Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals.

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment of the carbon nitride-supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via a facile supermolecular self-assembly strategy. Short-distance S coordination boosts the peroxymonosulfate (PMS) activation and selectively generates high-valent iron-oxo species (FeIV=O) along with singlet oxygen (1O2), significantly increasing the 1O2 yield, PMS utilization, and p-chlorophenol reactivity by 6.0, 3.0, and 8.4 times, respectively. The composition of nonradicals is controllable by simply changing the S content. In contrast, long-distance S coordination generates both radicals and nonradicals, and could not promote reactivity. Experimental and theoretical analyses suggest that the short-distance S upshifts the d-band center of the Fe atom, i.e., being close to the Fermi level, which changes the binding mode between the Fe atom and O site of PMS to selectively generate 1O2 and FeIV=O with a high yield. The short-distance S-coordinated Fe SAC exhibits excellent application potential in various water matrices. These findings can guide the rational design of robust SACs toward a selective and controllable generation of nonradicals with high yield and PMS utilization.

Few-Atomic Zero-Valent Palladium Ensembles for Efficient Reductive Dehydrogenation and Dehalogenation Catalysis.

Single-atom catalysts (SACs) offer immense potential in heterogeneous catalysis due to their maximized atomic utilization and high selectivity but suffer the problem of low reactivity in catalytic reductive reactions due to their high-valent state. Here, we demonstrate that supported palladium (Pd) ensembles consisting of a few zero-valent Pd atoms (Pd1+c-red/CN) exhibit exceptional reactivity in formic acid (FA) dehydrogenation and 4-chlorophenol (4-CP) dechlorination. The initial FA dehydrogenation and 4-CP dechlorination rates of Pd1+c-red/CN are 42-104 and 16-210 times higher than that of supported Pd SACs (Pd1-ox/CN), respectively. Experimental results and density functional theory (DFT) calculations reveal that optimal adsorption sites of Pd1+c-red/CN stimulate the formation of H*, which is indispensable for 4-CP dechlorination. Moreover, direct electron transfer from Pd atoms to FA with a high electron density on Pd1+c-red/CN also contributes to the rapid 4-CP dechlorination. The superior dehalogenation capability of Pd1+c-red/CN for organohalides of great environmental and health concerns suggested its immense application potential in environmental remediation. This work highlights the pivotal roles of the structure and valence state of Pd ensembles in catalytic reductive reactions and provides a strategy to broaden the application of Pd-based catalysts for dehydrogenation and dehalogenation.

Efficient Degradation of Intracellular Antibiotic Resistance Genes by Photosensitized Erythrosine-Produced 1O2.

Intracellular antibiotic resistance genes (iARGs) constitute the important part of wastewater ARGs and need to be efficiently removed. However, due to the dual protection of intracellular DNA by bacterial membranes and the cytoplasm, present disinfection technologies are largely inefficient in iARG degradation. Herein, we for the first time found that erythrosine (ERY, an edible dye) could efficiently degrade iARGs by producing abundant 1O2 under visible light. Seven log antibiotic-resistant bacteria were inactivated within only 1.5 min, and 6 log iARGs were completely degraded within 40 min by photosensitized ERY (5.0 mg/L). A linear relationship was established between ARG degradation rate constants and 1O2 concentrations in the ERY photosensitizing system. Surprisingly, a 3.2-fold faster degradation of iARGs than extracellular ARGs was observed, which was attributed to the unique indirect oxidation of iARGs induced by 1O2. Furthermore, ERY photosensitizing was effective for iARG degradation in real wastewater and other photosensitizers (including Rose Bengal and Phloxine B) of high 1O2 yields could also achieve efficient iARG degradation. The findings increase our knowledge of the iARG degradation preference by 1O2 and provide a new strategy of developing technologies with high 1O2 yield, like ERY photosensitizing, for efficient iARG removal.

Shifts of surface-bound •OH to homogeneous •OH in BDD electrochemical system via UV irradiation for enhanced degradation of hydrophilic aromatic compounds.

