Soil carbon and nitrogen cycles driven by iron redox: A review.

Soil carbon and nitrogen cycles affect agricultural production, environmental quality, and global climate. Iron (Fe), regarded as the most abundant redox-active metal element in the Earth's crust, is involved in a biogeochemical cycle that includes Fe(III) reduction and Fe(II) oxidation. The redox reactions of Fe can be linked to the carbon and nitrogen cycles in soil in various ways. Investigating the transformation processes and mechanisms of soil carbon and nitrogen species driven by Fe redox can provide theoretical guidance for improving soil fertility, and addressing global environmental pollution as well as climate change. Although the widespread occurrence of these coupling processes in soils has been revealed, explorations of the effects of Fe redox on soil carbon and nitrogen cycles remain in the early stages, particularly when considering the broader context of global climate and environmental changes. The key functional microorganisms, mechanisms, and contributions of these coupling processes to soil carbon and nitrogen cycles have not been fully elucidated. Here, we present a systematic review of the research progress on soil carbon and nitrogen cycles mediated by Fe redox, including the underlying reaction processes, the key microorganisms involved, the influencing factors, and their environmental significance. Finally, some unresolved issues and future perspectives are addressed. This knowledge expands our understanding of the interconnected cycles of Fe, carbon and nitrogen in soils.

Efficient removal of As(III) from groundwaters through self-alkalization in an asymmetric flow-electrode electrochemical separation system.

It remains a great challenge to efficiently remove As(III) from groundwater using traditional technologies due to its stable electroneutral form. This study constructed an asymmetric flow-electrode electrochemical separation (AFES) system, which overcomes the drawback of H+ release from anodic carbon oxidation and achieves continuous self-alkalization function and highly efficient removal of As(III) from groundwater. At the applied voltage of 1.2 V and initial pH 7.5, the system could rapidly decrease the total As (T-As) concentration from 150.0 to 8.9 µg L-1 within 90 min, with an energy consumption of 0.04 kWh m-3. The self-alkalization was triggered by the generation of H2O2 from dissolved oxygen reduction and the adsorption of H+ on the cathode in the feed chamber, which significantly promoted the dissociation and oxidation of As(III), resulting in the removal of T-As predominantly in the form of As(V). The removal performance of T-As was slightly affected by the initial pH and coexisting ions in the feed chamber. The AFES system also exhibited considerable stability after 20 cycles of continuous experiments and superior performance in treating As-containing real groundwater. Moreover, the pH of the alkalized solution can be restored to the initial level by standing or aeration operation. This work offers a novel and efficient pathway for the detoxication of As(III)-contaminated groundwaters.

High-efficiency electrochemical removal of Cd(II) from wastewater using birnessite-biochar composites: Performance and mechanism.

Birnessite has been widely used for electrochemical removal of heavy metals due to its high pseudocapacitance. Incorporation of carbon-based materials into birnessite can enhance its conductivity and stability, and synergistically improve the electrochemical adsorption capacity due to the double-layer capacitor reaction derived from carbon-based materials. In this study, biochar was successfully incorporated with birnessite at various ratios to synthesize composites (BC-Mn) for effective electrochemical removal of cadmium (Cd(II)) from water. The effects of cell voltage, initial pH, and recycling performance of BC-Mn were evaluated. As a result, the electrosorption capacity of BC-Mn for Cd(II) exhibited gradual increases with increasing birnessite content and reached equilibrium at a Mn content of 20% (BC-Mn20). The Cd(II) adsorption capacity of BC-Mn20 rose at higher cell voltage, and reached the maximum at 1.2 V. At pH 3.0-6.0, the electrosorption capacity initially rose until pH 5.0 and then approached equilibrium with a further increase in pH value. The Cd(II) electrochemical adsorption capacity of BC-Mn20 in the solution could reach 104.5 mg g-1 at pH 5.0 for 8 h at 1.2 V. Moreover, BC-Mn20 exhibited excellent reusability with a stability of 95.4% (99.7 mg g-1) after five cycles of reuse. Due to its superior heavy metal adsorption capacity and reusability, BC-Mn20 may have a promising prospect in the remediation of heavy metal polluted water.

