1D/3D Heterogeneous Assembling Body of Cobalt Nitrides for Highly Efficient Overall Hydrazine Splitting and Supercapacitors.

Herein, the construction of a heterostructured 1D/3D CoN-Co2 N@NF (nickel foam) electrode used for thermodynamically favorable hydrazine oxidation reaction (HzOR), as an alternative to sluggish anodic oxygen evolution reaction (OER) in water splitting for hydrogen production, is reported. The electrode exhibits remarkable catalytic activities, with an onset potential of -0.11 V in HzOR and -71 mV for a current density of 10 mA cm-2 in hydrogen evolution reaction (HER). Consequently, an extraordinary low cell voltage of 53 mV is required to achieve 10 mA cm-2 for overall hydrazine splitting in a two-electrode system, demonstrating significant energy-saving advantages over conventional water splitting. The HzOR proceeds through the 4e- reaction pathway to release N2 while the 1e- pathway to emit NH3 is uncompetitive, as evidenced by differential electrochemical mass spectrometric measurements. The X-ray absorption spectroscopy, in situ Raman spectroscopy, and theoretical calculations identify cobalt nitrides rather than corresponding oxides/(oxy)hydroxides as catalytic species for HzOR and illustrate advantages of heterostructured CoN-Co2 N in optimizing adsorption energies of intermediates/reagents and promoting catalytic activities toward both HzOR and HER. The CoN-Co2 N@NF is also an excellent supercapacitive material, exhibiting an increased specific capacity (938 F g-1 at 1 A g-1 ) with excellent cycling stability (95.8%, 5000 cycles).

Do We Appropriately Detect and Understand Singlet Oxygen Possibly Generated in Advanced Oxidation Processes by Electron Paramagnetic Resonance Spectroscopy?

Electron paramagnetic resonance (EPR) spectroscopy using sterically hindered amine is extensively applied to detect singlet oxygen (1O2) possibly generated in advanced oxidation processes. However, EPR-detectable 1O2 signals were observed in not only the 1O2-dominated hydrogen peroxide (H2O2)/hypochlorite (NaClO) reaction but surprisingly also the 1O2-absent Fe(II)/H2O2, UV/H2O2, and ferrate [Fe(VI)] process with even stronger intensities. By taking advantage of the characteristic reaction between 1O2 and 9,10-diphenyl-anthracene and near-infrared phosphorescent emission of 1O2, 1O2 was excluded in the Fe(II)/H2O2, UV/H2O2, and Fe(VI) process. The false detection of 1O2 was ascribed to the direct oxidation of hindered amine to piperidyl radical by reactive species [e.g., •OH and Fe(VI)/Fe(V)/Fe(IV)] via hydrogen transfer, followed by molecular oxygen addition (forming a piperidylperoxyl radical) and back reaction with piperidyl radical to generate a nitroxide radical, as evidenced by the successful identification of a piperidyl radical intermediate at 100 K and theoretical calculations. Moreover, compared to the highly oxidative species (e.g., •OH and high-valence Fe), the much lower reactivity of 1O2 and the profound nonradiative relaxation of 1O2 in H2O resulted it too selective and inefficient in organic contaminant destruction. This study demonstrated that EPR-based 1O2 detection could be remarkably misled by common oxidative species and thereby jeopardize the understandings on 1O2.

Ru(III)-Periodate for High Performance and Selective Degradation of Aqueous Organic Pollutants: Important Role of Ru(V) and Ru(IV).

In this study, Ru(III) ions were utilized to activate periodate (PI) for oxidation of trace organic pollutants (TOPs, e.g., carbamazepine (CBZ)). The Ru(III)/PI system can significantly promote the oxidation of CBZ in a wide initial pH range (3.0-11.0) at 1 µM Ru(III), showing much higher performance than transition metal ions (i.e., Fe(II), Co(II), Zn(II), Fe(III), Cu(II), Ni(II), Mn(II), and Ce(III)) and noble metal ion (i.e., Ag(I), Pd(II), Pt(II), and Ir(III)) activated PI systems. Probe experiments, UV-vis spectra, and X-ray absorption near-edge structure (XANES) spectra confirmed high-valent Ru-oxo species (Ru(V)=O) as the dominant oxidant in the process. Because of the dominant role of Ru(V)=O, the Ru(III)/PI process exhibited a remarkable selectivity and strong anti-interference in the oxidation of TOPs in complex water matrices. The Ru(V)=O species can undertake 1-e- and 2-e- transfer reactions via the catalytic cycles of Ru(V)=O → Ru(IV) → Ru(III) and Ru(V)=O → Ru(III), respectively. The utilization efficiency of PI in the Ru(III)/PI process for the oxidation of TOPs can approach 100% under optimal conditions. PI stoichiometrically transformed into IO3- without production of undesired iodine species (e.g., HOI and I2). This study developed an efficient and environmentally benign advanced oxidation process for rapid removal of TOPs and enriched understandings on reactivity of Ru(V)=O and Ru catalytic cycles.

