer processes for electrocatalytic oxidation of ammonia to nitrogen by achieving efficient generation and utilization of active sites is the optimal strategy in ammonia-containing wastewater treatment. However, the limited number of accessible active sites and sluggish interfacial mass transfer are two main bottlenecks restricting conventional ammonia oxidation configurations. Herein, we develop a macroporous Ni foam electrode integrated with vertically aligned two-dimensional mesoporous Ni2P nanosheets to create sufficient exposure of active centers. A novel ammonia oxidation reactor with the developed hierarchical porous-structured electrodes was assembled to construct an intensified microfluidic process with flow-through operation to mitigate macroscopic mass transport limitations. The confined microreaction space in the hierarchical porous reactor further promotes spontaneous nanoscale diffusion/convection of the target contaminant to high-valence Ni sites and enhances the microscopic mass transfer. The combined results of electrochemical measurements and in situ Raman spectra showed that the ammonia degradation mechanism results from direct oxidation by the high-valence Ni, significantly different from the conventional indirect active-chlorine-species-mediated oxidation. The optimized reactor achieves high-efficiency three-electron-transfer ammonia conversion with an ammonia removal efficiency of ∼70% from an initial concentration of ∼1400 mg/L and byproduct production of ∼4%, significantly superior to a conversion unit comprising a featureless Ni-based electrode in the immersed configuration, which had >50% byproduct yield. 20 days of continuous operation under variable conditions achieved >90% ammonia degradation performance and an energy consumption of 25.42 kW h kg-1 N (1 order of magnitude lower than the active-chlorine-mediated process), showing the potential of the reactor in medium-concentration ammonia-containing wastewater treatment.

Synchronous Reduction-Oxidation Process for Efficient Removal of Trichloroacetic Acid: H* Initiates Dechlorination and ·OH Is Responsible for Removal Efficiency.

Degradation of chlorinated disinfection by-products using the electroreduction process has been considered as a promising approach for advanced water treatment, while the removal efficiency is restricted by a high barrier for dechlorination of intermediates only by reductive atomic hydrogen (H*) and excessive cost required for reducing atmosphere. In this paper, we predict that the dechlorination efficiency for trichloroacetic acid (TCA), a typical chlorinated disinfection by-product, can be accelerated via a synchronous reduction-oxidation process, where the dechlorination barrier can be lowered by the oxidation reactions toward the critical intermediates using hydroxyl radicals (·OH). Based on scientific findings, we constructed a synchronous reduction-oxidation platform using a Pd-loaded Cu/Cu2O/CuO array as the core component. According to the combined results of theoretical and experimental analyses, we found that the high dispersion of nano-sized Pd on a photocathode was beneficial for the production of a high concentration of H* at low overpotential, a perquisite for initiating the dechlorination reaction. Simultaneously, excess H* has the potential to convert O2 to H2O2 in ambient conditions (air condition), and H2O2 can be further activated by a Cu-containing substrate to ·OH for attacking the critical intermediates. In this system, ∼89.1% of TCA was completely dechlorinated and ∼26.8% mineralization was achieved in 60 min, which was in contrast to the value of ∼65.7% and mineralization efficiency of only ∼1.7% achieved through the reduction process (Ar condition).

Hydrogen-Bond-Mediated Self-Assembly of Carbon-Nitride-Based Photo-Fenton-like Membranes for Wastewater Treatment.

Graphitic carbon nitride has emerged as a promising material for high-performance membranes with both filtration and catalytic abilities. However, the scalable construction of carbon-nitride-based membranes is seriously restricted by the poor ability to tailor the structure and poor solvent solubility of bulk nanostructures. Herein, carbon nitride sol was prepared in high yield and used as a precursor to assemble photo-Fenton-like membranes. Intermolecular hydrogen-bond interactions between carbon nitride nanofibers were found to be vitally important for the repolymerization of hydrolyzed molecules into dense and solid membranes. Intercalated Fe-containing polyoxometalates (Fe-POMs) not only acted as molecular linkers to construct carbon nitride membranes but also provided new opportunities for the catalytic functionality. Benefiting from the hydrophobic nanocapillaries in 2D carbon nitride for ultralow water-carbon friction, self-assembled membranes effectively rejected pollutant molecules with high water permeation flux. The integration of carbon nitride photocatalysts with Fenton-like Fe-POMs contributed to the in situ degradation of retained pollutants. Thus, our work manifested a facile bottom-up strategy to construct photo-Fenton-like membranes with antifouling abilities for wastewater treatment.

The effects of hydrogen peroxide pre-oxidation on ultrafiltration membrane biofouling alleviation in drinking water treatment.

Pre-oxidation is widely used to reduce ultrafiltration membrane fouling. However, the variation in the composition of microbial communities and extracellular polymeric substances (EPSs) accompanying pre-oxidation in drinking water treatment has received little attention. In this study, hydrogen peroxide (H2O2) was used in a coagulation-ultrafiltration process with Al2(SO4)3·18H2O. A long-term reactor experiment (60d) showed that pre-oxidation alleviated membrane fouling, mainly due to its inhibition of microbial growth, as observed by flow cytometry measurements of the membrane tank water. Further analysis of the formed cake layer demonstrated that the corresponding levels of EPS released from the microbes were lower with than without H2O2 treatment. In comparison to polysaccharides, proteins dominated the EPS. 2D-electrophoresis showed little difference (p>0.05, Student's t-test) in the composition of proteins in the cake layer between the treatments with and without H2O2. The molecular weights of proteins ranged from approximately 30-50kDa and the majority of isoelectric points ranged from 6 to 8. High-throughput sequencing showed that the predominant bacteria were Proteobacteria, Bacteroidetes, and Verrucomicrobia in both cake layers. However, the relative abundance of Planctomycetes was higher in the cake layer with H2O2 pre-oxidation, which was likely probably due to the strong oxidative resistance of its cell wall. Overall, our findings clarify the fundamental molecular mechanism in H2O2 pre-oxidation for ultrafiltration membrane bio-fouling alleviation in drinking water treatment.