Sustainable and reagent-free cathodic precipitation for high-efficiency removal of heavy metals from soil leachate.

Heavy metal pollution of soils has become a serious environmental problem. Soil washing with degradable reagents is an effective remediation technique of heavy metal pollution, and the generated leachate must be appropriately treated before discharge. However, the existing methods usually have the problems of large consumption of regents, high cost, and secondary pollution. This study proposed a reagent-free electrochemical precipitation method to remove mixed heavy metal ions extracted from soils by citrate using inert electrodes (IrO2-Ta2O5/Ti anode and graphite cathode). The results showed that the low potential of cathode led to the electrodeposition of Cd; the local alkaline environment provided by electro-mediated water reduction caused the hydrolytic precipitation of Zn and Pb; and the precipitation of Fe washed out from Fe-rich soil resulted in the coprecipitation of As on cathode surface. These combined cathodic precipitation processes decreased the concentrations of toxic heavy metals by over 99.4% after 12 h of electrolysis at 26 mA cm-2. The electrodes exhibited high stability after multiple successive cycles of reuse. The concentrations of As, Zn, Pb and Cd in the leachate decreased to below the limits of industrial wastewater discharge in each cycle, and those in soils could be reduced by 53.8%, 58.8%, 25.5%, and 70.2% at the initial concentrations of 1549, 1016, 310 and 50 mg kg-1, respectively. The heavy metal removal rate increased with increasing current density in the range of 0-52 mA cm-2. This work provides an efficient and sustainable method for the remediation of site soils polluted by mixed heavy metals.

Rapid photooxidation and removal of As(III) from drinking water using Fe-Mn composite oxide.

Fe-Mn composite oxide (FMO) is widely applied to the oxidation and removal of As(III) from water. However, As(III) can directly reduce manganese oxides, decreasing the oxidation capacity or reusability and thereby greatly limiting the applicability of FMO. Here, the oxidation capacity and reusability of FMO for As(III) were efficiently improved by light radiation, and the effect of typical coexisting ions (SO42- and Ca2+) on the removal of As(III) was also studied. O2•- produced from excited manganese oxide and ligand-to-metal charge transfer in iron oxide-As(III) complex enhanced As(III) oxidation and removal under light radiation. At an initial As(III) concentration of 1000 µg L-1, the total As concentration was respectively decreased to 11.5, 1.5 and 4.4 µg L-1 under darkness, UV light and sunlight at 180 min, and could be reduced to below the guideline limitation of drinking water (10 µg L-1) within 40 and 60 min under UV light and sunlight, respectively. SO42- exhibited negligible effect on As removal efficiency because FMO had obviously lower adsorption capacity and selectivity for SO42- than for As(V). The adsorption of coexisting Ca2+ on manganese oxide decreased the negative charge on the FMO surface, thereby improving As(III) adsorption and oxidation. FMO exhibited excellent reusability, and a total As removal efficiency of 99.1% was still maintained after five cycles of an adsorption-desorption process under UV light. This work elucidates the photochemical oxidation and removal mechanism of FMO for As(III), and proposes a low-cost and efficient method for the detoxification of As(III)-contaminated drinking water.

Resource utilization of rice husk biomass: Preparation of MgO flake-modified biochar for simultaneous removal of heavy metals from aqueous solution and polluted soil.