Highly-efficient molten NaOH-KOH for organochlorine destruction: Performance and mechanism.

Molten salt has been increasingly acknowledged to be useful in the destruction of chlorine-containing organic wastes (COWs), e.g., organochlorine. However, the operational temperatures are usually high, and local structure and thermodynamic property of the molten salt remain largely unclear. In this study, novel molten NaOH-KOH is developed for organochlorine destruction, and its eutectic point can be lowered to 453 K with 1:1 mol ratio of NaOH to KOH. Further experiment shows that this molten NaOH-KOH is highly-efficient towards the destructions of both trichlorobenzene and dichlorophenol, acquiring the final dechlorination efficiencies as 88.2% and 94.1%, respectively. The organochlorine destruction and chloride salt enrichment are verified by fourier-transform infrared spectrometer. Molten NaOH-KOH not only eliminates the C-Cl and CC bonds, but also traps generated CO2, other acidic gases, and possibly particulate matters as a result of the high surface area and high viscosity. This makes it possibly advantageous over incineration for organic waste destruction for carbon neutrality. To sufficiently reveal the inherent mechanism for the temperature dependent performance, molecular dynamics simulation is further adopted. Results show that the radial distance between ions increases with temperature, causing larger molar volume and lower resistance to shear deformation. Moreover, thermal expansion coefficient, specific heat capacity, and ion self-diffusion coefficient of the molten NaOH-KOH are found to increase linearly with temperature. All these microscopic alterations contribute to the organochlorine destruction. This study benefits to develop highly-efficient molten system for COWs treatment via a low-carbon approach.

Dissemination of antibiotic resistance genes through fecal sewage treatment facilities to the ecosystem in rural area.

Infection of antibiotic-resistant pathogens mostly occurs in rural areas. In this paper, the dissemination of antibiotic resistance genes (ARGs) through fecal sewage treatment facilities to the ecosystem in a typical rural area is investigated. Household three-chamber septic tanks (TCs), household biogas digesters (BDs), wastewater treatment plants (WWTPs), vegetable plots, water ponds, etc. Are taken into account. The relative abundance of ARGs in fecal sewage can be reduced by BDs and WWTPs by 80% and 60%, respectively. While TCs show no reduction ability for ARGs. Fast expectation-maximization microbial source tracking (FEAST) analysis revealed that TCs and BDs contribute a considerable percentage (15-22%) of ARGs to the surface water bodies (water ponds) in the rural area. Most ARGs tend to precipitate in the sediments of water bodies and stop moving downstream. Meanwhile, the immigration of microorganisms is more active than that of ARGs. The results provide scientific basic data for the management of fecal sewage and the controlling of ARGs in rural areas.

Redox Behavior of Secondary Solid Iron Species and the Corresponding Effects on Hydroxyl Radical Generation during the Pyrite Oxidation Process.

During the pyrite oxidation process, aqueous ferrous/ferric ions (Fe2+/Fe3+), as well as surface-adsorbed Fe2+/Fe3+, have been widely recognized to dominate hydroxyl radical (•OH) generation, while this study reveals that the secondary solid iron species also play non-negligible roles. Based on the different forms and the presence of sites, the secondary solid iron species were classified as Fecoat (iron-containing coating on the pyrite surface) and Fedep (ex situ-deposited iron (oxyhydr)oxide that is not in contact with pyrite). Instead of participating in building a stubborn passivation layer on the pyrite surface, Fecoat is easy to fall off from the pyrite surface as the oxidation of pyrite deepens, while large fractions of Fedep and Fecoat are found to be extractable with nitrilotriacetic acid (NTA). Achieved by cyclically oxidizing pyrite within different NTA levels (0/0.1/10 mM), Fecoat and Fedep were proved to have distinct redox behavior during the pyrite oxidation process. Amorphous Fedep, originated from the hydrolyzation of dissolved Fe3+, accelerates the nonradical decay of hydrogen peroxide (H2O2); as a result, the accumulation of Fedep always decreases the •OH production during the pyrite oxidation process. However, part of Fedep adsorbs on the pyrite surface through electrostatic attraction and converts into Fecoat. The electron conduction between Fecoat and pyrite was verified, which accelerates the oxidative dissolution of pyrite, produces reactive Fe(II), and therefore favors •OH generation. This study improves our understanding of the redox behavior of pyrite in complex media such as natural processes and practical engineering systems.

