Design and Fabrication of Biomass Derived Black Carbon Modified g-C3N4/FeIn2S4 Heterojunction as Highly Efficient Photocatalyst for Wastewater Treatment.

The environmental deterioration caused by dye wastewater discharge has received considerable attention in recent decades. One of the most promising approaches to addressing the aforementioned environmental issue is the development of photocatalysts with high solar energy consumption efficiency for the treatment of dye-contaminated water. In this study, a novel low-cost π-π biomass-derived black carbon modified g-C3N4 coupled FeIn2S4 composite (i.e., FeInS/BC-CN) photocatalyst is successfully designed and fabricated that reveals significantly improved photocatalytic performance for the degradation of Eosin Yellow (EY) dye in aqueous solution. Under dark and subsequent visible light irradiation, the amount optimized composite reveals 99% removal performance for EY dye, almost three-fold compared to that of the pristine FeInS and BC-CN counterparts. Further, it is confirmed by means of the electron spin resonance spectrometry, quenching experiments, and density functional theory (DFT) calculations, that the hydroxyl radicals (•OH) and superoxide radicals (•O2 -) are the dominant oxidation species involved in the degradation process of EY dye. In addition, a systematic photocatalytic degradation route is proposed based on the resultant degradation intermediates detectedduring liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. This work provides an innovative idea for the development of advanced photocatalysts to mitigate water pollution.

Designing State-of-the-Art Gas Sensors: From Fundamentals to Applications.

Gas sensors are crucial in environmental monitoring, industrial safety, and medical diagnostics. Due to the rising demand for precise and reliable gas detection, there is a rising demand for cutting-edge gas sensors that possess exceptional sensitivity, selectivity, and stability. Due to their tunable electrical properties, high-density surface-active sites, and significant surface-to-volume ratio, nanomaterials have been extensively investigated in this regard. The traditional gas sensors utilize homogeneous material for sensing where the adsorbed surface oxygen species play a vital role in their sensing activity. However, their performance for selective gas sensing is still unsatisfactory because the employed high temperature leads to the poor stability. The heterostructures nanomaterials can easily tune sensing performance and their different energy band structures, work functions, charge carrier concentration and polarity, and interfacial band alignments can be precisely designed for high-performance selective gas sensing at low temperature. In this review article, we discuss in detail the fundamentals of semiconductor gas sensing along with their mechanisms. Further, we highlight the existed challenges in semiconductor gas sensing. In addition, we review the recent advancements in semiconductor gas sensor design for applications from different perspective. Finally, the conclusion and future perspectives for improvement of the gas sensing performance are discussed.

Thermo-Chemical Modification of Cellulose for the Adsorptive Removal of Titan Yellow from Wastewater.

This research work focuses on the isolation and thermo-chemical modification of cellulose and its application as an adsorbent for the removal of organic pollutants. The used cellulose was collected from a locally available plant (Olive Europa) commonly called Zaitoon. The stem branches of Zaitoon were collected and then kept in water for 40-45 days at room temperature to extract the cellulose fibers. These cellulose fibers were then kept in the Soxhlet apparatus for washing in n-hexane for 72 h. The purified cellulose was divided into three parts: one part was subjected to thermal activation (TAC), the second was modified chemically (CMC) with Benzyl Chloride, while the last one remained un-functionalized (UFC). All the three forms of cellulose were characterized via FTIR and SEM, then utilized for the removal of Titan Yellow (TY) dye from aqueous media via adsorption process by varying the contact time, temperature, concentration of dye and type, and dose of adsorbent. The adsorption efficiencies of all adsorbents were compared under different experimental variables. Thermally activated cellulose showed the best results for the removal of TY compared with other materials. The calculated removal percentage of TY was found to be 97.69, 94.83, 94.83, and 98% under equilibrium conditions of contact time, temperature, adsorbent dose, and TY concentration. Similarly, the uptake capacities of TAC under optimal experimental conditions were found to be 19.56, 18.96, 18.52, and 18.75 mg/g. Thermodynamic studies of TAC, CMC, and UFC showed that the values of ΔG are negative, while those of ΔH and ΔS are positive in all cases and at all temperatures. This indicates that the TY elimination process is endothermic and spontaneous with an entropy-driven nature. The obtained results indicate that the as-fabricated low-cost biomaterials can effectively remove dyes from wastewater through physicochemical interactions. The removal process was influenced by the nature of the adsorbent and the operating variables.