In general, the remediation performance of heavy metals can be further improved by metal-oxide modified biochar. This work used MgO-modified rice husk biochar (MgO-5%@RHB-450 and MgO-5%@RHB-600) with high surface activity for simultaneous remediation and removal of heavy metals in soil and wastewater. The adsorption of MgO-5%@RHB-450/MgO-5%@RHB-600 for Cd(II), Cu(II), Zn(II) and Cr(VI) followed the pseudo-second order, with the adsorption capacities reaching 91.13/104.68, 166.68/173.22, 80.12/104.38 and 38.88/47.02 mg g-1, respectively. The addition of 1.0% MgO-5%@RHB-450 and MgO-5%@RHB-600 could effectively decrease the CaCl2-extractable Cd concentration (CaCl2-Cd) by 66.2% and 70.0%, respectively. Moreover, MgO-5%@RHB-450 and MgO-5%@RHB-600 facilitated the transformation of exchangeable fractions to carbonate-bound and residual fractions, and reduced the exchangeable fractions by 8.1% and 9.6%, respectively. The mechanisms for the removal of heavy metals from wastewater by MgO-5%@RHB-450 and MgO-5%@RHB-600 mainly included complexation, ion exchange and precipitation, and the immobilization mechanisms in soil may be precipitation, complexation and pore filling. In general, this study provides high-efficiency functional materials for the remediation of heavy metal pollution.

Photooxidation of Fe(II) to schwertmannite promotes As(III) oxidation and immobilization on pyrite under acidic conditions.

Pollution of arsenic (As) in acid mine drainage (AMD) is a universal environmental problem. The weathering of pyrite (FeS2) and other sulfide minerals leads to the generation of AMD and accelerates the leaching of As from sulfide minerals. Pyrite can undergo adsorption and redox reactions with As, affecting the existing form and biotoxicity of As. However, the interaction process between As and pyrite in AMD under sunlight radiation remains unclear. Here, we found that the oxidation and immobilization of arsenite (As(III)) on pyrite can be obviously promoted by the reactive oxygen species (ROS) in sunlit AMD, particularly by OH. The reactions between hole-electron pairs and water/oxygen adsorbed on excited pyrite resulted in the production of H2O2, OH and O2-, and OH was also generated through the photo-Fenton reaction of Fe2+/FeOH2+. Weakly crystalline schwertmannite formed from the oxidation of Fe2+ ions by OH contributed much to the adsorption and immobilization of As. In the mixed system of pyrite (0.75 g L-1), Fe2+ (56.08 mg L-1) and As(III) (1.0 mg L-1) at initial pH 3.0, the decrease ratio of dissolved total As concentration was 1.6% under dark conditions, while it significantly increased to 69.0% under sunlight radiation. The existence of oxygen or increase in initial pH from 2.0 to 4.0 accelerated As(III) oxidation and immobilization due to the oxidation of more Fe2+ and production of more ROS. The present work shows that sunlight significantly affects the transformation and migration of As in AMD, and provides new insights into the environmental behaviors of As.

Combined remediation effects of biochar, zeolite and humus on Cd-contaminated weakly alkaline soils in wheat farmland.

Threats posed by Cd-contaminated arable soils to food security have attracted increasing attention. The combination of organic and inorganic amendments has been extensively applied to immobilize Cd in paddy soils. However, the regulatory mechanism of Cd fractionation under these combined amendments and the effect on wheat Cd accumulation remain unclear in upland soils. In this work, different combinations of organic and inorganic amendments were prepared with biochar, zeolite and humus, and the Cd-immobilization mechanism was also investigated in field experiments. The results demonstrated that the mixture of biochar, zeolite and humus had excellent Cd immobilization performance in highly Cd-contaminated (4.26 ± 1.25 mg kg-1) weakly alkaline soils, resulting in 76.5-84.8% decreases in soil available Cd. The contribution of single components to Cd immobilization in the combined amendment follows the order of humus > biochar > zeolite. The combined amendment converted the acid soluble Cd to the Cd bound to the reducible fraction with higher stability, thereby decreasing Cd bioavailability. The maximum Cd decrease rate in wheat roots, straw and grains could reach 68.2%, 45.0% and 59.3%, respectively, and the Cd content in grains (0.098 mg kg-1) was lower than the food security standards of China (0.1 mg kg-1). Wheat planting for two successive years in a large-scale field further verified the superior Cd immobilization performance and stability of the combined amendment in moderately to slightly Cd-contaminated soil. The present study provides references for the remediation of Cd-contaminated weakly alkaline upland soils and certain guidance for safe food production.

UV-induced highly efficient removal of As(III) through synergistic photo-oxidation in the presence of Fe(II).

