Directional Separation of Highly Reductive Electrons to the Reactive Center in a Magnetic S-Scheme ZnFe2O4/A-MoS2 Heterojunction for Enhanced Peroxymonosulfate Activation toward Pharmaceuticals and Personal Care Product Removal.

Pharmaceuticals and personal care products (PPCPs) are ubiquitous in sewage, adversely affecting ecosystems and human health. In this study, an S-scheme magnetic ZnFe2O4/ammoniated MoS2 (ZnFe2O4/A-MoS2) heterojunction as a visible-light-driven PMS activator for PPCP degradation was developed. ZnFe2O4/A-MoS2 achieves improved photocatalytic activity because the construction of S-scheme heterojunction promotes the separation of the highly reductive photogenerated electrons. The optimized photocatalyst (10%-ZnFe2O4/A-MoS2, 0.2 g/L) achieved 100% removal of 2 ppm carbamazepine (CBZ) within 2.5 min at a PMS dosage of 0.5 mM (initial pH 7.0). Mechanistic investigation revealed that the separated electrons to the ZnFe2O4 reactive center of the heterojunction facilitated PMS activation and generated SO4·- as the dominant reactive species for CBZ degradation. The system exhibited excellent practicability in various samples of actual sewage, where most sewage components negatively impacted CBZ degradation. Further, the chloride ions in high-salinity sewage could be activated to generate additional reactive chlorine species for PPCP degradation. The heterojunction possesses outstanding reusability and stability in treating various water conditions. This work provides mechanistic and practical perspectives in developing novel S-type heterojunctions for recalcitrant pollutant treatment.

Immobilization of heavy metals in biochar by co-pyrolysis of sludge and CaSiO3.

Sludge pyrolysis has become an important method of sludge recycling. Stabilizing heavy metals in sludge is key to sludge recycling. Currently, research on the co-pyrolysis of sludge and industrial waste is limited. This study aims to explore the impact and mechanism of the co-pyrolysis of sludge and CaSiO3 (the main component of slag) and to achieve the concept of "treating waste with waste". To this end, we added different proportions of CaSiO3 (0%, 3%, 6%, 9%, 12%, and 15%) for the co-pyrolysis with sludge, and varied the pyrolysis temperatures (300, 400, 500, 600, and 700 °C) and retention times (15, 30, 60, and 120 min) to study heavy-metal stabilization in sludge. Consequently, the optimum dosage of CaSiO3 required for the immobilization of different heavy metals was 9% (Cu, Zn, Pb, and Cr) and 15% (Ni). The contents of Cu, Zn, Pb, Cr, and Ni in the stable state (oxidized and residual states) were 92.73%, 79.23%, 99.55%, 92.43% and 90.33% respectively. At a pyrolysis temperature of 700 °C, the steady-state proportions of Cr, Pb, and Zn were 88.12%, 90.21%, and 77.21%, respectively. At a pyrolysis temperature of 400 °C, the stable-Cu and -Ni contents were 97.21% and 99.43%, respectively. The optimal dwelling time was 15 min. The results showed that the CaSiO3 addition weakened the O-H stretching vibration peak intensity, promoted the formation of aromatic and epoxy ring structures, and enhanced the heavy-metal immobilization. Furthermore, the CaSiO3 decomposition during co-pyrolysis produced SiO2, CaO, and Ca(OH)2, which helped stabilize heavy metals.

In Situ Confined Synthesis of a Copper-Encapsulated Silicalite-1 Zeolite for Highly Efficient Iodine Capture.

Effective capture of radioactive iodine is highly desirable for decontamination purposes in spent fuel reprocessing. Cu-based adsorbents with a low cost and high chemical affinity for I2 molecules act as a decent candidate for iodine elimination, but the low utilization and stability remain a significant challenge. Herein, a facile in situ confined synthesis strategy is developed to design and synthesize a copper-encapsulated flaky silicalite-1 (Cu@FSL-1) zeolite with a thickness of ≤300 nm. The maximum iodine uptake capacity of Cu@FSL-1 can reach 625 mg g-1 within 45 min, which is 2 times higher than that of a commercial silver-exchanged zeolite even after nitric acid and NOX treatment. The Cu nanoparticles (NPs) confined within the zeolite exert superior iodine adsorption and immobilization properties as well as high stability and fast adsorption kinetics endowed by the all-silica zeolite matrix. This study provides new insight into the design and controlled synthesis of zeolite-confined metal adsorbents for efficient iodine capture from gaseous radioactive streams.