Comparison of the effects of aluminum and iron(III) salts on ultrafiltration membrane biofouling in drinking water treatment.

Coagulation plays an important role in alleviating membrane fouling, and a noticeable problem is the development of microorganisms after long-time operation, which gradually secrete extracellular polymeric substances (EPS). To date, few studies have paid attention to the behavior of microorganisms in drinking water treatment with ultrafiltration (UF) membranes. Herein, the membrane biofouling was investigated with different aluminum and iron salts. We found that Al2(SO4)3·18H2O performed better in reducing membrane fouling due to the slower growth rate of microorganisms. In comparison to Al2(SO4)3·18H2O, more EPS were induced with Fe2(SO4)3·xH2O, both in the membrane tank and the sludge on the cake layer. We also found that bacteria were the major microorganisms, of which the concentration was much higher than those of fungi and archaea. Further analyses showed that Proteobacteria was dominant in bacterial communities, which caused severe membrane fouling by forming a biofilm, especially for Fe2(SO4)3·xH2O. Additionally, the abundances of Bacteroidetes and Verrucomicrobia were relatively higher in the presence of Al2(SO4)3·18H2O, resulting in less severe biofouling by effectively degrading the protein and polysaccharide in EPS. As a result, in terms of microorganism behaviors, Al-based salts should be given preference as coagulants during actual operations.

Dechlorination of Trichloroacetic Acid Using a Noble Metal-Free Graphene-Cu Foam Electrode via Direct Cathodic Reduction and Atomic H.

A three-dimensional graphene-copper (3D GR-Cu) foam electrode prepared by chemical vapor deposition method exhibited superior electrocatalytic activity toward the dechlorination of trichloroacetic acid (TCAA) as compared to the Cu foam electrode. The cyclic voltammetry and electrochemical impedance spectra analysis confirmed that GR accelerated the electron transfer from the cathode surface to TCAA. With the applied cathode potential of -1.2 V (vs SCE), 95.3% of TCAA (500 µg/L) was removed within 20 min at pH 6.8. TCAA dechlorination at the Cu foam electrode was enhanced at acidic pH, while a slight pH effect was observed at the GR-Cu foam electrode with a significant inhibition for Cu leaching. The electrocatalytic dechlorination of TCAA was accomplished via a combined stepwise and concerted pathway on both electrodes, whereas the concerted pathway was efficiently promoted on the GR-Cu foam electrode. The direct reduction by electrons was responsible for TCAA dechlorination at Cu foam electrode, while at GR-Cu foam electrode, the surface-adsorbed atomic H* also contributed to TCAA dechlorination owing to the chemical storage of hydrogen in the GR structure. Finally, the potential applicability of GR-Cu foam was revealed by its stability in the electrocatalytic dechlorination over 25 cycles.

Enhanced Electroreductive Removal of Bromate by a Supported Pd-In Bimetallic Catalyst: Kinetics and Mechanism Investigation.

In this work, the electroreductive removal of bromate by a Pd1-In4/Al2O3 catalyst in a three-dimensional electrochemical reactor was investigated. A total of 96.4% of bromate could be efficiently reduced and completely converted into bromide within 30 min under optimized conditions. On the basis of the characterization results and kinetics analysis, a synergistic effect of Pd and In was observed, and Pd1-In4/Al2O3 had the highest reaction rate constant of 0.1275 min-1 (vs 0.0413, 0.0328, and 0.0253 min-1 for In/Al2O3, Pd/Al2O3, and Al2O3). The results of electron spin resonance and scavenger experiments confirmed that both direct electron transfer and indirect reduction by atomic H* were involved in the bromate removal process, while the direct reduction played a more important role. Moreover, the introduction of In could increase the zeta potential of Pd1-In4/Al2O3, facilitating bromate adsorption and its subsequent reduction on the catalyst. Finally, a reaction mechanism for bromate reduction by Pd1-In4/Al2O3 was proposed based on all the experimental results.

Fabrication of FeOOH hollow microboxes for purification of heavy metal-contaminated water.

FeOOH, a frequently used adsorbent, has been widely applied in purifying aqueous heavy metals, and its performance can be greatly improved by enlarging the number of surface active sites. To this end, we fabricated FeOOH hollow microboxes constructed from numerous 2D nanosheets via a template-engaged reaction between Prussian blue (PB) and NaOH solution. With combined observations from X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), we confirmed that the hollow microboxes corroded from PB were composed of ample frizzy FeOOH nanosheets, which ensured extensive exposure of the surface active sites. Moreover, the FeOOH microboxes were utilized as an adsorbent in the removal of heavy metals (As(III), As(V) and Se(IV)) from water and the maximum adsorption capacities were reached up to 192.19 mg g(-1), 250.0 mg g(-1) and 169.9 mg g(-1) at pH = 7.0, 4.0 and 5.0, respectively. The superior adsorptive performance of the FeOOH microboxes was derived from their large content of reactive exposed hydroxyl groups, which was unambiguously confirmed by X-ray adsorption fine structure spectroscopy (XAFS), as well as by surface site density analysis.