Membrane-Current Collector-Based Flow-Electrode Capacitive Deionization System: A Novel Stack Configuration for Scale-Up Desalination.

The stack configuration in flow-electrode capacitive deionization (FCDI) has been verified to be an attractive and feasible strategy for scaling up the desalination process. However, challenges still exist when attempting to simultaneously improve the desalination scale and the cell configuration. Here, we describe a novel stack FCDI configuration (termed a gradient FCDI system) based on a membrane-current collector assembly, in which the charge neutralization enables the in situ regeneration of the flow electrodes in the single cycle operation, thereby realizing a considerable increase in the desalinating performance. By evaluating standardized metrics such as the salt rejection, productivity (P), average salt removal rate (ASRR), energy-normalized removed salt (ENRS), and TEE, the results indicated that the gradient FCDI system could be a performance-stable and energy-efficient alternative for scale-up desalination. Under optimal operating conditions (carbon content = 10 wt %, feed salinity = 3000 mg L-1, cell voltage = 1.2 V, and productivity = 56.7 L m-2 h-1), the robust desalination performance (ASRR = 1.07 µmol cm-2 min-1) and energy consumption (ENRS = 7.8 µmol J-1) of the FCDI system with a desalination unit number of four were verified at long-term operation. In summary, the stacked gradient FCDI system and its operation mode described here may be an innovative and promising strategy capable of enlarging the scale of desalination while realizing performance improvement and device simplification.

Enhanced Oxidation of Organic Contaminants by Iron(II)-Activated Periodate: The Significance of High-Valent Iron-Oxo Species.

Potassium periodate (PI, KIO4) was readily activated by Fe(II) under acidic conditions, resulting in the enhanced abatement of organic contaminants in 2 min, with the decay ratios of the selected pollutants even outnumbered those in the Fe(II)/peroxymonosulfate and Fe(II)/peroxydisulfate processes under identical conditions. Both 18O isotope labeling techniques using methyl phenyl sulfoxide (PMSO) as the substrate and X-ray absorption near-edge structure spectroscopy provided conclusive evidences for the generation of high-valent iron-oxo species (Fe(IV)) in the Fe(II)/PI process. Density functional theory calculations determined that the reaction of Fe(II) with PI followed the formation of a hydrogen bonding complex between Fe(H2O)62+ and IO4(H2O)-, ligand exchange, and oxygen atom transfer, consequently generating Fe(IV) species. More interestingly, the unexpected detection of 18O-labeled hydroxylated PMSO not only favored the simultaneous generation of ·OH but also demonstrated that ·OH was indirectly produced through the self-decay of Fe(IV) to form H2O2 and the subsequent Fenton reaction. In addition, IO4- was not transformed into the undesired iodine species (i.e., HOI, I2, and I3-) but was converted to nontoxic iodate (IO3-). This study proposed an efficient and environmental friendly process for the rapid removal of emerging contaminants and enriched the understandings on the evolution mechanism of ·OH in Fe(IV)-mediated processes.

Unraveling the Overlooked Involvement of High-Valent Cobalt-Oxo Species Generated from the Cobalt(II)-Activated Peroxymonosulfate Process.