Co-pyrolysis of sewage sludge and Ca(H2PO4)2: heavy metal stabilization, mechanism, and toxic leaching.

The presence of unstable heavy metals in sewage sludge (SS) restricts its resource utilization. In this study, Ca(H2PO4)2 and SS were co-pyrolyzed to produce biochar, which contained relatively stable heavy metals. X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and inductively coupled plasma atomic emission techniques were used to analyze the physical and chemical properties and heavy metal content of the biochar. The results indicated that co-pyrolysis of SS with Ca(H2PO4)2 resulted in the production of more stable heavy metals in the SS. The optimal co-pyrolysis conditions were a blended ratio of 15% Ca(H2PO4)2, 650 °C final temperature, 15 °C min-1, and 60 min retention time. The potential stabilization mechanisms of heavy metals were as follows: (1) organic decomposition and moisture (sourced from Ca(H2PO4)2 decomposition) evaporation resulted in greater biochar surface porosity; (2) phosphorous substances were complexed with heavy metals to form metal phosphates; and (3) the mixture reactions among inorganic substances, pyrolysis products of organics, and heavy metals resulted in the formation of highly aromatic metallic compounds. Additionally, the potential environmental risks posed by the heavy metals decreased from 65.73 (in SS) to 4.39 (in biochar derived from co-pyrolysis of SS and 15% of Ca(H2PO4)2). This study reports on a good approach for the disposal of SS and the reduction of its environmental risk.

Toward an Understanding of Fundamentals Governing the Elemental Mercury Sequestration by Metal Chalcogenides.

The lack of fundamental understanding of the chemistry governing elemental mercury (Hg0) immobilization over metal chalcogenides (MChals) is the key challenge impeding the interpretations of Hg0 behaviors in global cycles. This work therefore made the first endeavor toward the establishment of a roadmap capable of describing and depicting Hg0 sequestrations by various MChals. The results suggest that the binding energy between the metal cations and chalcogen anions is a proper descriptor that could predict the immobilization behaviors of Hg0 over zinc chalcogenides (ZnS and ZnSe) that exhibit an identical molecular structure, i.e., the lower the binding energy was, the higher the Hg0 sequestration performance that was obtained. The validity of this descriptor was further demonstrated over a series of MChals sharing structural similarities. A scaling relationship was thus established, which further proved the Hg0 immobilization performance of MChals was generally in reverse proportion to the above-mentioned binding energy. Although there is still a long way toward the proposal of a full roadmap that can predict and depict the Hg0 immobilization behaviors over all MChals, this work marks the first step on this road and provides guides for further studies by understanding the fundamentals governing Hg0 sequestration over MChals with structural similarities.

Pb Stabilization by a New Chemically Durable Orthophosphate Phase: Insights into the Molecular Mechanism with X-ray Structural Analysis.

The rapid progression of piezoelectric technology and the upgradation of electronic devices have resulted in a global increase in Pb-based piezoelectric ceramic materials. In this study, the feasibility of incorporating Pb into a PbZr(PO4)2 double orthophosphate structure was evaluated by investigating the interaction mechanism of the perovskite with phosphate. The unique combination of X-ray absorption spectroscopy, selected area electronic diffraction, and Pawley refinement revealed that Pb was incorporated into a hexagonal structure and tetra-coordinated with oxygen in the phosphate-treated product. The chemical durability was enhanced through the structural alterations via Zr-O-P and Pb-O-P bond linkages. The stable phase encapsulating both Pb and phosphate showed effectiveness not only in stabilizing Pb but also in inhibiting P release as a secondary pollution risk within a wide pH range (1 ≤ pH ≤ 13). Despite the excellent chemical durability of the robust PbZr(PO4)2 crystalline phase, the increased Ti doping amounts at the Zr site resulted in a slight decrease in the lattice parameters and further enhanced the Pb stabilization effect through the formation of PbZrxTi(1-x)(PO4)2 solid solutions. This study demonstrates that the newly robust crystalline structure, developed through a well-designed thermal treatment scheme, provides an effective strategy for the treatment of Pb frequently encountered in electronic wastes.