In polluted waters, arsenic (As) poses substantial risks to the environment and human health. Inorganic As mainly exists as As(V) and As(III), and As(III) usually shows higher mobility and toxicity and is more difficult to be removed by coagulation. The oxidation of coexisting Fe(II) can accelerate As(III) oxidation and removal by promoting the generation of reactive intermediates and Fe(III) coagulant in the presence of dissolved oxygen. However, the removal efficiency of As from acidic wastewaters is far from satisfactory due to the low Fe(II) oxidation rate by dissolved oxygen. Herein, UV irradiation was applied to stimulate the synergistic oxidation of Fe(II)/As(III), and the effects of coexisting Fe(II) concentration and pH were also evaluated. The synergistic oxidation of Fe(II)/As(III) significantly enhanced the removal of As from acidic waters. Under UV irradiation, Fe(II) significantly promoted the generation of reactive oxygen species (ROS), thereby facilitating As(III) oxidation. In addition, the formation of ferric arsenate and amorphous ferric (hydr)oxides contributed much to As removal. In the As(III)-containing solution with 200 µmol L-1 Fe(II) at initial pH 4.0, the total arsenic (As(T)) concentration decreased from 67.0 to 1.3 and 0.5 µmol L-1, respectively, at 25 and 120 min under UV irradiation. The As(T) removal rate increased with increasing Fe(II) concentration, and first increased and then decreased with increasing initial pH from 2.0 to 6.0. This study clarifies the mechanism for the synergistic photo-oxidation of Fe(II)/As(III) under UV irradiation, and proposes a new strategy for highly efficient As(III) removal from acidic industrial and mining wastewaters.

Preparation, adsorption performance and mechanism of MgO-loaded biochar in wastewater treatment: A review.

Biochar is a low cost, porous and solid material with an extremely high carbon content, various types of functional groups, a large specific surface area and many other desirable characteristics. Thus, it is often used as an adsorbent or a loading matrix. Nano-magnesium oxide is a crystalline material with small particles and strong ion exchangeability. However, due to the high surface chemical energy, it easily forms agglomerates of particles. Therefore, to combine the advantages of biochar and magnesium, metal magnesium nanoparticles can be loaded onto the surface of biochar with different modification techniques, resulting in biochars with low cost and high adsorption performance to be used as an adsorption matrix (collectively referred to as Mg@BC). This review presents the effects of different Mg@BC preparation methods and synthesis conditions and summarizes the removal capabilities and adsorption mechanisms of Mg@BC for different types of pollutants in water. In addition, the review proposes the prospects for the development of Mg@BC to solve various problems in the future.

Sulfate-accelerated photochemical oxidation of arsenopyrite in acidic systems under oxic conditions: Formation and function of schwertmannite.

The weathering of arsenopyrite is closely related to the generation of acid mine drainage (AMD) and arsenic (As) pollution. Solar radiation can accelerate arsenopyrite oxidation, but little is known about the further effect of SO42- on the photochemical process. Here, the photooxidation of arsenopyrite was investigated in the presence of SO42- in simulated AMD environments, and the effects of SO42- concentration, pH and dissolved oxygen on arsenopyrite oxidation were studied as well. SO42- could accelerate the photooxidation of arsenopyrite and As(III) through complexation between nascent schwertmannite and As(III). Fe(II) released from arsenopyrite was oxidized to form schwertmannite in the presence of SO42-, and the photooxidation of arsenopyrite occurred through the ligand-to-metal charge-transfer process in schwertmannite-As(III) complex along with the formation of reactive oxygen species in the presence of O2. The photooxidation rate of arsenopyrite first rose and then fell with increasing SO42- concentration. In the pH range of 2.0-4.0, the photooxidation rate of arsenopyrite progressively increased in the presence of SO42-. This study reveals how SO42- promotes the photooxidation of arsenopyrite and As release in the AMD environment, and improves the understanding of the transformation and migration of As in mining areas.

Removal of As(V) from wastewaters using magnetic iron oxides formed by zero-valent iron electrocoagulation.

