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.

Laser-Synthesized Ru-Anchored Few-Layer Black Phosphorus for Superior Hydrogen Evolution: Role of Acoustic Levitation.

Electrochemical water splitting, driven by processed catalysts, is the most reasonable method for hydrogen production. This study demonstrates an activation phenomenon with ruthenium (Ru) nanoclusters on few-layered black phosphorus (BP), greatly enhancing the electrocatalytic hydrogen evolution reaction (HER). Efficient BP exfoliation was achieved using acoustic levitators and pulsed laser irradiation in liquids (PLIL), yielding charge-transfer Ru-nanoclusters on modulated surfaces. Various PLIL parameters were examined for the optimal BP sheet size. After ruthenization, Ru's d-band center facilitated hydrogen adsorption via Ru-H bonding. Synergy between BP's charge-carrier properties and Ru's active sites boosted HER kinetics with an ultralow overpotential of 84 mV at 10 mA/cm2 in KOH. Additionally, the RuO2 || RuBP-2 electrolyzer demonstrated remarkable overall water splitting performance at ∼1.60 V at 10 mA/cm2. These results highlight the pivotal role of metal nanoclusters on exfoliated BP surfaces and offer a refined strategy for high-density electrocatalysts in energy conversion.

In-situ monitoring of thiazine molecular aggregation in various solvents via a free-standing acoustic levitator.

In this work, we explored the in-situ reaction modeling of the molecular self-aggregation of methylene blue (MB), which is a cationic thiazine dye, in different solvents via a container-less acoustic levitator by floating of a single droplet. Our in-situ spectroscopic study revealed that the dimer essentially has a sandwich structural geometry with a deviation from parallel stacking and horizontal arrangements in the molecular planes. The real time conversion of the monomer in MB into a dimer and their dynamics in water and ethanol media were monitored using a free-standing acoustic levitator droplet system. The absorption spectra revealed changes in the two resolved peaks (monomer and dimer) and orderliness when water and ethanol were used as the media. Interestingly, the enhancement in the dimerization of MB could be attributed to droplet evaporation, which is difficult to observe in typical reactor containers. Moreover, acidic protonation resulted in a change in the aggregation orientation direction of the MB molecules, forming an unusual J-aggregation. Theoretical DFT calculations revealed that MB underwent typical H-aggregation and J-aggregation in the different solvent environments, and their orientations well matched the spectroscopic data.

Electrochemical detection of arsenic (III) hazardous chemicals using cubic CsPbBr3 single crystals: Structural insights from DFT study.

Long-term exposure to the highly toxic heavy metal arsenic can harm ecological systems and pose serious health risks to humans. Arsenic pollutant in water and the food chain must be addressed, and active prompt detection of As(III) is essential. The development of an effective detection method for As(III) ions is urgently needed to slow the alarming growth of arsenic pollution in the environment and safeguard the well-being of future generations. This study presents the results of our exhaustive investigation into cubic CsPbBr3 single crystals, the glassy carbon (GC) electrode modification with CsPbBr3 single crystals prepared by direct solvent evaporation, as well as our observations of the material's remarkable electrocatalytic properties and exceptional anti-interference sensing of As(III) ions in neutral pH media. The developed CsPbBr3/GC is exceptionally useful for the ultra-sensitive and specific identification of arsenic in water, exhibiting a detection limit of 0.381 µmol/L, a rapid response across a defined range of 0.1-25 µmol/L, and an ultra-sensitivity of 0.296 µA/µmolL-1. CsPbBr3/GCE (prepared without a specific reagent) is superior to other modified electrodes used as sensors in electrocatalytic activity, detection limit, analytical sensitivity, and stability response.

In situ studies on free-standing synthesis of nanocatalysts via acoustic levitation coupled with pulsed laser irradiation.

Acoustic levitation is a distinctive and versatile tool for levitating and processing free-standing single droplets and particles. Liquid droplets suspended in an acoustic standing wave provide container-free environments for understanding chemical reactions by avoiding boundary effects and solid surfaces. We attempted to use this strategy for the production of well-dispersed uniform catalytic nanomaterials in an ultraclean confined area without the addition of external reducing agents or surfactants. In this study, we report on the synthesis of gold and silver nanoparticles (NPs) via acoustic levitation coupled with pulsed laser irradiation (PLI). In situ UV-Visible and Raman spectroscopic techniques were performed to monitor the formation and growth of gold and silver NPs. The PLI was used for the photoreduction of targeted metal ions present in the levitated droplets to generate metal NPs. Additionally, the cavitation effect and bubble movement accelerate the nucleation and decrease the size of NPs. The synthesized Au NPs with âˆ¼ 5 nm size showed excellent catalytic behavior towards the conversion of 4-nitrophenol to 4-aminophenol. This study may open a new door for synthesizing various functional nanocatalysts and for achieving new chemical reactions in suspended droplets.