Sulfate radical (SO4•-) is widely recognized as the predominant species generated from the cobalt(II)-activated peroxymonosulfate (PMS) process. However, in this study, it was surprisingly found that methyl phenyl sulfoxide (PMSO) was readily oxidized to the corresponding sulfone (PMSO2) with a transformation ratio of ∼100% under acidic conditions, which strongly implied the generation of high-valent cobalt-oxo species [Co(IV)] instead of SO4•- in the Co(II)/PMS process. Scavenging experiments using methanol (MeOH), tert-butyl alcohol, and dimethyl sulfoxide further suggested the negligible role of SO4•- and hydroxyl radical (•OH) but favored the generation of Co(IV). By employing 18O isotope-labeling technique, the formation of Co(IV) was conclusively verified and the oxygen atom exchange reaction between Co(IV) and H2O was revealed. Density functional theory calculation determined that the formation of Co(IV) was thermodynamically favorable than that of SO4•- and •OH in the Co(II)/PMS process. The generated Co(IV) species was indicated to be highly reactive due to the existence of oxo-wall and capable of oxidizing the organic pollutant that is rather recalcitrant to SO4•- attack, for example, nitrobenzene. Additionally, the degradation intermediates of sulfamethoxazole (SMX) in the Co(II)/PMS process under acidic conditions were identified to further understand the interaction between Co(IV) and the representative contaminant. The developed kinetic model successfully simulated PMSO loss, PMSO2 production, SMX degradation, and/or PMS decomposition under varying conditions, which further supported the proposed mechanism. This study might shed new light on the Co(II)/PMS process.

Comparative performance of green rusts generated in Fe0-electrocoagulation for Cd2+ removal from high salinity wastewater: Mechanisms and optimization.

The treatment of wastewater containing high concentration of inorganic salts has always been one of the focuses of environmental researchers. In this work, the effect of Cl- and SO42- on the removal of Cd2+ from wastewater using Fe0-electrocoagulation (Fe0-EC) were investigated by evaluating the transformation of Fe mineral. The experimental results indicated that the removal of Cd2+ from wastewater was depended on the property of Fe minerals. The generation of sulfate green rust (GRSO4) produced in the presence of SO42- showed stronger adsorption than the chloride green rust (GRCl) for Cd2+, and GRSO4 was obtained even in the mixture Cl- and SO42- solutions, because Fe(II)-Fe(III) GRs (layered double hydroxides, LDHs) showed stronger affinity for divalent SO42- than monovalent Cl-. High concentration of inorganic anions in wastewater resulted in the negative charged Fe flocs. High concentration of Cl- promoted the oxidation of Fe(II) to Fe(III) by chlorine-containing oxidants, and increased the proportion of Fe(III)/Fe(II) in Fe flocs, secondary Fe mineral magnetite (Fe3O4) was formed because of the increase of pH. Therefore, the presence of GRSO4 intermediate increased the Cd2+ removal by adsorption (coagulation and coprecipitation), and then the generated GRSO4 were gradually transformed into lepidocrocite (γ-FeOOH) by oxygen from air. Finally, the parameter optimization were conducted by adjusting the ratio of Cl- and SO42- (RC:S), current density (j), initial pH (pHi), initial Cd2+ concentration (C0), and temperature (T0). The removal efficiency of Cd2+ reached 99.5% after 10 min Fe0-EC under the optimal parameters: RC:S = 25:50 mmoL/mmol, j = 6 mA/cm2, pHi = 7-9, and T0 = 40 °C.

Continuous-flow ozonation over modified ceramsite: implications for the degradation of cation red x-GRL.

Catalytic ozonation has been widely used for refractory dye wastewater treatment due to highly reactive HO·. In this study, a kind of low-cost and environmental-friendly modified ceramsite sphere derived from pyrite cinder, silty clay and kaolin was prepared as ozonation catalyst. The degradation performances of cation red x-GRL were performed under a continuous mode. Being close to the practical treatment, continuous-flow ozonation study is vital for applying heterogeneous catalytic ozonation in wastewater treatment at a large industrial scale. Results showed that the absorption capacity of this modified ceramsite towards cation red x-GRL was confirmed to be slight. The mineralization efficiency was high, accounting for 48.0% of 200 mg/L cation red x-GRL at a constant flow rate of 0.18 L/min (hydraulic retention time = 16 min), while only 7.8% during ozonation alone. Furthermore, this novel catalytic ozonation can maintain high mineralization efficiency in a wide range of pH (3-10), which was ascribed to the synergistic catalytic performance of various oxides. The reaction mechanism is ascribed to the promotion of ·OH production from O3 molecules' decomposition. Moreover, ozone utilization efficiency at hydraulic retention time of 16 min during catalytic ozonation was 2.0 times as high as that during ozonation alone.

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.

Continuous Bulk FeCuC Aerogel with Ultradispersed Metal Nanoparticles: An Efficient 3D Heterogeneous Electro-Fenton Cathode over a Wide Range of pH 3-9.