Electrocoagulation of zero-valent iron has been widely applied to the removal of dissolved arsenic, but the solid-liquid separation of arsenic-containing precipitates remains technically challenging. In this work, zero-valent iron was electrochemically oxidized to magnetic iron oxides for the removal of As(Ⅴ) from simulated and actual mining wastewaters. The results indicated that lepidocrocite was formed when zero-valent iron was oxidized by dissolved oxygen, but ferrihydrite and green rust were first formed and then transformed to magnetic iron oxides (mainly magnetite and maghemite) in the electrochemical oxidation from 0 to 0.9 V (vs. SCE), which facilitates the adsorption of As(V) and subsequent solid-liquid separation under a magnetic field. In simulated As(V)-containing solution with initial pH 7.0, zero-valent iron was electrochemically oxidized to magnetite and maghemite at 0.6 V (vs. SCE) for 2 h. The As(V) concentration first decreased from 5127.5 to 26.8 µg L-1 with a removal ratio of 99.5%. In actual mining wastewaters, zero-valent iron was electrochemically oxidized to maghemite at 0.6 V (vs. SCE) for 24 h, and the As(V) concentration decreased from 5486.4 to 3.6 µg L-1 with a removal ratio of 99.9%. The removal ratio of As(V) increased slightly with increasing potential, and increased first and then decreased with increasing initial pH. Compared with that of SO42- and NO3-, the presence of Cl- significantly enhanced the removal of As(V). This work provides a highly efficient, facile and low-cost technique for the treatment of arsenic-containing wastewaters.

Remediation of As-contaminated soils using citrate extraction coupled with electrochemical removal.

Arsenic (As) pollution of soils poses serious threats to the ecological environment. In this study, organic acid (citrate) washing and electrochemical removal (manganese oxide cathode) were combined to remediate highly As-contaminated soils, and the effect of voltage was investigated as well. Citrate could extract the As bound to iron and aluminum oxides and enhance As mobility by indirectly reducing As(V) to As(III) in the soils. During the electrochemical removal of As, the rhodochrosite produced from the reduction of birnessite at the cathode, the birnessite generated from the re-oxidation of released Mn(II) and the ferrihydrite formed from the hydrolysis of Fe(III) at the anode together contributed to the adsorption and fixation of As in the leachate. After three successive rounds of combined remediation by citrate (0.1 mol L-1) washing and electrochemical removal with birnessite electrode at 1.5 V, the As was totally removed in the leachate and the content of As bound to iron and aluminum (hydr)oxides was reduced by 84.2% in soils. Correspondingly, the contents of total and bioavailable As in the soil decreased from 1981.4 and 242.0 to 563.2 and 86.0 mg kg-1, respectively. The As removal efficiency from the leachate and soil increased with increasing voltage from 0 to 1.5 V. This study provides a new method for the effective treatment of As-contaminated soils.

Electrosorption of cadmium and arsenic from wastewaters using nitrogen-doped biochar: Mechanism and application.

Biochar has been widely applied as an adsorbent, whose electrochemical capacity and heavy metal adsorption performance can be improved by nitrogen doping. In this work, nitrogen-doped biochar (NBC) was synthesized by calcinating sodium humate with sodium bicarbonate (NaHCO3) and urea as the activation agent and nitrogen source, respectively. The NBC was then used to electrochemically adsorb Cd(II) and As(III,V) from simulated and actual wastewaters, respectively. The results indicated that NaHCO3 activation and nitrogen doping could increase the surface area and nitrogen content of the biochar, contributing to the enhancement of adsorption performance for Cd(II) and As(III,V). The electrosorption capacities for Cd(II) and total arsenic (As(T)) increased first and then reached equilibrium with increasing nitrogen content, increased first and then decreased with increasing calcination temperature, and consistently increased with increasing voltage. The Cd(II) electrosorption capacity (79.0 mg g-1) and As(T) removal ratio (94.0%) at 1.2 V in actual As-contaminated wastewater (1.16 mg L-1) were about 4 and 2.6 folds of their inorganic adsorption capacities, respectively. After five cycles of reuse, the Cd(II) and As(T) removal ratio could be maintained at 65.8% and 51.7% of the initial electrosorption capacity. This work expands the application of NBC for heavy metal removal.