Moving beyond Ti2C3Tx MXene to Pt-Decorated TiO2@TiC Core-Shell via Pulsed Laser in Reshaping Modification for Accelerating Hydrogen Evolution Kinetics.

Phase engineering of nanocatalysts on specific facets is critical not only for enhancing catalytic activity but also for intensely understanding the impact of facet-based phase engineering on electrocatalytic reactions. In this study, we successfully reshaped a two-dimensional (2D) MXene (Ti3C2Tx) obtained by etching Ti3AlC2 MAX via a pulsed laser irradiation in liquid (PLIL) process. We produced a TiO2@TiC core-shell structure in spheres with sizes of 200-350 nm, and then ∼2 nm ultrasmall Pt NPs were decorated on the surface of the TiO2@TiC core-shell using the single-step PLIL method. These advances allow for a significant increase in electrocatalytic hydrogen evolution reaction (HER) activity under visible light illumination. The effect of optimal Pt loading on PLIL time was identified, and the resulting Pt/TiO2@TiC/Pt-5 min sample demonstrated outstanding electrochemical and photoelectrochemical performance. The photoelectrochemical HER activity over Pt/TiO2@TiC/Pt-5 min catalyst exhibits a low overpotential of 48 mV at 10 mA/cm2 and an ultralow Tafel slope of 54.03 mV/dec with excellent stability of over 50 h, which is hydrogen production activity even superior to that of the commercial Pt/C catalysts (55 mV, 62.45 mV/dec). This investigation not only serves as a potential for laser-dependent phase engineering but also provides a reliable strategy for the rational design and fabrication of highly effective nanocatalysts.

Current trends and prospects in catalytic upgrading of lignocellulosic biomass feedstock into ultrapure biofuels.

Eco-friendly renewable energy sources have recommended as fossil fuel alternatives in recent years to reduce environmental pollution and meet future energy demands in various sectors. As the largest source of renewable energy in the world, lignocellulosic biomass has received considerable interest from the scientific community to advance the fabrication of biofuels and ultrafine value-added chemicals. For example, biomass obtained from agricultural wastes could catalytically convert into furan derivatives. Among furan derivatives, 5-hydroxymethylfurfural (HMF) and 2, 5-dimethylfuran (DMF) are considered the most useful molecules that can be transformed into desirable products such as fuels and fine chemicals. Because of its exceptional properties, e.g., water insolubility and high boiling point, DMF has studied as the ideal fuel in recent decades. Interestingly, HMF, a feedstock upgraded from biomass sources can easily hydrogenate to produce DMF. In the present review, the current state of the art and studies on the transformation of HMF into DMF using noble metals, non-noble metals, bimetallic catalysts, and their composites have discussed elaborately. In addition, comprehensive insights into the operating reaction conditions and the influence of employed support over the hydrogenation process have demonstrated.

Correction: Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries.

Correction for 'Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries' by Mohan Gopalakrishnan et al., Nanoscale, 2022, 14, 17908-17920, https://doi.org/10.1039/D2NR04933C.

Modulating the Combinatorial Target Power of MgSnN2 via RF Magnetron Sputtering for Enhanced Optoelectronic Performance: Mechanistic Insights from DFT Studies.

The unique structural features of many ternary nitride materials with strong chemical bonding and band gaps above 2.0 eV are limited and are experimentally unexplored. It is important to identify candidate materials for optoelectronic devices, particularly for light-emitting diodes (LEDs) and absorbers in tandem photovoltaics. Here, we fabricated MgSnN2 thin films, as promising II-IV-N2 semiconductors, on stainless-steel, glass, and silicon substrates via combinatorial radio-frequency magnetron sputtering. The structural defects of the MgSnN2 films were studied as a function of the Sn power density, while the Mg and Sn atomic ratios remained constant. Polycrystalline orthorhombic MgSnN2 was grown on the (120) orientation within a wide optical band gap range of ∼2.20-2.17 eV. The carrier densities of 2.18× 1020 to 1.02 × 1021 cm-3, mobilities between 3.75 and 2.24 cm2/Vs, and a decrease in resistivity from 7.64 to 2.73 × 10-3 Ω cm were confirmed by Hall-effect measurements. These high carrier concentrations suggested that the optical band gap measurements were affected by a Burstein-Moss shift. Furthermore, the electrochemical capacitance properties of the optimal MgSnN2 film exhibited an areal capacitance of 152.5 mF/cm2 at 10 mV/s with high retention stability. The experimental and theoretical results showed that MgSnN2 films were effective semiconductor nitrides toward the progression of solar absorbers and LEDs.