Indirect electrochemical oxidation by hydroxyl radicals is the predominant degradation mechanism in electrolysis with a boron-doped diamond (BDD) anode. However, this electrochemical method exhibits low reactivity in removal of hydrophilic aromatic pollutants owing to mass transfer limitation. In this study, the combination of ultraviolet light and BDD electrolysis could increase the degradation rate of hydrophilic aromatic pollutants by approximately 8-10 times relative to electrolysis alone. According to the results of the scavenging experiments and identification of benzoic acid oxidation products, surface-bound hydroxyl radical (•OH(surface)) was the primary reactive species degrading aromatic pollutants in the BDD electrolysis process, whereas freely-diffusing homogeneous hydroxyl radical (•OH(free)) was the major reactive species in the UV-assisted BDD electrolysis process. Cyclic voltammetry revealed that UV light decomposed H2O2 formed on the BDD anode surface, thus retarding O2 evolution and facilitating •OH(free) generation. This work also explored the potential application of UV-assisted BDD electrolysis in removing COD from bio-pretreated landfill leachate containing high concentrations of hydrophilic aromatic pollutants. This study shed light on the importance of the existing state of •OH on removal of pollutants during BDD electrolysis, and provided a facile and efficient UV-assisted strategy for promoting degradation of hydrophilic aromatic pollutants.

Mineralization of cyanides via a novel Electro-Fenton system generating •OH and •O2.

Traditional methods of cyanides' (CN-) mineralization cannot overcome the contradiction between the high alkalinity required for the inhibition of hydrogen cyanide evolution and the low alkalinity required for the efficient hydrolysis of cyanate (CNO-) intermediates. Thus, in this study, a novel Electro-Fenton system was constructed, in which the free cyanides released from ferricyanide photolysis can be efficiently mineralized by the synergy of •OH and •O2-. The complex bonds in ferricyanide (100 mL, 0.25 mM) were completely broken within 80 min under ultraviolet radiation, releasing free cyanides. Subsequently, in combination with the heterogeneous Electro-Fenton process, •OH and •O2- were simultaneously generated and 92.9% of free cyanides were transformed into NO3- within 120 min. No low-toxic CNO- intermediates were accumulated during the Electro-Fenton process. A new conversion mechanism was proposed that CN- was activated into electron-deficient cyanide radical (•CN) by •OH, and then the •CN intermediates reacted with •O2- via nucleophilic addition to quickly form NO3-, preventing the formation of CNO- and promoting the mineralization of cyanide. Furthermore, this new strategy was used to treat the actual cyanide residue eluent, achieving rapid recovery of irons and efficient mineralization of cyanides. In conclusion, this study proposes a new approach for the mineralization treatment of cyanide-containing wastewater.

Carbon Nitride Supported High-Loading Fe Single-Atom Catalyst for Activation of Peroxymonosulfate to Generate 1 O2 with 100 % Selectivity.

Singlet oxygen (1 O2 ) is an excellent active species for the selective degradation of organic pollutions. However, it is difficult to achieve high efficiency and selectivity for the generation of 1 O2 . In this work, we develop a graphitic carbon nitride supported Fe single-atoms catalyst (Fe1 /CN) containing highly uniform Fe-N4 active sites with a high Fe loading of 11.2 wt %. The Fe1 /CN achieves generation of 100 % 1 O2 by activating peroxymonosulfate (PMS), which shows an ultrahigh p-chlorophenol degradation efficiency. Density functional theory calculations results demonstrate that in contrast to Co and Ni single-atom sites, the Fe-N4 sites in Fe1 /CN adsorb the terminal O of PMS, which can facilitate the oxidization of PMS to form SO5 .- , and thereafter efficiently generate 1 O2 with 100 % selectivity. In addition, the Fe1 /CN exhibits strong resistance to inorganic ions, natural organic matter, and pH value during the degradation of organic pollutants in the presence of PMS. This work develops a novel catalyst for the 100 % selective production of 1 O2 for highly selective and efficient degradation of pollutants.

Silver Single Atom in Carbon Nitride Catalyst for Highly Efficient Photocatalytic Hydrogen Evolution.