Removal of heavy metals from wastewaters with biochar pyrolyzed from MgAl-layered double hydroxide-coated rice husk: Mechanism and application.

This study reports a MgAl-LDH rice husk biochar composite (MgAl-LDH@RHB) with a regular hydrotalcite structure synthesized by a simple hydrothermal method, which was then used to remove Cd(II) and Cu(II) from water. The influencing factors on the adsorption performance were determined through batch adsorption experiments, and the adsorption characteristics and cycling capacity were evaluated with eight models and adsorption-desorption experiments. The results showed that the adsorption of Cd(II) and Cu(II) by MgAl-LDH@RHB conformed to the Langmuir-Freundlich model and PSO kinetics model, indicating single-layer chemical adsorption. In addition, the experimental maximum adsorption capacities for Cd(II) and Cu(II) were 125.34 and 104.34 mg g-1, respectively. The adsorption of Cd(II) and Cu(II) by MgAl-LDH@RHB was dominated by surface precipitation and ion exchange. The findings reveal the mechanism for the heavy metal removal by MgAl-LDH@RHB and provide a theoretical reference for agricultural waste disposal and water pollution control.

Solar irradiation induced oxidation and adsorption of arsenite on natural pyrite.

The migration and bioavailability of toxic elemental arsenic (As) are influenced by the adsorption and redox processes of sulfide minerals in waters around mining areas. Pyrite is the most abundant sulfide mineral in the Earth's crust and exhibits certain photochemical activity. However, the adsorption and redox behaviors of arsenite (As(III)) on pyrite surface under solar irradiation remain unclear. Here, the interaction between As(III) and natural pyrite was investigated under light irradiation. The results indicated that solar irradiation promotes As(III) oxidation and adsorption on pyrite surface due to reactive oxygen species (ROS) intermediates. The reactions between H2O/O2 and hole-electron pairs (hvb+-ecb-) on excited pyrite and the oxidation of Fe2+ released from pyrite by dissolved O2 contributed much to the generation of OH•, O2•- and H2O2 under light irradiation. ROS production and As(III) oxidation were accelerated by dissolved O2. An increase in pH within 5.0 to 9.0 decreased the concentration of OH• but increased that of H2O2 and the amount of oxidized As(III). In weakly acidic and neutral environments, OH• was mainly responsible for As(III) oxidation, while H2O2 contributed much to As(III) oxidation in weakly alkaline environments. Partial arsenate (As(V)) was adsorbed on pyrite and newly formed ferrihydrite. The present work enriches the understanding of As migration and transformation in the waters around mining areas, and provides a potential method for As(III) removal by using pyrite under solar irradiation.

Synergistic oxidation of dissolved As(III) and arsenopyrite in the presence of oxygen: Formation and function of reactive oxygen species.

As an important source of arsenic (As) pollution in mine drainage, arsenopyrite undergoes redox and adsorption reactions with dissolved As, which further affects the fate of As in natural waters. This study investigated the interactions between dissolved As(III) and arsenopyrite and the factors influencing the geochemical behavior of As, including initial As(III) concentration, dissolved oxygen and pH. The hydrogen peroxide (H2O2) and hydroxyl radical (OH•) generated from the interaction between Fe(II) on arsenopyrite surface and oxygen were found to facilitate the rapid oxidation of As(III), and the production of As(V) in the reaction system increased with increasing initial As(III) concentration. An increase of pH from 3.0 to 7.0 led to a gradual decrease in the oxidation rate of As(III). At pH 3.0, the presence of As(III) accelerated the oxidation rate of arsenopyrite; while at pH 5.0 and 7.0, As(III) inhibited the oxidative dissolution of arsenopyrite. This work reveals the potential environmental process of the interaction between dissolved As(III) and arsenopyrite, and provides important implications for the prevention and control of As(III) pollution in mine drainage.