Atomic layer encapsulation of ferrocene into zeolitic imidazolate framework-67 for efficient arsenic removal from aqueous solutions.

Arsenic (As(V))-contaminated water is a major global threat to human health and the ecosystem because of its enormous toxicity, carcinogenicity, and high distribution in water streams. Thus, As(V) removal in the environmental samples has received considerable attention. Till now, numerous metal-organic framework materials have been used for the As(V) removal from the aqueous medium, but low As(V) removal and instability of the adsorbents have severely cut off their practical applications. In this study, a ferrocene-encapsulated zeolitic imidazolate framework-67 (Fc-ZIF-67) material was synthesized for As(V) removal from an aqueous solution at neutral pH using a simple solution mixing process. The ferrocene encapsulation provides water-stable and structural defects to ZIF-67. Furthermore, the ferrocene molecule and imidazole linker can enhance As(V) adsorption via both chemisorption and physisorption. The novel Fc-ZIF-67 adsorbent exhibited superior As(V) adsorption performance with an adsorption capacity of 63.29 mg/g at neutral pH. The Langmuir and Freundlich isotherm models were also used to analyze adsorption behavior.

Construction of direct FeMoO4/g-C3N4-2D/2D Z-scheme heterojunction with enhanced photocatalytic treatment of textile wastewater to eliminate the toxic effect in marine environment.

A novel FeMoO4/g-C3N4-2D/2D Z-scheme heterojunction photocatalyst was prepared via wet chemical method. The observed structural morphology of FeMoO4/g-C3N4 reveals the 2D-iron molybdate (FeMoO4) nanoplates compiled with the 2D-graphitic carbon nitride (g-C3N4) nanosheets like structure. The photocatalytic activity of the g-C3N4, FeMoO4, and FeMoO4/g-C3N4 composites were studied via the degradation of Rhodamine B (RhB) as targeted textile dye under visible light irradiation (VLI). The optimal FeMoO4/g-C3N4 (1:3 ratio of g-C3N4 and FeMoO4) composite show an enhanced degradation performance with rate constant value of 0.02226 min-1 and good stability even after three cycles. Thus, the h+ and O2•－are the key radicals in the degradation of RhB under VLI. It is proposed that the FeMoO4/g-C3N4 Z-scheme heterojunction effectively enhances the transfer and separation ability of e-/h+ pairs, by the way increasing the photocatalytic efficiency towards the RhB degradation. Thus, the newly constructed Z-scheme FeMoO4/g-C3N4 heterojunction photocatalyst is a promising material for the remediation of wastewater relevant to elimination of toxic effect in marine environment.

Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries.

Due to their affordability and good catalytic activity for oxygen reactions, MOF-derived carbon composites containing metal alloys have piqued interest. However, during synthesis, MOFs have the disadvantage of causing significant carbon evaporation, resulting in a reduction of active sites and durability. This study proposes tailoring the molecular structure of MOFs by optimizing bipyridine and flexible 4-aminodiacetic terephthalic acid ligands, which have numerous coordination modes and framework structures, resulting in fascinating architectures. MOF frameworks having optimized N and O units are coordinated with Co and Ni ions to provide MOF precursors that are annealed at 700 °C in argon. The MOF-derived Co9S8/Co-Nx/CoNi/Ni3S2@CNS-4 catalyst exhibits excellent catalytic activity, revealing an ORR half-wave potential of 0.86 V and an overpotential (OER) of 196 mV at 10 mA cm-2, a potential gap of 0.72 V and a Tafel slope of 79 mV dec-1. The proposed strategy allows for the rational design of N-coordinated Co and CoNi alloys attached to ultrathin N, S co-doped graphitic carbon sheets to enhance bifunctional activity and sufficient active sites. Consequently, the zinc-air battery using the synthesized catalyst shows a high peak power density of 206.9 mW cm-2 (Pt/C + RuO2 116.1 mW cm-2), a small polarization voltage of 0.96 V after 370 h at 10 mA cm-2, and an outstanding durability of over 2400 cycles (400 h). The key contributions to the superior performance are the synergetic effects of the CoNi alloys plus the N,S-incorporated carbon skeleton, due to the small charge transfer resistances and enhanced active sites of CoNi, metal-S, and pyridinic N.

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+.

Fundamentals and comprehensive insights on pulsed laser synthesis of advanced materials for diverse photo- and electrocatalytic applications.

