Deciphering Indirect Nitrite Reduction to Ammonia in High-Entropy Electrocatalysts Using In Situ Raman and X-ray Absorption Spectroscopies.

This research adopts a new method combining calcination and pulsed laser irradiation in liquids to induce a controlled phase transformation of Fe, Co, Ni, Cu, and Mn transition-metal-based high-entropy Prussian blue analogs into single-phase spinel high-entropy oxide and face-centered cubic high-entropy alloy (HEA). The synthesized HEA, characterized by its highly conductive nature and reactive surface, demonstrates exceptional performance in capturing low-level nitrite (NO2 -) in an electrolyte, which leads to its efficient conversion into ammonium (NH4 +) with a Faradaic efficiency of 79.77% and N selectivity of 61.49% at -0.8 V versus Ag/AgCl. In addition, the HEA exhibits remarkable durability in the continuous nitrite reduction reaction (NO2 -RR), converting 79.35% of the initial NO2 - into NH4 + with an impressive yield of 1101.48 µm h-1 cm-2. By employing advanced X-ray absorption and in situ electrochemical Raman techniques, this study provides insights into the indirect NO2 -RR, highlighting the versatility and efficacy of HEA in sustainable electrochemical applications.

Unraveling the Synergy of Anion Modulation on Co Electrocatalysts by Pulsed Laser for Water Splitting: Intermediate Capturing by In Situ/Operando Raman Studies.

Herein, the authors produce Co-based (Co3 (PO4 )2 , Co3 O4 , and Co9 S8 ) electrocatalysts via pulsed laser ablation in liquid (PLAL) to explore the synergy of anion modulation on phase-selective active sites in the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Co3 (PO4 )2 displays an ultralow overpotential of 230 mV at 10 mA cm-2 with 48.5 mV dec-1 Tafel slope that outperforms the state-of-the-art Ir/C in OER due to its high intrinsic activity. Meanwhile, Co9 S8 exhibits the highest HER performance known to the authors among the synthesized Co-based catalysts, showing the lowest overpotential of 361 mV at 10 mA cm-2 with 95.8 mV dec-1 Tafel slope in the alkaline medium and producing H2 gas with ≈500 mmol g-1 h-1 yield rate under -0.45 V versus RHE. The identified surface reactive intermediates over in situ electrochemical-Raman spectroscopy reveal that cobalt(hydr)oxides with higher oxidation states of Co-cation forming under oxidizing potentials on the electrode-electrolyte surface of Co3 (PO4 )2 facilitate the OER, while Co(OH)2 facilitate the HER. Notably, the fabricated two-electrode electrolyzers using Co3 (PO4 )2 , Co3 O4 , and Co9 S8 electrocatalysts deliver the cell potentials ≈2.01, 2.11, and 1.89 V, respectively, at 10 mA cm-2 . This work not only shows PLAL-synthesized electrocatalysts as promising candidates for water splitting, but also provides an underlying principle for advanced energy-conversion catalysts and beyond.

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+.

Nanogap-tailored Au nanoparticles fabricated by pulsed laser ablation for surface-enhanced Raman scattering.

Herein, gold nanoparticles (Au NPs) were synthesized by pulsed laser ablation (PLA) in a mixed-phase solvent of acetonitrile and water. The size of Au NPs and the number of graphitic carbon (GC) layers were controlled by varying the ratio of the solvent mixture. The surface-enhanced Raman scattering (SERS) of the Au NPs was investigated using 10-3 M 4-aminobenzenethiol and 10-4 M 4-nitrobenzenethiol as probe molecules. The SERS activity strongly depended on the nanogaps between particles owing to the formation of hot spots. In the present work, the nanogaps were controlled by changing the amount of GC layers. No GC layers were produced in water, resulting low SERS intensity. In contrast, Au NPs prepared in 30 vol% of acetonitrile showed significant SERS enhancement, which was attributed to the optimal size of the GC-coated NPs and a reasonable gap between them. The obtained results revealed that Au NPs produced by PLA in liquid could be applied in SERS-based microsensors.

Facile one-pot synthesis of CuCN by pulsed laser ablation in nitrile solvents and mechanistic studies using quantum chemical calculations.

Binding energies of different nitrile solvents and their utilization for CuCN formation were investigated through quantum chemical calculations. A pulsed laser ablation in liquid (PLAL) method for CuCN synthesis was developed herein. Initially, the interaction between the pulsed laser and the Cu-target generated Cu-ions and electrons at the point of contact. The laser beam also exhibited sufficient energy to dissociate the bonds of the respective solvents. In the case of acetonitrile, the oxidized Cu-ions bonded with CN- to produce CuCN with a cube-like surface structure. Other nitrile solvents generated spherically-shaped Cu@graphitic carbon (Cu@GC) nanoparticles. Thus, the production of CuCN was favorable only in acetonitrile due to the availability of the cyano group immediately after the fragmentation of acetonitrile (CH3+ and CN-) under PLAL. Conversely, propionitrile and butyronitrile released large amounts of hydrocarbons, which deposited on Cu NPs surface to form GC layers. Following the encapsulation of Cu NPs with carbon shells, further interaction with the cyano group was not possible. Subsequently, theoretical study on the binding energies of nitrile solvents was confirmed by highly correlated basic sets of B3LYP and MP2 which results were consistent with the experimental outcomes. The findings obtained herein could be utilized for the development of novel metal-polymer materials.

Production of copper nanoparticles exhibiting various morphologies via pulsed laser ablation in different solvents and their catalytic activity for reduction of toxic nitroaromatic compounds.