Novel iron-copper-carbon (FeCuC) aerogel was fabricated through a one-step process from metal-resin precursors and then activated with CO2 and N2 in environmentally friendly way. The activated FeCuC aerogel was applied in a heterogeneous electro-Fenton (EF) process and exhibited higher mineralization efficiency than homogeneous EF technology. High total organic carbon (TOC) removal of organic pollutants with activated FeCuC aerogel was achieved at a wide range of pH values (3-9). The chemical oxygen demand (COD) of real dyeing wastewater was below China's discharge standard after 30 min of treatment, and the specific energy consumption was low (9.2 kW·h·kg(-1)COD(-1)), corresponding to a power consumption of only ∼0.34 kW·h per ton of wastewater. The enhanced mineralization efficiency of FeCuC aerogel was mostly attributable to ultradispersed metallic Fe-Cu nanoparticles embedded in 3D carbon matrix and the CO2-N2 treatment. The CO2 activation enhanced the accessibility of the aerogel's pores, and the secondary N2 activation enlarged the porosity and regenerated the ultradispersed zerovalent iron (Fe(0)) with reductive carbon. Cu(0) acted as a reduction promoter for interfacial electron transfer. Moreover, activated FeCuC aerogel presented low iron leaching (<0.1 ppm) in acidic solution and can be molded into different sizes with high flexibility. Thus, this material could be used as a low-cost cathode and efficient heterogeneous EF technology for actual wastewater treatment.

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.

Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.

A pyrite-catalyzed reaction was used to degrade chloramphenicol. Chloramphenicol could be almost 100% removed within 60 minutes when 1 mM H2O2 and 0.1 g/L pyrite were added at an initial pH=3. During oxidation, intermediates such as nitrobenzaldehyde and dichloroacetamide were identified by gas chromatography/mass spectrometry (GC/MS). The •OH was identified by electron spin-resonance spectroscopy. Pyrite was digested to determine elements by ICP (inductive coupled plasma emission spectrometer). To understand the reaction mechanism and the role of natural pyrite in these processes, techniques including scanning electron microscopy and energy dispersive spectrometry were employed to characterize the solid sample. The results explain that pyrite acts as a 'bond' between Fe3+ and H2O2, and this pathway continues to form •OH and inhibit the quenching reaction. Therefore, pyrite-catalyzed reactions would proceed even in low concentrations of H2O2.

Effects of Cu2+, Ag+, and Pd2+ on the reductive debromination of 2,5-dibromoaniline by the ferrous hydroxy complex.

The ferrous hydroxy complex (FHC), composed of structural FeⅡ, has been shown to reduce a range of organic and inorganic contaminants. This study focused on the catalytic effects of Cu2+, Ag+, or Pd2+ on the reactivity of FHC suspensions towards 2,5-debromination (2,5-DBA). It was found that the target compound (2,5-DBA, 50 mg/L) could hardly be debrominated by FHC alone. However, Cu2+, Ag+, or Pd2+ had a significant promotion effect on the catalytic reactivity of structural FeⅡ on 2,5-DBA reduction. Pd2+ exhibited the best catalytic activity followed by Ag+ and Cu2+ in this study and the reductive debromination by Pd/FHC and Ag/FHC followed the pseudo-first-order kinetic model. Products distribution was highly dependent on the metal ions used. A reaction pathway was proposed in which the by-products were produced by hydrogenolysis and the elution order of bromines depended on the metal ions used. The enhanced reduction of 2,5-DBA by FHC suspensions modified by metal ions may prove useful in the development of improved materials for the treatment of halogenated organic compounds.

Pyrite cinder as a cost-effective heterogeneous catalyst in heterogeneous Fenton reaction: decomposition of H(2)O(2) and degradation of Acid Red B.

Pyrite cinder (PyC) was employed as a heterogeneous Fenton-like catalyst, and its catalytic activity was evaluated in view of the effects of catalyst dosage, pH and leaching metal ions. PyC showed significant reactivity, and the pseudo-first-order kinetic rate constant for decomposition of H(2)O(2) and degradation of Acid Red B (ARB) were 3.4 and 14.89 (10⁻³ min⁻¹) respectively when pH = 5. When 20 g/L PyC was added into 10 mM H(2)O(2) solution in neutral pH, H(2)O(2) could be completely degraded within 4 h, and more than 90% ARB was removed. Leaching metal ions from PyC were found to have little effect on decomposition of H(2)O(2) or on degradation of ARB. PyC still had high catalytic activity after five successive runs. The decomposition mechanism of H(2)O(2) was analyzed and the Haber-Weiss mechanism was employed in this paper. The electron spin resonance image showed •OH was produced and increased between 3 and 5 min in the PyC catalyzing H(2)O(2) reaction, which demonstrated that PyC had a durable ability to produce •OH.

