Controllable Pyridine N-Oxidation-Nucleophilic Dechlorination Process for Enhanced Dechlorination of Chloropyridines: The Cooperation of HCO4- and HO2.

Dechlorination of chloropyridines can eliminate their detrimental environmental effects. However, traditional dechlorination technology cannot efficiently break the C-Cl bond of chloropyridines, which is restricted by the uncontrollable nonselective species. Hence, we propose the carbonate species-activated hydrogen peroxide (carbonate species/H2O2) process wherein the selective oxidant (peroxymonocarbonate ion, HCO4-) and selective reductant (hydroperoxide anion, HO2-) controllably coexist by manipulation of reaction pH. Taking 2-chloropyridine (Cl-Py) as an example, HCO4- first induces Cl-Py into pyridine N-oxidation intermediates, which then suffer from the nucleophilic dechlorination by HO2-. The obtained dechlorination efficiencies in the carbonate species/H2O2 process (32.5-84.5%) based on the cooperation of HCO4- and HO2- are significantly higher than those in the HO2--mediated sodium hydroxide/hydrogen peroxide process (0-43.8%). Theoretical calculations confirm that pyridine N-oxidation of Cl-Py can effectively lower the energy barrier of the dechlorination process. Moreover, the carbonate species/H2O2 process exhibits superior anti-interference performance and low electric energy consumption. Furthermore, Cl-Py is completely detoxified via the carbonate species/H2O2 process. More importantly, the carbonate species/H2O2 process is applicable for efficient dehalogenation of halogenated pyridines and pyrazines. This work offers a simple and useful strategy to enhance the dehalogenation efficiency of halogenated organics and sheds new insights into the application of the carbonate species/H2O2 process in practical environmental remediation.

Targeted Decomplexation of Metal Complexes for Efficient Metal Recovery by Ozone/Percarbonate.

Traditional methods cannot efficiently recover Cu from Cu(II)-EDTA wastewater and encounter the formation of secondary contaminants. In this study, an ozone/percarbonate (O3/SPC) process was proposed to efficiently decomplex Cu(II)-EDTA and simultaneously recover Cu. The results demonstrate that the O3/SPC process achieves 100% recovery of Cu with the corresponding kobs value of 0.103 min-1 compared with the typical •OH-based O3/H2O2 process (81.2%, 0.042 min-1). The carbonate radical anion (CO3•-) is generated from the O3/SPC process and carries out the targeted attack of amino groups of Cu(II)-EDTA for decarboxylation and deamination processes, resulting in successive cleavage of Cu-O and Cu-N bonds. In comparison, the •OH-based O3/H2O2 process is predominantly responsible for the breakage of Cu-O bonds via decarboxylation and formic acid removal. Moreover, the released Cu(II) can be transformed into stable copper precipitates by employing an endogenous precipitant (CO32-), accompanied by toxic-free byproducts in the O3/SPC process. More importantly, the O3/SPC process exhibits excellent metal recovery in the treatment of real copper electroplating wastewater and other metal-EDTA complexes. This study provides a promising technology and opens a new avenue for the efficient decomplexation of metal-organic complexes with simultaneous recovery of valuable metal resources.

A general strategy via chemically covalent combination for constructing heterostructured catalysts with enhanced photocatalytic hydrogen evolution.

A general strategy via chemically covalent combination was reported to fabricate heterostructured catalysts of carbon nitride/covalent organic frameworks (CNFs), which show superior photocatalytic activity and higher stability as compared to the conventional heterostructures of CN and COFs connected via van der Waals forces.

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.

Electrochemical oxidation and advanced oxidation processes using a 3D hexagonal Co3O4 array anode for 4-nitrophenol decomposition coupled with simultaneous CO2 conversion to liquid fuels via a flower-like CuO cathode.

A novel electrocatalytic system was developed to realize one-pot conversion of organic pollutants into liquid fuels such as methanol (CH3OH) and ethanol (C2H5OH). The process combines the catalytic oxidation of organic pollutants with electrocatalytic reduction of CO2. We first coupled the electrocatalytic process with SO4•--based advanced oxidation processes (AOPs) for the degradation of 4-nitrophenol (4-NP) using a 3D-hexagonal Co3O4 anode. In this step, 4-NP was mineralized to CO2, and then the CO2 was converted to CH3OH and C2H5OH by electrocatalytic reduction using a flower-like CuO cathode. The experimental results show the destruction of 4-NP (60 mL, 10 mg/L) can be as high as 99%. In addition, the yields of CH3OH and C2H5OH were 98.29 µmol/L and 40.95 µmol/L, respectively, which represents a conversion of 41.8% of 4-NP into liquid fuels; the electron efficiency was 73.1%. In addition, we found that 3D-hexagonal arrays of Co3O4 with different morphologies can be obtained by adding different amounts of urea. We also investigated the formation mechanism of novel 3D-hexagonal Co3O4 arrays for the first time. A mechanism was proposed to explain the electrocatalytic steps involved in the conversion of 4-NP to CH3OH and C2H5OH and the synergetic effects between AOPs and electrocatalysis.

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.