Comparative experiments were conducted to determine the effects of various solvents (i.e., deionized water, methanol, ethanol, 1-propanol, butanol, ethylene glycol, hexane, and acetonitrile) on the final compositions, morphologies, and catalytic activities of copper-based nanoparticles (NPs). The NPs were effectively synthesized by pulsed laser ablation (PLA) using a copper plate as the target. The obtained copper NPs were characterized utilizing various analytical techniques. It was established that the developed methodology allows for the production of NPs with different morphologies and compositions in a safe and simple manner. When laser ablation of a solid copper plate was performed in acetonitrile, the formation of copper(I) cyanide cubes was observed. On the other hand, in deionized water and methanol, spherical and rod-like particles of copper(I) and copper(II) oxide were detected, respectively. The catalytic activity of the prepared copper NPs in the reduction of aromatic nitro compounds, such as 4-nitrophenol and nitrobenzene, was also evaluated. A high k value was determined for the reduction over the copper(II) oxide NPs produced in methanol. Moreover, particles with graphitic carbon (GC) layers exhibited superior catalytic performance in the reduction of a hydrophobic substance, i.e., nitrobenzene, over the reduction of 4-nitrophenol. The enhanced catalytic activity of this catalyst may be due its unique surface morphology and the synergistic effects between the copper nanostructure and the GC layer. Lastly, a detailed reduction pathway mechanism for the catalytic reduction of 4-nitrophenol and nitrobenzene has been proposed.

Enhanced photocatalytic activity at multidimensional interface of 1D-Bi2S3@2D-GO/3D-BiOI ternary nanocomposites for tetracycline degradation under visible-light.

Structural dimensionality and surface morphology are key properties that greatly affect the functionalities of materials. Herein, we report a synthesis of dimensionally coupled ternary nanocomposites from three-dimensional (3D) bismuth oxyiodide (BiOI), two-dimensional (2D) graphene oxide (GO), and one-dimensional (1D) bismuth sulfide (Bi2S3) nanomaterials for tetracycline degradation under visible-light irradiation. The 2%-Bi2S3@1%-GO/BiOI ternary nanocomposites show higher degradation efficiency than neat 3D-BiOI. The coupling of neat 1D-Bi2S3 with the 1%-GO/BiOI binary nanocomposite does not increase the specific surface area of the resulting 2%-Bi2S3@1%-GO/3D-BiOI ternary nanocomposite, but enhances notably its charge carrier separation and migration, according to the analysis of the higher photocurrent, smaller arc radius of the electrochemical impedance spectroscopy and lower photoluminescence intensity. The observed results suggest that the combination of dimensionally coupled composites provides a synergistic effect through an efficient charge transfer process. This work offers new insights into the design and construction of dimensionally coupled ternary nanocomposites for environmental remediation applications.

Plasmonic ZnO/Au/g-C3N4 nanocomposites as solar light active photocatalysts for degradation of organic contaminants in wastewater.

In the present study, novel ZnO/Au/graphitic carbon nitride (g-C3N4) nanocomposites were fabricated via a facile and eco-friendly liquid phase pulsed laser process followed by calcination. Notably, the approach did not necessitate the use of any capping agents or surfactants. The as-prepared photocatalysts were evaluated by various electron microscopy and spectroscopy techniques. The obtained results confirmed good dispersion of the Au nanoparticles (NPs) on the surface of spherical ZnO particles deposited on the g-C3N4 nanosheets. The ZnO/Au/g-C3N4 nanocomposite exhibited substantially enhanced catalytic activity toward the degradation of methylene blue (MB) under simulated solar light irradiation. In particular, the ZnO/Au15/g-C3N4 composite containing 15 wt% Au displayed a rate constant, which was approximately 3 and 5 times greater than those of pristine g-C3N4 and ZnO, respectively. This improved photocatalytic activity of ZnO/Au15/g-C3N4 was attributed to the surface plasmon resonance of Au NPs and the synergistic effects between ZnO and g-C3N4. The boundary between ZnO/Au and g-C3N4 enabled direct migration of the photogenerated electrons from g-C3N4 to ZnO/Au, which hindered the recombination of electron-hole pairs and enhanced the carrier separation efficiency. Additionally, a plausible MB degradation mechanism over the ZnO/Au/g-C3N4 photocatalyst is proposed based on the results of the conducted scavenger study.

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.

Pulsed laser synthesis of reduced graphene oxide supported ZnO/Au nanostructures in liquid with enhanced solar light photocatalytic activity.

ZnO/Au/rGO ternary nanocomposites possessing a high photocatalytic response under solar irradiation were synthesized by a two-step process via a pulsed laser synthesis and a wet chemical process. The crystalline structure, surface morphology, size distribution, elemental composition, and optical properties of the prepared ZnO/Au/rGO ternary nanocomposites were characterized using X-ray diffraction, field-emission scanning electron microscope, high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, UV-vis diffuse reflectance spectra, and photoluminescence analysis. The photocatalytic activity of the as synthesized nanocomposites was evaluated for the degradation of methylene blue (MB) under solar light irradiation (SLI). The density of the elemental and carbonaceous components, such as the Au nanoparticles (NPs) and the rGO nano-matrix on ZnO, could be altered by changing the concentration of HAuCl4.3H2O (5, 10, 15, and 20 wt%) or rGO (2.5, 5, and 7.5 wt%) using the same synthetic processes. The ZnO/Au15/rGO5 nanocomposite showed the highest photocatalytic degradation efficiency of 95% MB after 120 min under SLI, potentially due to the increased absorption of solar light or the efficient separation and migration of charge carriers by the anchored Au NPs and rGO onto the ZnO NPs. Further, the observed results and reusability of ZnO/Au15/rGO5 makes it an exceptionally promising material for diverse applications in the field of wastewater treatment and other types of environmental remediation.