Biosynthesis of Nanoparticles Using Plant Extracts and Essential Oils.

Plant extracts and essential oils have a wide variety of molecules with potential application in different fields such as medicine, the food industry, and cosmetics. Furthermore, these plant derivatives are widely interested in human and animal health, including potent antitumor, antifungal, anti-inflammatory, and bactericidal activity. Given this diversity, different methodologies were needed to optimize the extraction, purification, and characterization of each class of biomolecules. In addition, these plant products can still be used in the synthesis of nanomaterials to reduce the undesirable effects of conventional synthesis routes based on hazardous/toxic chemical reagents and associate the properties of nanomaterials with those present in extracts and essential oils. Vegetable oils and extracts are chemically complex, and although they are already used in the synthesis of nanomaterials, limited studies have examined which molecules are effectively acting in the synthesis and stabilization of these nanostructures. Similarly, few studies have investigated whether the molecules coating the nanomaterials derived from these extracts and essential oils would bring benefits or somehow reduce their potential activity. This synergistic effect presents a promising field to be further explored. Thus, in this review article, we conducted a comprehensive review addressing the main groups of molecules present in plant extracts and essential oils, their extraction capacity, and available methodologies for their characterization. Moreover, we highlighted the potential of these plant products in the synthesis of different metallic nanomaterials and their antimicrobial capacity. Furthermore, we correlated the extract's role in antimicrobial activity, considering the potential synergy between molecules from the plant product and the different metallic forms associated with nanomaterials.

Removal of Basic Fuchsin from water by using mussel powdered eggshell membrane as novel bioadsorbent: Equilibrium, kinetics, and thermodynamic studies.

This study aims to remove organic cationic dye Basic Fuchsin (BF) by adsorption onto a low cost eggshell membrane (ESM) in batch mode at 293 K. XRD analysis confirms the amorphous nature of ESM meanwhile FTIR spectroscopy reveals the presence of several functional groups such as hydroxyl (-OH), sulfhydryl (-SH), carboxyl (-COOH), and amino (-NH2). Morphological observations by SEM indicate its fibrous microstructure. BET analysis shows a surface area of 11.56 m2 g-1 and the presence of mesopores with a volume of 6.173 10-3 cm3 g-1. The value of pHPZC of ESM is 7.05. The influence of adsorbent dose, contact time, pH, temperature and dye concentration is examined. The highest adsorption capacity around 48 mg.g-1is achieved for a dye concentration 250 ppm, pH 6 and 25 °C. In addition, adsorption has been found to follow pseudo-second order kinetics. The analysis of the experimental data using linear forms based on Langmuir, Freundlich and Temkin isotherm models indicate that the best fit is obtained with Freundlich model. Thermodynamic parameters (Gibbs free energy, enthalpy, and entropy) reveal that the adsorption of BF onto ESM is an exothermic and spontaneous process. A comprehensive mechanism for BF adsorption by ESM has been proposed.

Magnesium Magic: State-of-the-Art Nanocrystalline Materials Paving the Way for Hydrogen Storage.

Hydrogen has been regarded as a promising alternative to traditional fossil fuels, presenting itself as a viable and environmentally friendly energy choice. The design and fabrication of highly efficient hydrogen storage materials is crucial to the wide utilization of hydrogen-based technologies. Magnesium-based nanocrystalline materials have received significant interest in the field of hydrogen storage due to their remarkable hydrogen storage capabilities and release efficiency. This review emphasizes on the most useful techniques including vapor deposition, sol-gel synthesis, electrochemical deposition, magnetron sputtering, and template-assisted approaches used for the fabrication of Magnesium-based nanocrystalline hydrogen storage materials (Mg-NHSMs), stressing their advantages, limitations, and recent advancements. These cutting-edge techniques demonstrate their significance in offering useful insights into the performance of Mg-NHSMs. Further, this review describes various applications of Mg-NHSMs. In addition, this review highlights the conclusion and future perspectives on the improvement of magnesium based nanocrystalline materials for efficient hydrogen storage.

New Functionalized Di-substituent Imidazolium Ionic Liquids as Superior Faster Absorbents for Carbon Dioxide Gas.

