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1.
Environ Res ; 215(Pt 1): 114154, 2022 12.
Article in English | MEDLINE | ID: mdl-36037916

ABSTRACT

The biochemical reduction of nitrite (NO2-) ions to ammonia (NH3) requires six electrons and is catalyzed by the cytochrome c NO2- reductase enzyme. This biological reaction inspired scientists to explore the reduction of nitrogen oxyanions, such as nitrate (NO3-) and NO2- in wastewater, to produce the more valuable NH3 product. It is widely known that copper (Cu)-based nanoparticles (NPs) are selective for the NO3- reduction reaction (NO3-RR), but the NO2-RR has not been well explored. Therefore, we attempted to address the electrocatalytic conversion of NO2- to NH3 using Cu@Cu2O core-shell NPs to simultaneously treat wastewater by removing NO2- and producing valuable NH3. The Cu@Cu2O core-shell NPs were constructed using the pulsed laser ablation of Cu sheet metal in water. The core-shell nanostructure of these particles was confirmed by various characterization techniques. Subsequently, the removal of NO2- and the ammonium (NH4+)-N yield rate were estimated using the Griess and indophenol blue methods, respectively. Impressively, the Cu@Cu2O core-shell NPs exhibited outstanding NO2-RR activity, demonstrating a maximum NO2- removal efficiency of approximately 94% and a high NH4+-N yield rate of approximately 0.03 mmol h-1.cm-2 at -1.6 V vs. a silver/silver chloride reference electrode under optimal conditions. The proposed NO2-RR mechanism revealed that the (111) facet of Cu favors the selective conversion of NO2- to NH3 via a six-electron transfer. This investigation may offer a new insight for the rational design and detailed mechanistic understanding of electrocatalyst architecture for the effective conversion of NO2- to NH4+.


Subject(s)
Ammonium Compounds , Nanostructures , Ammonia/chemistry , Copper/chemistry , Cytochromes c/metabolism , Indophenol , Lasers , Nitrates/analysis , Nitrites , Nitrogen , Nitrogen Dioxide , Oxidation-Reduction , Oxidoreductases/metabolism , Silver , Wastewater , Water
2.
Environ Res ; 203: 111841, 2022 01.
Article in English | MEDLINE | ID: mdl-34380049

ABSTRACT

TiO2, ZnO, and SnO2 metal oxides were synthesized by the sol-gel method and heterojunctions were fabricated by combining TiO2 with either ZnO or SnO2 in a 1:1 ratio using mechanochemical ball milling process. The ball milling process promotes phase transition of TiO2 from anatase to rutile and yields ternary heterojunction of the type TiO2(A)/TiO2(R)/ZnO and TiO2(A)/TiO2(R)/SnO2 (A-anatase and R-rutile). These ternary heterojunctions were characterized by various analytical techniques and its photocatalytic efficiency is evaluated using 4-Chloro Phenol as a model compound under UV and solar light. The enhanced catalytic activity of TiO2(A)/TiO2(R)/ZnO heterojunction is attributed to the formation of Ti3+-Vo defect states which leads to the efficient charge carrier separation. During the ball milling process severe crystal deformation takes place in TiO2 and ZnO lattices by creating crystal lattice distortion which leads to the formation of defects due to valency mismatch between Ti4+ and Zn2+. A mechanistic pathway is proposed for the enhanced photocatalytic activity of the ternary heterojunctions.