Zeolite-supported manganese oxides decrease the Cd uptake of wheat plants in Cd-contaminated weakly alkaline arable soils.

Cd pollution in arable soils has posed serious threats to food safety and human health. Mn oxides and Mn oxide-based materials have been widely applied to the removal of heavy metals for their high adsorption capacity, especially in water treatment. However, the performance and stability of Mn oxide-based materials and the underlying mechanism of Cd immobilization in upland soils remain unclear. Here, zeolite-supported Mn oxides were used as amendment to investigate their impact on the availability of soil Cd in wheat pot experiments. The decrease in soil available Cd content (by 44.3%) and increase in soil available Mn content (by 61.9%) significantly inhibited Cd accumulation in wheat plant tissues under the application of zeolite-supported Mn oxides. The exchangeable Cd was transformed to more stable fractionation of Fe-Mn oxide bound Cd, and the maximum decrease of Cd content in wheat grains, straw and roots reached 65.0%, 11.7% and 55.3%, respectively. Besides, zeolite-supported Mn oxides exhibited high chemical stability and stable Cd immobilization performance in two successive years of wheat pot experiments. These findings improve our understanding of Mn oxide-based materials for soil remediation and indicate that zeolite-supported Mn oxides have great potential for the remediation of Cd-contaminated alkaline upland soils.

Oxygen vacancy-rich hierarchical BiOBr hollow microspheres with dramatic CO2 photoreduction activity.

Conversion of carbon dioxide into useful chemicals has attracted great attention. However, the significant bottlenecks facing in the field are the poor conversion efficiency of CO2 and low selectivity of products. Herein, hierarchical BiOBr hollow microspheres are fabricated by a solvothermal method using ethylene glycol (EG) as solvent in presence of polyvinyl pyrrolidone (PVP). The hollow BiOBr microspheres prepared at 120 °C exhibit the best performance for CO2 photoreduction. The evolution rates of product CO and CH4 are up to 88.1 µmol g-1h-1 and 5.8 µmol g-1h-1, which are 8.8 times and 5.8 times higher than that of plate-like BiOBr respectively. The hollow microspheres possess larger specific area and generate multiple reflections of light in the cavity, thus enhancing the utilization efficiency of light. The modulated electronic structure by oxygen vacancy (OVs) is beneficial to the transfer of photogenerated electrons and holes. Especially, the enriched charge density of BiOBr by OVs is conductive to the adsorption and activation of CO2, which could lower the overall activation energy barrier of CO2 photoreduction. In summary, the synergistic effect of the hollow structure with OVs plays a vital role in boosting the photoreduction of CO2 for BiOBr. This work provides a new opportunity for designing the high efficiency catalyst by morphology engineering with defects at the atomic level for CO2 photoreduction.

Arsenic detoxification by iron-manganese nodules under electrochemically controlled redox: Mechanism and application.

Iron-manganese binary oxides are characterized by high oxidation and adsorption capability and widely applied to arsenic (As) detoxification in contaminated waters. Despite of their lower preparation cost relative to synthesized iron-manganese binary oxides, the low adsorption capacity of natural iron-manganese oxides largely hinders their application. Here, electrochemically controlled redox was employed to improve the As(III,V) removal performance of iron-manganese nodules in a symmetric electrode system, and the removal mechanism and electrode reusability were also examined. Experimental results showed that both the electrochemical reduction and oxidation of birnessite in iron-manganese nodules contributed much to As(III,V) removal. Higher cell voltage facilitated a higher removal efficiency of total As within 0-1.2 V, which reached 94.7% at 1.2 V for actual As-containing wastewater (4068 µg L-1). The efficiency was obviously higher than that at open circuit (81.4%). Under electrode polarity reversal, the alternating reduction dissolution and oxidation recrystallization of birnessite in iron-manganese nodules promoted their contact with As, enhancing the total As removal efficiency from 75.6% to 91.8% after five times of repeated adsorption. This research clarifies the effect of electrochemical redox on As(III,V) detoxification by iron-manganese oxides, and expands the application of natural iron-manganese nodules in the treatment of As-contaminated wastewaters.