Functionalization of room temperature liquids based on disubstituted imidazolium ionic liquids represents a promising avenue for tailoring their tunable physicochemical properties and expanding their potential application as green solvents to capture carbon dioxide as a greenhouse gas. In this work, new hydroxyl functionalized imidazolium ionic liquids were prepared from condensation of ethanolamine with glyoxal and formalin in the presence of acetic acid as catalyst. The chemical modification of the hydroxyl groups with epichlorohydrine added new hydroxylpropanoxychloride groups on the imidazolium cation that were quaternized with N-methylimidazolium chloride to produce new imidazolium acetate ionic liquids. The chemical structures, thermal stability, and thermal characteristics of the prepared imidazolium ionic liquids were evaluated. The incorporation of functionalized 1-chloro-2-hydroxypropanoxy and N-methylimidazolium chloride groups into the chemical structure of the imidazolium cations improved the thermal properties of the prepared ionic liquids. The application of the prepared ionic liquids as pure or mixed solvents with saline water to capture CO2 under atmospheric and 55.2 bar pressures was evaluated at room temperature. The data indicate that the prepared ionic liquids have superior CO2 adsorption/desorption rate in short time during 30 and 15 min and that their CO2 capture efficiency increased from 6.2 to 16.8 molCO2/kgIIL and from 9.1 to 20.0 molCO2/kgIIL at atmospheric and 55.2 bar pressures, respectively.

Rapid synthesis of ZnO nanoparticles via gliding arc discharge: unveiling the impact of discharge time on particle properties and photocatalytic performance.

Herein, we present a novel approach for the synthesis of ZnO nanoparticles (ZnO NPs) using a non-thermal plasma source generated by the gliding arc discharge-air system. The effect of discharge time on the physical and optical properties, as well as the photocatalytic performance of the as-fabricated ZnO NPs, was investigated. The characterization techniques revealed that the as-synthesized ZnO exhibit hexagonal Wurtzite structure, with a wide energy gap and peak intensities of UV-vis absorption with longer discharge times. A decrease in particle size from 29 to 25 nm was also observed with increasing discharge time, while all samples were thermally stable between 25 and 700 °C. The photocatalytic performance of the ZnO NPs was evaluated by degrading Congo Red (CR) dye with a concentration of 20 ppm under sunlight at a dose of 1 mg/mL. The as-synthesized ZnO NPs revealed exceptional photocatalytic performance by degrading ~ 97% of CR dye after irradiation for 150 min. This work presents an easy and simple method for synthesizing NPs in a short time and pave the way for other potential ideas on the application of plasma gliding arc discharge.

Multifunctional assessment of copper-doped ZnO nanoparticles synthesized via gliding arc discharge plasma technique: antioxidant, antibacterial, and photocatalytic performance.

In this paper, undoped and copper-doped ZnO nanoparticles (NPs) were successfully synthesized using a gliding arc discharge (GAD) plasma technique, which is a sustainable, cost-effective, and scalable method. This method offers several advantages over traditional synthesis methods. The synthesized NPs were characterized by various techniques to understand their physicochemical properties. XRD analysis confirmed the presence of characteristic peaks of pure ZnO, while doped samples exhibited additional peaks corresponding to CuO crystal planes, indicating the successful incorporation of Cu into the lattice. As obvious, bare ZnO showed absorption peak at 378 nm corresponding to the band gap of 3.21 eV. The band gap of Cu-doped samples increased systematically, i.e., 3.35 eV for 2% Cu, 3.47 eV for 4% Cu, and 3.66 eV for 6% Cu. SEM images revealed aggregation and increase in particle size with the increasing in Cu concentration. EDAX analysis revealed a decrease in the weight percentage of oxygen and zinc with the increase in Cu concentration, suggesting structural changes within the lattice. Furthermore, the antibacterial activity against Gram-positive and Gram-negative bacteria, antioxidant activity, and photocatalytic activity against three different organic dyes such as Brilliant Cresyl Blue (BCB), Methylene Blue (MB), and Congo Red (CR) was studied. It is found that the photocatalytic activity of ZnO NPs varies with Cu concentration, leading to a decrease in its performance. The antibacterial activity of the NPs was also assessed, with undoped ZnO NPs showing dose-dependent effects against bacteria, while the Cu-doped ZnO NPs exhibited decreased efficacy. Interestingly, Cu doping significantly enhanced the antioxidant activity of the NPs compared to the undoped ZnO.

