Sustainable removal of nitrite waste to value-added ammonia on Cu@Cu2O core-shell nanostructures by pulsed laser technique.

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+.

Solvent-mediated synthesis of BiOI with a tunable surface structure for effective visible light active photocatalytic removal of Cr(VI) from wastewater.

The present study investigated the effect of various solvents on the tunable surface morphology and photocatalytic activity (PCA) of bismuth oxyiodide (BiOI), which could be used for the reduction of Cr(VI) under visible light irradiation (VLI). BiOI samples exhibiting different morphologies, i.e., two-dimensional square-like nanosheet and three-dimensional hierarchical flower-like morphology, were synthesized by a hydro/solvothermal process using different solvents, namely H2O, MeOH, EtOH, and ethylene glycol (EG). The crystal structure, surface morphology, surface area, light-absorption capability, and recombination rate of the photogenerated charge carriers were examined by X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller analysis, UV-vis diffuse reflectance spectroscopy, photoluminescence, and transient photocurrent analyses, respectively. The BiOI sample fabricated in EG showed excellent photocatalytic efficiency (~99%) for the reduction of Cr(VI) after 90 min under VLI. The enhanced PCA demonstrated that the high surface area and well-structured surface characteristics of flower-like 3D BiOI microspheres played important roles in the photoreduction process. Moreover, a plausible mechanism for the reduction of Cr(VI) over the EG-BiOI photocatalyst was proposed. The results of the PCA evaluation and recycle test revealed that 3D EG-BiOI microspheres could serve as promising materials for the efficient removal of Cr(VI) from wastewater. Additionally, EG-BiOI could be utilized in other environmental remediation processes.

Pulsed laser-assisted synthesis of metal and nonmetal-codoped ZnO for efficient photocatalytic degradation of Rhodamine B under solar light irradiation.

Solar light-active silver nanoparticle (Ag NP) and nonmetal nitrogen (N)-codoped zinc oxide (ZnO:N/Ag) nanocomposites were fabricated by a pulsed laser-assisted method. N was considered as a promising candidate for tailoring the bandgap of ZnO due to the similar atomic radius as well as lower ionization energy and electronegativity compared to oxygen, which resulted in the formation of a shallow acceptor level in ZnO. Moreover, Ag NPs could enhance the optical properties of the ZnO materials as a consequence of the surface plasmon resonance (SPR) effect. The synthesized ZnO:N/Ag composite materials were characterized by X-ray diffraction (XRD), micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray spectroscopy (EDS), UV-vis diffuse reflectance spectroscopy (UV-DRS), and photoluminescence (PL) analysis. The photocatalytic activity of the ZnO:N/Ag materials was evaluated for the efficient degradation of Rhodamine B (Rh.B) under solar light irradiation. The optimized ZnO:N/Ag-2 nanocomposite exhibited six times higher Rh·B degradation rate than pure ZnO. This was attributed to the enhanced absorption behavior in the solar region as well as the formation of the Schottky junction between ZnO:N and Ag NPs, which resulted in effective charge separation. In addition, the scavenger study revealed that •O2- radicals facilitated the degradation of Rh.B. The reusability test of the ZnO:N/Ag nanocomposite confirmed high photostability and efficiency of the material in each successive cycle. The present investigation illustrates a rational design of metal and nonmetal-codoped ZnO nanostructures employing a pulsed laser-assisted technique for effective application in photocatalytic remediation of wastewater.

Eco-friendly synthesis of lignin mediated silver nanoparticles as a selective sensor and their catalytic removal of aromatic toxic nitro compounds.

The development of an eco-friendly and reliable process for the production of nanomaterials is essential to overcome the toxicity and exorbitant cost of conventional methods. As such, a facile and green synthesis method is introduced for the preparation of lignin mediated silver nanoparticles (L-Ag NPs). This is produced by reducing Ag precursors using lignin biopolymers which are formulated by pulsed laser irradiation and an ultrasonication process. Lignin operates as both a reducing and stabilizing agent. The various analytical techniques of ultraviolet-visible spectroscopy, transmission electron microscope and X-ray diffractometer studies were employed to verify the formation of non-aggregated spherical L-Ag NPs with an average size as small as 7-8 nm. The selective sensing capability of the synthesized L-Ag NPs was examined for the detection of hydrogen peroxide and mercury ions in an aqueous environment. Furthermore, the superior catalytic performance of L-Ag NPs was demonstrated by the rapid conversion of toxic 4-nitrophenol and nitrobenzene as targeted pollutants to the corresponding amino compounds. A plausible catalytic reduction mechanism for the removal of toxic nitro-organic pollutants over L-Ag NPs is proposed. This research coincides with existing studies and affirms that L-Ag NPs are an effective sensor that be applied as a catalytic material within environmental remediation and also alternative biomedical applications.

Efficient recovery of palladium nanoparticles from industrial wastewater and their catalytic activity toward reduction of 4-nitrophenol.

Discharge of heavy metals from various sources of industrial wastewater poses significant environmental and health concerns. Thus, efficient recovery of precious metals from wastewater employing sustainable, rapid, and cost-effective treatment methods is highly desirable. In this work, palladium nanoparticles (Pd NPs) were successfully recovered from industrial wastewater using a pulsed laser process in the absence of additives or reducing agents. Notably, the developed approach is faster and more environmentally friendly than other conventional recovery methods. The recovered Pd NPs were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and inductively coupled plasma optical emission spectroscopy (ICP-OES). Various pulsed laser parameters (i.e., laser wavelength, power, and irradiation time) were optimized to obtain ideal conditions for the pulsed laser ablation process. Effective recovery of the Pd metal from industrial wastewater was achieved at a laser wavelength of 355 nm, power of 40 mJ/pulse, and irradiation time of 30 min. The Pd NPs exhibited excellent catalytic activity toward the reduction of 4-nitrophenol. Thus, the recovered materials showed remarkable potential for application in degradation of toxic aromatic nitro compounds in the environment.