Unraveling the Structure of the Poly(triazine imide)/LiCl Photocatalyst: Cooperation of Facile Syntheses and a Low-Temperature Synchrotron Approach.

Graphitic carbon nitride (g-C3N4)-based materials have attracted interdisciplinary attention from many fields. However, their crystal structures have not yet been described well. Poly(triazine imide)/LiCl (PTI/LiCl) of good crystallinity synthesized from salt melts enables a confident structural solution for a better understanding of g-C3N4-based materials. In this study, we synthesize PTI/LiCl of high crystallinity in air without byproducts and confirm the orthorhombic feature, which is not observed in powder X-ray diffraction (PXRD) patterns at room temperature, by employing low-temperature synchrotron PXRD. Together with spectroscopic techniques (X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and Fourier-transform infrared/Raman), the orthorhombic structure (space group Cmc21, No. 36) was determined and found to be a superstructure of the previously reported hexagonal structure, as confirmed by electron diffraction. The temperature-dependent synchrotron PXRD data also reveal a highly anisotropic expansion. This work also shows the much higher activity of PTI/LiCl than of g-C3N4 for the photocatalytic degradation of methyl orange under ultraviolet irradiation, especially so for PTI/LiCl with a densely packed (001) plane. This study demonstrates the structural complexity of the g-C3N4 class of materials and illustrates how their temperature-dependent anisotropies facilitate the discovery of the structural features in resolving the structure of g-C3N4-related materials and their structure-property relationship.

Role of Sulfur Trioxide (SO3) in Gas-Phase Elemental Mercury Immobilization by Mineral Sulfide.

Mineral sulfide based sorbents were superior alternatives to traditional activated carbons for elemental mercury (Hg0) immobilization in industrial flue gas. A systematical study concerning the influence of sulfur trioxide (SO3) on Hg0 adsorption over a nanosized copper sulfide (Nano-CuS) was for the first time conducted. SO3 was found to significantly inhibit the Hg0 removal over Nano-CuS partially because SO3 oxidized the reduced sulfur species (sulfide) with high affinity to mercury to its oxidized sulfur species (sulfate). Moreover, a brand new "oxidation-reduction" mechanism that led to a simultaneous oxidation of sulfide and reduction of mercury on the immobilized mercury sulfide (HgS) was responsible for the inhibitory effect. Even though the released Hg0 from the reduction of mercury in HgS could be oxidized by SO3 into its sulfate form (HgSO4) and recaptured by the sorbent, the "oxidation-reduction" mechanism still compromised the Hg0 capture performance of the Nano-CuS because HgSO4 deposited on the sorbent surface could be easily leached out when environmentally exposed. These new insights into the role of SO3 in Hg0 capture over Nano-CuS can help to determine possible solutions and facilitate the application of mineral sulfide sorbents as outstanding alternatives to activated carbons for Hg0 immobilization in industrial flue gas.

Recoverable impacts of ocean acidification on the tubeworm, Hydroides elegans: implication for biofouling in future coastal oceans.

Ocean uptake of anthropogenic CO2 causes ocean acidification (OA), which not only decreases the calcification rate, but also impairs the formation of calcareous shells or tubes in marine invertebrates such as the dominant biofouling tubeworm species, Hydroides elegans. This study examined the ability of tubeworms to resume normal tube calcification when returned to ambient pH 8.1 from a projected near-future OA level of pH 7.8. Tubeworms produced structurally impaired and mechanically weaker calcareous tubes at pH 7.8 compared to at pH 8.1, but were able to recover when the pH was restored to ambient levels. This suggests that tubeworms can physiologically recover from the impacts of OA on tube calcification, composition, density, hardness and stiffness when returned to optimal conditions. These results help understanding of the progression of biofouling communities dominated by tubeworms in future oceans with low pH induced by OA.