Metal/Covalent Organic Framework Encapsulated Lead-Free Halide Perovskite Hybrid Nanocatalysts: Multifunctional Applications, Design, Recent Trends, Challenges, and Prospects.

Perovskites are bringing revolutionization in a various fields due to their exceptional properties and crystalline structure. Most specifically, halide perovskites (HPs), lead-free halide perovskites (LFHPs), and halide perovskite quantum dots (HPs QDs) are becoming hotspots due to their unique optoelectronic properties, low cost, and simple processing. HPs QDs, in particular, have excellent photovoltaic and optoelectronic applications because of their tunable emission, high photoluminescence quantum yield (PLQY), effective charge separation, and low cost. However, practical applications of the HPs QDs family have some limitations such as degradation, instability, and deep trap states within the bandgap, structural inflexibility, scalability, inconsistent reproducibility, and environmental concerns, which can be covered by encapsulating HPs QDs into porous materials like metal-organic frameworks (MOFs) or covalent-organic frameworks (COFs) that offer protection, prevention of aggregation, tunable optical properties, flexibility in structure, enhanced biocompatibility, improved stability under harsh conditions, consistency in production quality, and efficient charge separation. These advantages of MOFs-COFs help HPs QDs harness their full potential for various applications. This review mainly consists of three parts. The first portion discusses the perovskites, halide perovskites, lead-free perovskites, and halide perovskite quantum dots. In the second portion, we explore MOFs and COFs. In the third portion, particular emphasis is given to a thorough evaluation of the development of HPs QDs@MOFs-COFs based materials for comprehensive investigations for next-generation materials intended for diverse technological applications, such as CO2 conversion, pollutant degradation, hydrogen generation, batteries, gas sensing, and solar cells. Finally, this review will open a new gateway for the synthesis of perovskite-based quantum dots.

Molecularly imprinted polymer composite membranes: From synthesis to diverse applications.

This review underscores the fundamentals of MIP-CMs and systematically summarizes their synthetic strategies and applications, and potential developments. MIP-CMs are widely acclaimed for their versatility, finding applications in separation, filtration, detection, and trace analysis, as well as serving as scaffolds in a range of analytical, biomedical and industrial contexts. Also characterized by extraordinary selectivity, remarkable sensitivity, and outstanding capability to bind molecules, those membranes are also cost-effective, highly stable, and configurable in terms of recognition and, therefore, inalienable in various application fields. Issues relating to the potential future for the paper are discussed in the last section with the focus on the improvement of resource practical application across different areas. Hence, this review can be seen as a kind of cookbook for the design and fabrication of MIP-CMs with an intention to expand the scope of their application.

A critical review on metal-organic frameworks (MOFs) based nanomaterials for biomedical applications: Designing, recent trends, challenges, and prospects.

Nanomaterials (NMs) have garnered significant attention in recent decades due to their versatile applications in a wide range of fields. Thanks to their tiny size, enhanced surface modifications, impressive volume-to-surface area ratio, magnetic properties, and customized optical dispersion. NMs experienced an incredible upsurge in biomedical applications including diagnostics, therapeutics, and drug delivery. This minireview will focus on notable examples of NMs that tackle important issues, demonstrating various aspects such as their design, synthesis, morphology, classification, and use in cutting-edge applications. Furthermore, we have classified and outlined the distinctive characteristics of the advanced NMs as nanoscale particles and hybrid NMs. Meanwhile, we emphasize the incredible potential of metal-organic frameworks (MOFs), a highly versatile group of NMs. These MOFs have gained recognition as promising candidates for a wide range of bio-applications, including bioimaging, biosensing, antiviral therapy, anticancer therapy, nanomedicines, theranostics, immunotherapy, photodynamic therapy, photothermal therapy, gene therapy, and drug delivery. Although advanced NMs have shown great potential in the biomedical field, their use in clinical applications is still limited by issues such as stability, cytotoxicity, biocompatibility, and health concerns. This review article provides a thorough analysis offering valuable insights for researchers investigating to explore new design, development, and expansion opportunities. Remarkably, we ponder the prospects of NMs and nanocomposites in conjunction with current technology.