Single atom catalysts (SACs) with the maximized metal atom efficiency have sparked great attention. However, it is challenging to obtain SACs with high metal loading, high catalytic activity, and good stability. Herein, we demonstrate a new strategy to develop a highly active and stable Ag single atom in carbon nitride (Ag-N2 C2 /CN) catalyst with a unique coordination. The Ag atomic dispersion and Ag-N2 C2 configuration have been identified by aberration-correction high-angle-annular-dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and extended X-ray absorption. Experiments and DFT calculations further verify that Ag-N2 C2 can reduce the H2 evolution barrier, expand the light absorption range, and improve the charge transfer of CN. As a result, the Ag-N2 C2 /CN catalyst exhibits much better H2 evolution activity than the N-coordinated Ag single atom in CN (Ag-N4 /CN), and is even superior to the Pt nanoparticle-loaded CN (PtNP /CN). This work provides a new idea for the design and synthesis of SACs with novel configurations and excellent catalytic activity and durability.

High selective reduction of nitrate into nitrogen by novel Fe-Cu/D407 composite with excellent stability and activity.

In this study, we develop a new composite material of Fe-Cu/D407 composite via using nanoscale zero-valent iron (nZVI) with copper deposited on chelating resin (D407) to remove nitrate from the water. The experimental results show that a remarkable nitrate removal and the selectivity of N2 are 99.9% and 89.7%, respectively, under the anaerobic conditions of Cu/Fe molar ratio of 1:2, pH = 3.0. Even without of inert gas and adjusting the initial pH of the solution, the removal rate of nitrate by Fe-Cu/D407 reached to 85% and the selectivity of nitrogen reached to 55%. Meanwhile, the Fe-Cu/D407 maintained preferable removal efficiency of nitrate (100% - 92%) over a wide pH range of 3-11. In addition, the removal rate of the drinking water, lake water and wastewater from the Fe-Cu/D407 is still very high and the reactivity of Fe-Cu/D407 was relatively unaffected by the presence of dissolved ions in the waters tested. Moreover, the synergetic effect of Fe, Cu and D407 in the composite Fe-Cu/D407 were well investigated for the first time according to the analyses of TPR, XPS and EIS. The catalytic mechanism and denitrification routes were also proposed.

Three-Dimensional Reduced Graphene Oxide Coupled with Mn3O4 for Highly Efficient Removal of Sb(III) and Sb(V) from Water.

Highly porous, three-dimensional (3D) nanostructured composite adsorbents of reduced graphene oxides/Mn3O4 (RGO/Mn3O4) were fabricated by a facile method of a combination of reflux condensation and solvothermal reactions and systemically characterized. The as-prepared RGO/Mn3O4 possesses a mesoporous 3D structure, in which Mn3O4 nanoparticles are uniformly deposited on the surface of the reduced graphene oxide. The adsorption properties of RGO/Mn3O4 to antimonite (Sb(III)) and antimonate (Sb(V)) were investigated using batch experiments of adsorption isotherms and kinetics. Experimental results show that the RGO/Mn3O4 composite has fast liquid transport and superior adsorption capacity toward antimony (Sb) species in comparison to six recent adsorbents reported in the literature and summarized in a table in this paper. Theoretical maximum adsorption capacities of RGO/Mn3O4 toward Sb(III) and Sb(V) are 151.84 and 105.50 mg/g, respectively, modeled by Langmuir isotherms. The application of RGO/Mn3O4 was demonstrated by using drinking water spiked with Sb (320 µg/L). Fixed-bed column adsorption experiments indicate that the effective breakthrough volumes were 859 and 633 mL bed volumes (BVs) for the Sb(III) and Sb(V), respectively, until the maximum contaminant level of 5 ppb was reached, which is below the maximum limits allowed in drinking water according to the most stringent regulations. The advantages of being nontoxic, highly stable, and resistant to acid and alkali and having high adsorption capacity toward Sb(III) and Sb(V) confirm the great potential application of RGO/Mn3O4 in Sb-spiked water treatment.