The global energy crisis is increasing the demand for innovative materials with high purity and functionality for the development of clean energy production and storage. The development of novel photo- and electrocatalysts significantly depends on synthetic techniques that facilitate the production of tailored advanced nanomaterials. The emerging use of pulsed laser in liquid synthesis has attracted immense interest as an effective synthetic technology with several advantages over conventional chemical and physical synthetic routes, including the fine-tuning of size, composition, surface, and crystalline structures, and defect densities and is associated with the catalytic, electronic, thermal, optical, and mechanical properties of the produced nanomaterials. Herein, we present an overview of the fundamental understanding and importance of the pulsed laser process, namely various roles and mechanisms involved in the production of various types of nanomaterials, such as metal nanoparticles, oxides, non-oxides, and carbon-based materials. We mainly cover the advancement of photo- and electrocatalytic nanomaterials via pulsed laser-assisted technologies with detailed mechanistic insights and structural optimization along with effective catalytic performances in various energy and environmental remediation processes. Finally, the future directions and challenges of pulsed laser techniques are briefly underlined. This review can exert practical guidance for the future design and fabrication of innovative pulsed laser-induced nanomaterials with fascinating properties for advanced catalysis applications.

Silane-treated BaTiO3 ceramic powders for multilayer ceramic capacitor with enhanced dielectric properties.

Silane/ceramic combination provides the composites with several advantages from the advancements of new ceramic composite materials with good thermal conductivity, high mechanical and dielectric properties have wide significant applications in electrical and electronic industries. In this study, to enhance the dispersibility of dielectric barium titanate (BaTiO3) ceramic powder and additives for the fabrication of multilayer ceramic capacitors (MLCCs), surface treatment of the precursor of ceramic powder was performed using silane coupling agents. Dielectric ceramic sheets fabricated from ceramic powders that had been surface-treated with different amounts of N-[3-(trimethoxysilyl)propyl]aniline (TMSPA) which increased the surface gloss. In particular, the dielectric properties of the multilayer ceramic sheet fabricated by stacking sheets from the TMSPA-treated ceramic powder sintering at 1200 °C, it was confirmed that the dielectric constant increased from 881 to 2382 and the dielectric loss dropped from 1.96 to 1.34% with utilization of the TMSPA treatment. The physical and dielectric properties of the TMSPA-treated multilayer ceramic sheet were also determined by Fourier-transform infrared spectroscopy, X-ray diffraction, field-emission scanning electron microscopy, glossmetry, and electrochemical impedance analysis. The results revealed that the TMSPA-modified BaTiO3 surfaces considerably increased the dielectric property of the fabricated nanocomposite.

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.

Improved visible light photocatalytic degradation of yttrium doped NiMgAl layered triple hydroxides for the effective removal of methylene blue dye.

Fabrication of layered triple hydroxides (LTH) is a typical and remarkable approach to produce new functionalities passionately investigated for photocatalytic removal of organic pollutants from industrial wastewater. The hydrothermal method was used to prepare different weight percentages of yttrium (Y) doped NiMgAl LTH. The structural, functional, optical, and morphological properties of the prepared samples were investigated using X-ray diffraction, Fourier transformed-infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, and scanning electron microscopy. The photocatalytic degradation of the different percentages of Y-doped LTH samples were assessed through the photocatalytic degradation of methylene blue dye under the visible light irradiation. When compared to other lower concentrations of Y doping, the photocatalytic degradation efficiency of 1 wt.% Y-doped LTH was higher. Thus, the optimized LTH's improved photocatalytic performance was attributed to increased visible light absorption with low transmission and improved electron-hole separation.

Method development and mechanistic study on direct pulsed laser irradiation process for highly effective dechlorination of persistent organic pollutants.

Chlorine-based compounds are typical persistent organic pollutants (POPs) that are widely generated in industrial production. This paper reports an effective and rapid pulsed laser irradiation technique for the dechlorination of hexachlorobenzene (HCB), a model pollutant, without additional catalysts or supports. The effects of the laser parameters, including the laser wavelength and power, on the dechlorination efficiency, were also investigated. The optimized results showed that a lower laser wavelength of 266 nm with 10 mJ/pulse power exhibited the highest dechlorination efficiency with 95% within 15 min. In addition, the laser beam effect was examined by designing the direct-pulsed laser single and multipath irradiation system. The results showed that improving the laser beam profile resulted in more than 95% dechlorination efficiency within 5 min. Thus, the dechlorination reaction proceeded much faster as the surface area that the laser beam came in contact with increased due to the multipath system than the single pathway. Gas chromatography identified benzene as the final product of HCB with pentachlorobenzene (PCB), tetrachlorobenzene (TeCB), trichlorobenzene (TCB), dichlorobenzene (DCB), and chlorobenzene (CB) as intermediate products. The mechanism of HCB dechlorination was explained by a comparison of theoretical calculations with the experimental results. The present study reports an advanced technique for the complete dechlorination of chlorobenzenes, which holds great application potential in environmental remediation.