Insight into microplastics in the aquatic ecosystem: Properties, sources, threats and mitigation strategies.

Globally recognized as emergent contaminants, microplastics (MPs) are prevalent in aquaculture habitats and subject to intense management. Aquaculture systems are at risk of microplastic contamination due to various channels, which worsens the worldwide microplastic pollution problem. Organic contaminants in the environment can be absorbed by and interact with microplastic, increasing their toxicity and making treatment more challenging. There are two primary sources of microplastics: (1) the direct release of primary microplastics and (2) the fragmentation of plastic materials resulting in secondary microplastics. Freshwater, atmospheric and marine environments are also responsible for the successful migration of microplastics. Until now, microplastic pollution and its effects on aquaculture habitats remain insufficient. This article aims to provide a comprehensive review of the impact of microplastics on aquatic ecosystems. It highlights the sources and distribution of microplastics, their physical and chemical properties, and the potential ecological consequences they pose to marine and freshwater environments. The paper also examines the current scientific knowledge on the mechanisms by which microplastics affect aquatic organisms and ecosystems. By synthesizing existing research, this review underscores the urgent need for effective mitigation strategies and further investigation to safeguard the health and sustainability of aquatic ecosystems.

Effective Removal of Nile Blue Dye from Wastewater using Silver-Decorated Reduced Graphene Oxide.

Nile blue (NB) dye is a highly toxic substance that when discharged into sewage presents a significant risk to the environment and human health. Carbon-based nanomaterials, such as graphene oxide (GO), reduced graphene oxide (rGO), and their nanocomposites, offer considerable potential for eliminating hazardous pollutants from aqueous systems. In this study, we have successfully fabricated bare GO and rGO, and then, the rGO was decorated with silver (Ag) nanoparticles to develop the Ag-rGO composite. The as-prepared materials were characterized by various techniques, such as UV-visible (UV-vis) and Fourier transform infrared (FTIR) spectroscopies, X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and scanning electron microscopy (SEM) to elucidate their structure, morphology, and chemical composition. The pollutant removal performance of the as-prepared materials was evaluated through a batch approach under the effect of various experimental variables for removal of NB dye from wastewater. As obvious, the Ag-rGO composite revealed exceptional performance for NB dye removal from wastewater, with a maximum removal percentage of 94% within 60 min, which is remarkably higher than those of the rGO (i.e., 59%) and GO (i.e., 22%), under the same experimental conditions. The adsorption data was analyzed with thermodynamics, isotherms, and kinetics models to better understand the physicochemical mechanisms driving the effective removal of the NB dye. The results reveal that Ag-rGO nanocomposite exhibit excellent adsorption ability as well as favorable thermodynamic and kinetic parameters for NB dye removal. It was also found that the presence of light enhanced the adsorptive removal of NB while using Ag-rGO as an adsorbent. The present study noted significant reusability of the Ag-rGO nanocomposite, likely due to minimal Ag leaching and/or the robust stability of the Ag-rGO. It is suggested that Ag-rGO-based hybrid materials could serve as promising candidates for efficiently adsorbing and catalytically removing various toxic pollutants from wastewater.

Preparation of visible-light active MOFs-Perovskites (ZIF-67/LaFeO3) nanocatalysts for exceptional CO2 conversion, organic pollutants and antibiotics degradation.

Modern industries rapid expansion has heightened energy needs and accelerated fossil fuel depletion, contributing to global warming. Additionally, organic pollutants present substantial risks to aquatic ecosystems due to their stability, insolubility, and non-biodegradability. Scientists are currently researching high-performance materials to address these issues. LaFeO3 nanosheets (LFO-NS) were synthesized in this study using a solvothermal method with polyvinylpyrrolidone (PVP) as a soft template. The LFO-NS demonstrate superior performance, large surface area and charge separation than that of LaFeO3 nanoparticles (LFO-NP). The LFO-NS performance is further upgraded by incorporating ZIF-67. Our results confirmed the ZIF-67/LFO-NS nanocomposite have superior performances than pure LFO-NP and ZIF-67. The integration of ZIF-67 has enhanced the charge separation and promote the surface area of LFO-NSwhich was confirmed by various characterization techniques including TEM, HRTEM, DRS, EDX, XRD, FS, XPS, FT-IR, BET, PL, and RAMAN. The 5ZIF-67/LFO-NS sample showed significant activities for CO2 conversion, malachite green degradation, and antibiotics (cefazolin, oxacillin, and vancomycin) degradation. Furthermore, stability tests have confirmed that our optimal sample very active and stable. Furthermore, based on scavenger experiments and the photocatalytic degradation pathways, it has been established that H+ and •O2- are vital in the decomposition of MG and antibiotics. Our research work will open new gateways to prepare MOFs-Perovskites nanocatalysts for exceptional CO2 conversion, organic pollutants and antibiotics degradation.