Subject(s)
Zinc Oxide , Light , Semiconductors , Titanium
3.
J Hazard Mater ; 420: 126648, 2021 10 15.
Article in English | MEDLINE | ID: mdl-34329090

ABSTRACT

The intensive research on the synthesis and characterization of gold (Au) nanostructures has been extensively documented over the last decades. These investigations allow the researchers to understand the relationships between the intrinsic properties of Au nanostructures such as particle size, shape, morphology, and composition to synthesize the Au nano/hybrid nanostructures with novel physicochemical properties. By tuning the properties above, these nanostructures are extensively employed to detect and remove trace amounts of toxic pollutants from the environment. This review attempts to document the achievements and current progress in Au-based nanostructures, general synthetic and fabrication strategies and their utilization in electrochemical sensing and environmental remediation applications. Additionally, the applications of Au nanostructures (e.g., as adsorbents, sensing platforms, catalysts, and electrodes) and advancements in the field of electrochemical sensing of different target analytes (e.g., proteins, nucleic acids, heavy metals, small molecules, and antigens) are summarized. The literature survey concludes the existing methods for the detection of toxic contaminants at various concentration levels. Finally, the existing challenges and future research directions on electrochemical sensing and degradation of toxic contaminants using Au nanostructures are defined.


Subject(s)
Biosensing Techniques , Environmental Pollutants , Nanostructures , Catalysis , Electrochemical Techniques , Electrodes , Gold
4.
Environ Res ; 197: 111079, 2021 06.
Article in English | MEDLINE | ID: mdl-33775684

ABSTRACT

In this study, 2D/2D/2D heterostructured r-GO/LTH/ZnO/g-C3N4 nanohybrid were synthesized through hydrothermal method. The strong electrostatic interaction between the negatively charged g-C3N4 and r-GO nanosheets with positively charged layered triple hydroxide (LTH) nanosheets are effectively influences the successful formation of heterojunction. The LTH nanosheets are well spread on the g-C3N4 nanosheets combined with r-GO. In particular, the as prepared heterojunction shows a better photocatalytic degradation activity compared to pristine samples and the significant enhancement in the photocatalytic performance is mainly accredited to the large interfacial charge transition of photogenerated charge carriers under the visible light irradiation. Although the 2D/2D/2D heterojunction effectively hinders the charge carrier recombination resulting high photocatalytic activity with good stability. In addition, the r-GO supported LTH/ZnO/g-C3N4 heterojunction shows high photo-stability after sequential experimental runs with no obvious change in the dye degradation process. Consequently, the role of active species was investigated over the r-GO/LTH/ZnO/g-C3N4 heterojunction with the help of different scavengers.


Subject(s)
Zinc Oxide , Catalysis , Graphite , Hydroxides , Light
5.
Chemosphere ; 271: 129475, 2021 May.
Article in English | MEDLINE | ID: mdl-33460899

ABSTRACT

In this present work, we report the green synthesis of mixed bimetal oxides (CuO/NiO) for the efficient reduction of toxic nitrophenols (NP, DNP and TNP) in aqueous medium. The CuO/NiO NPs were synthesized by green hydrothermal method combined calcination process. The physiochemical properties of the synthesized CuO/NiO NPs were systematically characterized by using XRD, XPS, FTIR, SEM, and HR-TEM techniques. The calcinated CuO/NiO NPs XRD pattern and SEM morphology show the high crystalline nature than the non-calcinated. Whereas, the XPS and FTIR results confirmed the formation of the metal oxide bonding and the interaction of the bimetals. The HR-TEM images showed the spherical crystals with average particle size about 25 nm. In addition, the SAED pattern confirmed the polycrystalline nature of CuO/NiO NPs. The catalytic reduction of nitro compounds to amino derivative was studied with reducing agent (NaBH4). The CuO/NiO NPs showed the high catalytic activity and completed the reduction reaction of NP, DNP and TNP with in 2, 5 and 10 min respectively. In addition, CuO/NiO NPS exhibited the excellent kinetic rate constant k value about 1.519, 0.5102, 0.4601 min-1 for NP, DNP and TNP respectively. Furthermore, the conversion product aminophenol was observed for these three nitro compounds. The proposed CuO/NiO NPs showed excellent crystal stability after the nitrophenol reduction reactions. An inexpensive CuO/NiO NPs is a promising catalysts for reduction of toxic nitro compounds to useful products in aqueous or non-aqueous medium.


Subject(s)
Metal Nanoparticles , Nanoparticles , Catalysis , Copper , Nitro Compounds
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