Enhanced anaerobic digestion of human feces by ferrous hydroxyl complex (FHC): Stress factors alleviation and microbial resistance improvement.

Anaerobic digestion (AD) offers a reliable strategy for resource recovery from source-separated human feces (HF), but is limited by a disproportionate carbon/nitrogen (C/N) ratio. Ferrous hydroxyl complex (FHC) was first introduced into the HF-AD system to mediate methanogenesis. Mono-digestion of undiluted HF was inhibited by high levels of volatile fatty acids (VFAs), ammonia, and hydrogen sulfide (H2S). FHC addition at optimum dosage (500-1000 mg/L) increased the cumulative methane (CH4) yield by 22.7%, enhanced the peak value of daily CH4 production by 60.5%, and shortened the lag phase by 24.7%. H2S concentration in biogas was also greatly decreased by FHC via precipitation. FHC mainly facilitated the hydrolysis, acidification, and methanogenesis processes. The production and transformation of VFAs were optimized in the presence of FHC, thus relieving acid stress. FHC elevated the activities of alkaline protease, cellulase, and acetate kinase by 32.3%, 18.2%, and 30.3%, respectively. Microbial analysis revealed that hydrogenotrophic methanogens prevailed in mono-digestion at high HF loading but were weakened after FHC addition. FHC also enriched Methanosarcina, thereby expanding the methanogenesis pathway and improving the resistance to ammonia stress. This work would contribute to improving the methanogenic performance and resource utilization for HF anaerobic digestion.

Enhanced hydrodechlorination of 4-chlorophenol through carboxymethylcellulose-modified Pd/Fe nanosuspension synthesized by one-step methods.

Palladized iron (Pd/Fe) represents one of the most common modification strategies for nanoscale zero-valent iron (nZVI). Most studies prepared Pd/Fe by reducing iron salts and depositing Pd species on the surface of pre-synthesized nZVI, which can be called the two-step method. In this study, we proposed a one-step method to obtain Pd/Fe by the concurrent formation of Fe0 and Pd0 and investigated the effects of these two methods on 4-chlorophenol (4-CP) removal, with carboxymethylcellulose (CMC) coated as a surface modifier. Results indicated that the one-step method, not only streamlined the synthesis process, but also Pd/Fe-CMCone-step, synthesized by it, exhibited a higher 4-CP removal rate (97.9%) compared to the two-step method material Pd/Fe-CMCtwo-step (82.4%). Electrochemical analyses revealed that the enhanced activity of Pd/Fe-CMCone-step was attributed to its higher electron transfer efficiency and more available reactive species, active adsorbed hydrogen species (Hads*). Detection of intermediate products demonstrated that, under the influence of Pd/Fe-CMCone-step, the main route of 4-CP was through hydrodechlorination (HDC) to form phenol and H* was the main active specie, supported by EPR tests, quenching experiments and product analysis. Additionally, the effects of initial 4-CP concentration, initial pH, O2 concentration, anions such as Cl-, SO42-, HCO3-, and humic acid (HA) were also investigated. In conclusion, the results of this study suggest that Pd/Fe-CMCone-step, synthesized through the one-step method, is a convenient and efficient nZVI-modifying material suitable for the HDC of chlorinated organic compounds.

ZnS-embedded porous carbon for peroxydisulfate activation: Enhanced electron transfer for bisphenol A degradation.

Transition metal sulfides have garnered increasing attention for their role in persulfate activation, a crucial process in environmental remediation. However, the function of metal sulfides without reversible valence changes, such as ZnS, remains largely unexplored in this context. Here we report ZnS-embedded porous carbon (ZnS-C), synthesized through the pyrolysis of Zn-MOF-74 and dibenzyl disulfide. ZnS-C demonstrates remarkable activity in activating peroxydisulfate (PDS) across a wide pH range, enabling the efficient mineralization removal of bisphenol A (BPA). Through electrochemical investigation and theoretical simulations of charge density distributions, we unveil that the electron transfer from BPA to PDS mediated by the ZnS-C catalyst governs the reaction. This study, both in theory and experiment, demonstrates metal sulfide as electron pump that enhances electron transfer efficiency in PDS activation. These findings redefine the role of metal sulfide catalysts, shedding new light on their potential for regulating reaction pathways in PDS activation processes.