Electrophoretic deposition of polyvinyl alcohol, C-H NRs along with moringa on an SS substrate for orthopedic implant applications.

Metals are commonly used in bone implants due to their durability and load-bearing capabilities, yet they often suffer from biofilm growth and corrosion. To overcome these challenges, implants with enhanced biocompatibility, bioactivity, and antimicrobial properties are preferred. Stainless steel (SS) implants are widely favored in orthopedics for their mechanical strength and cost-effectiveness. To address the issues related to SS implants, we developed composite coatings using synthetic biopolymer polyvinyl alcohol (PVA), calcium hydrate (C-H) nanorods for improved bioactivity and antibacterial properties, and Moringa oleifera to enhance osteogenic induction. These coatings were deposited on 316L SS through electrophoretic deposition (EPD), providing protection against body fluids and enhancing the corrosion resistance of the SS. X-ray diffraction (XRD) confirmed the presence of the desired tobermorite crystal structure, while scanning electron microscopy (SEM) revealed nanorod-like C-H structures, a film thickness of 29 microns, and a hedgehog-like morphology in the composite particles. The coated sample demonstrated a contact angle of 64°, optimal for protein attachment and cellular uptake. Additionally, the coating exhibited strong adhesion with less than 5% damage observed in cross-cut hatch testing and appropriate surface roughness for protein attachment. Differential Scanning Calorimetry (DSC) and thermogravimetric analysis (TGA) assessed the thermal response of the materials. The coating also showed antibacterial activity against both Gram-negative and Gram-positive bacteria. Furthermore, the sample exhibited rapid bioactivity by forming a hydroxyapatite (HA) layer within 24 hours, with 35.4% degradability within 24 hours and 44.5% within 48 hours. These findings confirm that the composite film enhances the biocompatibility, bioactivity, and antibacterial properties of SS orthopedic implants in a cost-effective manner.

Tailoring NiCoCu layered double hydroxide with Ag-citrate/polyaniline/functionalized SWCNTs nanocomposites for supercapacitor applications.

Supercapacitors have substantially altered the landscape of sophisticated energy storage devices with their exceptional power density along with prolonged cyclic stability. On the contrary, their energy density remains low, requiring research to compete with conventional battery storage devices. This study addresses the disparities between energy and power densities in energy storage technologies by exploring the integration of layered double hydroxides (LDH) and highly conductive materials to develop an innovative energy storage system. Four electrodes were fabricated via a hydrothermal process using NiCoCu LDH, Ag-citrate, PANI, and f-SWCNTs. The optimal electrode demonstrated exceptional electrochemical properties; at 0.5 A g-1, it possessed specific capacitances of 807 F g-1, twice as high as those of the pure sample. The constructed asymmetric supercapacitor device attained energy densities of 62.15 W h kg-1 and 22.44 W h kg-1, corresponding to power densities of 1275 W kg-1 and 11 900 W kg-1, respectively. Furthermore, it maintained 100% cyclic stability and a coulombic efficiency of 95% for 4000 charge-discharge cycles. The concept of a supercapacitor of the hybrid grade was reinforced by power law investigations, which unveiled b-values in the interval of 0.5 to 1. This research emphasizes the considerable potential of supercapacitor-grade NiCoCu LDH/Ag-citrate-PANI-f-SWCNTs nanocomposites for superior rate performance, robust cycle stability, and enhanced energy storage capacity.

Manipulation of Electron Spins with Oxygen Vacancy on Amorphous/Crystalline Composite-Type Catalyst.