Multiform Sulfur Adsorption Centers and Copper-Terminated Active Sites of Nano-CuS for Efficient Elemental Mercury Capture from Coal Combustion Flue Gas.

Nanostructured copper sulfide synthesized with the assistance of surfactant with nanoscale particle size and high Brunauer-Emmett-Teller surface area was for the first time applied for the capture of elemental mercury (Hg0) from coal combustion flue gas. The optimal operation temperature of nano-CuS for Hg0 adsorption is 75 °C, which indicates that injection of the sorbent between the wet flue gas desulfurization and the wet electrostatic precipitator systems is feasible. This assures that the sorbent is free of the adverse influence of nitrogen oxides. Oxygen (O2) and sulfur dioxide exerted a slight influence on Hg0 adsorption over the nano-CuS. Water vapor was shown to moderately suppress Hg0 capture efficiency via competitive adsorption. The simulated adsorption capacities of nano-CuS for Hg0 under pure nitrogen (N2), N2 + 4% O2, and simulated flue gas reached 122.40, 112.06, and 89.43 mgHg0/g nano-CuS, respectively. Compared to those of traditional commercial activated carbons and metal sulfides, the simulated adsorption capacities of Hg0 over the nano-CuS are at least an order of magnitude higher. Moreover, with only 5 mg loaded in a fixed-bed reactor, the Hg0 adsorption rate reached 11.93-13.56 µg/g min over nano-CuS. This extremely speedy rate makes nano-CuS promising for a future sorbent injection technique. The anisotropic growth of nano-CuS was confirmed by X-ray diffraction analysis and provided a fundamental aspect for nano-CuS surface reconstruction and polysulfide formation. Further X-ray photoelectron spectroscopy and Hg0 temperature-programmed desorption tests showed that the active polysulfide, S-S dimers, and copper-terminated sites contributed primarily to the extremely high Hg0 adsorption capacity and rate. With these advantages, nano-CuS appears to be a highly promising alternative to traditional sorbents for Hg0 capture from coal combustion flue gas.

Dual Roles of Nano-Sulfide in Efficient Removal of Elemental Mercury from Coal Combustion Flue Gas within a Wide Temperature Range.

Nanostructured zinc sulfide (Nano-ZnS) has been demonstrated to be an efficient adsorbent for removal of elemental mercury (Hg0). However, the Hg0 removal performance deteriorates once the flue gas temperature deviates from the optimal temperature of 180 °C. In this study, ultraviolet (UV) light, which is generally generated through corona discharge in electrostatic precipitators (ESPs), was adopted to enhance Hg0 removal by Nano-ZnS. With the UV irradiation, Nano-ZnS exhibited excellent performance in Hg0 removal within a much wide temperature range from room temperature to 240 °C. A Hg0 removal efficiency of 99% was achieved at 60 °C even under extremely adverse conditions, that is, gas flow with an extremely high gas hourly space velocity but without hydrogen chloride. At low temperatures, Hg0 was mainly oxidized by superoxide radicals (•O2-) and hydroxyl radicals (•OH) generated by UV photostimulation to form mercuric oxide (HgO). At high temperatures, most Hg0 was immobilized as mercuric sulfide (HgS), as both the enhanced chemisorption and the accelerated transformation of HgO to HgS facilitated the formation of HgS. Compared with commercial activated carbon, injection of Nano-ZnS can utilize the UV in ESPs to warrant a higher Hg0 removal efficiency within a much wider temperature range.

Incorporation of Cadmium and Nickel into Ferrite Spinel Solid Solution: X-ray Diffraction and X-ray Absorption Fine Structure Analyses.

The feasibility of incorporating Cd and Ni in hematite was studied by investigating the interaction mechanism for the formation of CdxNi1-xFe2O4 solid solutions (CNFs) from CdO, NiO, and α-Fe2O3. X-ray diffraction results showed that the CNFs crystallized into spinel structures with increasing lattice parameters as the Cd content in the precursors was increased. Cd2+ ions were found to occupy the tetrahedral sites, as evidenced by Rietveld refinement and extended X-ray absorption fine structure analyses. The incorporation of Cd and Ni into ferrite spinel solid solution strongly relied on the processing parameters. The incorporation of Cd and Ni into the CNFs was greater at high x values (0.7 < x ≤ 1.0) than at low x values (0.0 ≤ x ≤ 0.7). A feasible treatment technique based on the investigated mechanism of CNF formation was developed, involving thermal treatment of waste sludge containing Cd and Ni. Both of these metals in the waste sludge were successfully incorporated into a ferrite spinel solid solution, and the concentrations of leached Cd and Ni from this solid solution were substantially reduced, stabilizing at low levels. This research offers a highly promising approach for treating the Cd and Ni content frequently encountered in electronic waste and its treatment residues.

Quantification of the Partitioning Ratio of Minor Actinide Surrogates between Zirconolite and Glass in Glass-Ceramic for Nuclear Waste Disposal.

Zirconolite-based glass-ceramic is considered a promising wasteform for conditioning minor actinide-rich nuclear wastes. Recent studies on this wasteform have sought to enhance the partitioning ratio (PR) of minor actinides in zirconolite crystal. To optimize the PR in the SiO2-Al2O3-CaO-TiO2-ZrO2 system, a novel conceptual approach, which can be derived from the chemical composition and quantity of zirconolite crystal in glass-ceramic, was introduced based on the results of Rietveld quantitative X-ray diffraction analysis and transmission electron microscopy energy dispersive X-ray spectroscopy. To verify this new conceptual approach, the influences of the crystallization temperature, the concentration of additives, and ionic radii on the PR of various surrogates (Ce, Nd, Gd, and Yb) in zirconolite were examined. The results reveal that the PR of Nd3+ in zirconolite can be as high as 41%, but it decreases as the crystallization temperature increases. The quantities of all phases (including crystalline and amorphous) remained nearly constant when increasing the loading of Nd2O3 in glass-ceramic products crystallized at 1050 °C for 2 h. Correspondingly, the PR of Nd3+ decreases in a linear fashion with the loading contents of Nd2O3. The radius of ions also has a great influence on the PR, and an increase in the ionic radius leads to a decrease in the PR. This new approach will be an important tool to facilitate the exploration of a glass-ceramic matrix for the disposal of minor actinide-rich nuclear wastes.

Graphene-oxide-wrapped ZnMn2O4 as a high performance lithium-ion battery anode.

Cation distribution between tetrahedral and octahedral sites within the ZnMn2O4 spinel lattice, along with microstructural features, is affected greatly by the temperature of heat treatment. Inversion parameters can easily be tuned, from 5%-19%, depending on the annealing temperature. The upper limit of inversion is found for T = 400 °C as confirmed by x-ray powder diffraction and Raman spectroscopy. Excellent battery behavior is found for samples annealed at lower temperatures; after 500 cycles the specific capacity for as-prepared ZnMn2O4 is 909 mAh g-1, while ZnMn2O4 heat-treated at 300 °C is 1179 mAh g-1, which amounts to 101% of its initial capacity. Despite the excellent performance of a sample processed at 300 °C at lower charge/discharge rates (100 mAh g-1), a drop in the specific capacity is observed with rate increase. This issue is solved by graphene-oxide wrapping: the specific capacity obtained after the 400th cycle for graphene-oxide-wrapped ZnMn2O4 heat-treated at 300 °C is 799 mAh g-1 at a charge/discharge rate 0.5 A g-1, which is higher by a factor of 6 compared to samples without graphene -oxide wrapping.