By substituting the oxygen evolution reaction (OER) with the anodic urea oxidation reaction (UOR), it not only reduces energy consumption for green hydrogen generation but also allows purification of urea-rich wastewater. Spin engineering of the d orbital and oxygen-containing adsorbates has been recognized as an effective pathway for enhancing the performance of electrocatalysts. In this work, we report the fabrication of a bifunctional electrocatalyst composed of amorphous RuO2-coated NiO ultrathin nanosheets (a-RuO2/NiO) with abundant amorphous/crystalline interfaces for hydrogen evolution reaction (HER) and UOR. Impressively, only 1.372 V of voltage is required to attain a current density of 10 mA cm-2 over a urea electrolyzer. The increased oxygen vacancies in a-RuO2/NiO by incorporation of amorphous RuO2 enhance the total magnetization and entail numerous spin-polarized electrons during the reaction, which speeds up the UOR reaction kinetics. The density functional theory study reveals that the amorphous/crystalline interfaces promote charge-carrier transfer, and the tailored d-band center endows the optimized adsorption of oxygen-generated intermediates. This kind of oxygen vacancy induced spin-polarized electrons toward boosting HER and UOR kinetics and provides a reliable reference for exploration of advanced electrocatalysts.

A Full-Spectrum ZnS Photocatalyst with Gradient Distribution of Atomic Copper Dopants and Concomitant Sulfur Vacancies for Highly Efficient Hydrogen Evolution.

A rarely discussed phenomenon in the realm of photocatalytic materials involves the presence of gradient distributed dopants and defects from the interior to the surface. This intriguing characteristic has been successfully achieved in the case of ZnS through the incorporation of atomic monovalent copper ions (Cu+) and concurrent sulfur vacancies (Vs), resulting in a photocatalyst denoted as G-CZS1-x. Through the cooperative action of these atomic Cu dopants and Vs, G-CZS1-x significantly extends its photoabsorption range to encompass the full spectrum (200-2100 nm), which improves the solar utilization ability. This alteration enhances the efficiency of charge separation and optimizes Δ(H*) (free energy of hydrogen adsorption) to approach 0 eV for the hydrogen evolution reaction (HER). It is noteworthy that both surface-exposed atomic Cu and Vs act as active sites for photocatalysis. G-CZS1-x exhibits a significant H2 evolution rate of 1.01 mmol h-1 in the absence of a cocatalyst. This performance exceeds the majority of previously reported photocatalysts, exhibiting approximately 25-fold as ZnS, and 5-fold as H-CZS1-x with homogeneous distribution of equal content Cu dopants and Vs. In contrast to G-CZS1-x, the H adsorption on Cu sites for H-CZS1-x (ΔG(H*) = -1.22 eV) is excessively strong to inhibit the H2 release, and the charge separation efficiency for H-CZS1-x is relatively sluggish, revealing the positive role of a gradient distribution model of dopants and defects on activity enhancement. This work highlights the synergy of atomic dopants and defects in advancing photoactivity, as well as the significant benefit of the controllable distribution model of dopants and defects for photocatalysis.

Constructing copper Phthalocyanine/Molybdenum disulfide (CuPc/MoS2) S-scheme heterojunction with S-rich vacancies for enhanced Visible-Light photocatalytic CO2 reduction.

Constructing a heterojunction by combining two semiconductors with similar band structures is a successful approach to obtaining photocatalysts with high efficiency. Herein, a CuPc/DR-MoS2 heterojunction involving copper phthalocyanine (CuPc) and molybdenum disulfide with S-rich vacancies (13.66%) is successfully prepared by the facile hydrothermal method. Experimental results and theoretical calculations firmly demonstrated that photoelectrons exhibit an S-scheme charge transfer mechanism in the CuPc/DR-MoS2 heterojunction. The S-scheme heterojunction system has proven significant advantages in promoting the charge separation and transfer of photogenerated carriers, enhancing visible-light responsiveness, and achieving robust photoredox capability. As a result, the optimized 3CuPc/DR-MoS2 S-scheme heterojunction exhibits photocatalytic yields of CO and CH4 at 200 and 111.6 µmol g-1h-1, respectively. These values are four times and 4.5 times greater than the photocatalytic yields of pure DR-MoS2. This study offers novel perspectives on the advancement of innovative and highly effective heterojunction photocatalysts.