Rapid Selective Circumneutral Degradation of Phenolic Pollutants Using Peroxymonosulfate-Iodide Metal-Free Oxidation: Role of Iodine Atoms.

The development of environmentally friendly, oxidation-selective advanced oxidation processes (AOPs) for water decontamination is important for resource recovery, carbon dioxide abatement, and cost savings. In this study, we developed an innovative AOP using a combination of peroxymonosulfate (PMS) and iodide ions (I-) for the selective removal of phenolic pollutants from aqueous solutions. The results showed that nearly 100% degradation of phenol, bisphenol A, and hydroquinone was achieved after reaction for 4 min in the presence of 65 µM PMS and 50 µM I-. PMS-I- oxidation had a wide effective pH range, with the best performance achieved under circumneutral conditions. The ratio between [PMS] and [I-] influenced the degradation, and the optimal ratio was approximately 1.00 for the degradation of the phenols. Neither sulfate nor hydroxyl radicals were found to be the active species in PMS-I- oxidation. Instead, we found evidence that iodide atoms were the dominant oxidants. In addition, both Cl- and Br- also promoted the degradation of phenol in PMS solution. The results of this work may promote the application of reactive halogen species in water treatment.

Effect of Nitrogen Oxides on Elemental Mercury Removal by Nanosized Mineral Sulfide.

Because of its large surface area, nanosized zinc sulfide (Nano-ZnS) has been demonstrated in a previous study to be efficient for removal of elemental mercury (Hg0) from coal combustion flue gas. The excellent mercury adsorption performance of Nano-ZnS was found to be insusceptible to water vapor, sulfur dioxide, and hydrogen chloride. However, nitrogen oxides (NOX) apparently inhibited mercury removal by Nano-ZnS; this finding was unlike those of many studies on the promotional effect of NOX on Hg0 removal by other sorbents. The negative effect of NOX on Hg0 adsorption over Nano-ZnS was systematically investigated in this study. Two mechanisms were identified as primarily responsible for the inhibitive effect of NOX on Hg0 adsorption over Nano-ZnS: (1) active sulfur sites on Nano-ZnS were oxidized to inactive sulfate by NOX; and (2) the chemisorbed mercury, i.e., HgS, was reduced to Hg0 by NOX. This new insight into the role of NOX in Hg0 adsorption over Nano-ZnS can help to optimize operating conditions, maximize Hg0 adsorption, and facilitate the application of Nano-ZnS as a superior alternative to activated carbon for Hg0 removal using existing particulate matter control devices in power plants.

Stabilizing cadmium into aluminate and ferrite structures: Effectiveness and leaching behavior.

The inappropriate disposal of sludge, particularly for those enriched in heavy metals, is highly hazardous to the environment. Thermally converting sludge into useful products is a highly promising technique as heavy metals are immobilized and organic substances are mineralized. This work investigated the feasibility of stabilizing simulated cadmium-laden sludge by sintering with Al-and Fe-rich precursors. To simulate the process, cadmium oxide was alternatively mixed and sintered with γ-Al2O3 and α-Fe2O3. Cadmium was crystallographically incorporated into aluminate (CdAl4O7) monoclinic structure and ferrite (CdFe2O4) spinel, dependent on the type of precursor used. The CdFe2O4 formation was initialed at about 150-300 °C lower than that of CdAl4O7. With Rietveld refinement analysis of the collated XRD data, the weight percentages of crystalline phases in the fired samples were quantified. To evaluate the cadmium incorporation efficiency, a transformation ratio (TR) index was devised. The TR values revealed that, to effectively incorporate cadmium, 950 °C was favored by γ-Al2O3 and 850 °C was for α-Fe2O3 within a 3-h sintering treatment. Constant pH leaching test (CPLT) was used to assess the metal stabilization effects, revealing a remarkable reduction of cadmium by transformation into CdAl4O7 and CdFe2O4. Both CdAl4O7 and CdFe2O4 were incongruently dissolved in an acid solution. The overall finding indicated a potentially feasible technology in cadmium-laden sludge stabilization.

Solvent-Switching Gelation and Orange-Red Emission of Ultrasmall Copper Nanoclusters.

By tuning the Cu⋅⋅⋅Cu and hydrogen-bonding interactions, the small cluster Cu3 L can be selectively synthesized to develop a stable and highly fluorescent material, as confirmed by matrix-assisted laser desorption ionization-time of flight mass spectroscopy. Further characterizations, including absorbance spectroscopy, XPS, and XRD demonstrate the formation of tiny Cu nanoclusters (NCs). In water, the as-prepared Cu NCs can exhibit high orange fluorescence via solution evaporation to eliminate hydrogen-bonding, and in dimethylformamide, a strong orange fluorescent gel is obtained by solvent induction to enhance the Cu⋅⋅⋅Cu and hydrogen-bonding interactions. More importantly, the Cu NCs in their substantial form exhibit nonlinear optical properties upon two-photon excitation. These results will shed light on Cu and related cluster applications in two-photon biological imaging, optical power limiting, and solar energy conversion.

Sulfate Radical-Mediated Degradation of Sulfadiazine by CuFeO2 Rhombohedral Crystal-Catalyzed Peroxymonosulfate: Synergistic Effects and Mechanisms.

Copper-iron bimetallic oxides have shown great potential for powerful radical production by activating peroxides. In this work, CuFeO2 rhombohedral crystals (RCs) were synthesized and used as heterogeneous catalysts for peroxymonosulfate (PMS) activation under various conditions. Sulfadiazine, a widely used veterinary sulfonamide, was used as a target pollutant to evaluate the efficiency of this combination. The results showed that of all the catalysts tested, the CuFeO2 RCs had the greatest reactivity. Under conditions of 0.1 g L(-1) CuFeO2 RCs and 33.0 µM PMS, the nearly complete degradation of sulfadiazine occurred within 24 min. A synergistic catalytic effect was found between solid Cu(I) and Fe(III), probably due to the accelerated reduction of Fe(III). The two activation stages that produced different radicals (hydroxyl radicals followed by sulfate radicals) existed when solid Cu(I) was used as the catalyst. The CuFeO2 RCs had a higher PMS utilization efficiency than CuFe2O4, probably because the Cu(I)-promoted reduction of solid Fe(III). A total of 10 products were identified, and their evolution was explored. On the basis of the evidence of oxidative product formation, we proposed four possible pathways of sulfadiazine degradation.

Development of Nano-Sulfide Sorbent for Efficient Removal of Elemental Mercury from Coal Combustion Fuel Gas.

The surface area of zinc sulfide (ZnS) was successfully enlarged using nanostructure particles synthesized by a liquid-phase precipitation method. The ZnS with the highest surface area (named Nano-ZnS) of 196.1 m(2)·g(-1) was then used to remove gas-phase elemental mercury (Hg(0)) from simulated coal combustion fuel gas at relatively high temperatures (140 to 260 °C). The Nano-ZnS exhibited far greater Hg(0) adsorption capacity than the conventional bulk ZnS sorbent due to the abundance of surface sulfur sites, which have a high binding affinity for Hg(0). Hg(0) was first physically adsorbed on the sorbent surface and then reacted with the adjacent surface sulfur to form the most stable mercury compound, HgS, which was confirmed by X-ray photoelectron spectroscopy analysis and a temperature-programmed desorption test. At the optimal temperature of 180 °C, the equilibrium Hg(0) adsorption capacity of the Nano-ZnS (inlet Hg(0) concentration of 65.0 µg·m(-3)) was greater than 497.84 µg·g(-1). Compared with several commercial activated carbons used exclusively for gas-phase mercury removal, the Nano-ZnS was superior in both Hg(0) adsorption capacity and adsorption rate. With this excellent Hg(0) removal performance, noncarbon Nano-ZnS may prove to be an advantageous alternative to activated carbon for Hg(0) removal in power plants equipped with particulate matter control devices, while also offering a means of reusing fly ash as a valuable resource, for example as a concrete additive.