Search Results (312)

This study investigates the influence of vacancy engineering and nitrogen doping on the structural, electronic, and optical properties of T-graphene fragments (TFs) using density functional theory (DFT) and time-dependent DFT (TD-DFT). A central vacancy and five pyridinic nitrogen doping configurations are explored to modulate the optoelectronic behavior. All systems are thermodynamically stable, exhibiting tunable HOMO–LUMO gaps, orbital distributions, and charge transfer characteristics. Optical absorption spectra show redshifts and enhanced oscillator strengths in doped variants, notably v-NTF2 and v-NTF4. Nonlinear optical (NLO) analysis reveals significant enhancement in both static and frequency-dependent responses. v-NTF2 displays an exceptionally high first-order hyperpolarizability (⟨β⟩ = 1228.05 au), along with a strong electro-optic Pockels effect (β (−ω; ω, 0)) and second harmonic generation (β (−2ω; ω, ω)). Its third-order response, γ (−2ω; ω, ω, 0), also exceeds 1.2 × 10⁵ au under visible excitation. Conceptual DFT descriptors and energy decomposition analysis further supports the observed trends in reactivity, charge delocalization, and stability. These findings demonstrate that strategic nitrogen doping in vacancy-engineered TFs is a powerful route to tailor electronic excitation, optical absorption, and nonlinear susceptibility. The results offer valuable insight into the rational design of next-generation carbon-based materials for optoelectronic, photonic, and NLO device applications. Full article

The fundamental chemistries and electronic structures of platinum catalysts over nitrogen-doped carbon supports were examined to determine the subtle yet important roles graphitic defect-based and pyridinic defect-based nitrogen defects have in stabilizing platinum. These roles address and extend previously gathered incomplete knowledge of how combinations of graphitic defect and pyridinic defect affect the local electronic structure, leading to a greater unified understanding of platinum stability. A theoretical study was designed where different atomically sized platinum clusters were investigated over seven different nitrogen defect combinations on graphene carbon support. Differently sized platinum clusters offered parametric insights into the differences in metal–support interactions. Full article

Although lithium-ion batteries are considered an ideal postulant for renewable energy harvesting, storage and applications, these batteries show promising performance; however, at the same time, these harvesting devices suffer from some major limitations, including scarce lithium resources, high cost, toxicity and safety concerns. Potassium ion batteries (PIBs) can be proven a favorable alternative to metal ion batteries because of their widespread potassium reserves, low costs and enhanced protection against sparks. In this study, DFT simulations were employed using the B3LYP/6-311⁺⁺g(d p) method to explore the application of graphene and its doped variants (N,B,P-graphene) as potential anode materials for PIBs. Various key parameters such as adsorption energy, Gibbs free energy, molecular orbital energies, non-covalent interactions, cell voltage, electron density distribution and density of states were computed as a means to evaluate the suitability of materials for PIB applications. Among the four structures, nitrogen- and phosphorus-doped graphene exhibited negative Gibbs free energy values of −0.020056 and −0.021117 hartree, indicating the thermodynamic favorability of charge transfer processes. Doping graphene with nitrogen and phosphorus decreases the HOMO-LUMO gap energy, facilitating efficient ion storage and charge transport. The doping of nitrogen and phosphorus increases the cell voltage from −1.05 V to 0.54 V and 0.57 V, respectively, while boron doping decreases the cell voltage. The cell voltage produced by graphene and its doped variants in potassium ion batteries has the following order: P-graphene (0.57 V) > N-graphene (0.54 V) > graphene (−1.05 V) > B-graphene (−1.54 V). This study illustrates how nitrogen- and phosphorus-doped graphene can be used as a propitious anode electrode for PIBs. Full article

The functionalization of nitrogen-doped graphene with β-Cyclodextrin (designated β/N-rGO) was employed to enhance the dispersibility of graphene materials and to establish an adsorption-catalytic oxidation system using peroxymonosulfate (PMS) for the removal of trace antibiotics from water. The experimental results indicated that β-Cyclodextrin was effectively dispersed on the support structure of nitrogen-doped graphene, which enhanced the specific surface area and dispersibility of the material. The adsorption-catalytic oxidation system comprising β/N-rGO and PMS degraded 92.35% of sulfamethoxazole within 12 min and exhibited significant removal efficiency for sulfonamides, quinolones, macrolides, tetracyclines, β-lactams, and chloramphenicol antibiotics across a pH range of 3–12. The reaction time was reduced by over 10% compared to the unmodified material, with a more pronounced improvement in treatment efficiency, particularly under low-pH conditions. The activation energy of β/N-rGO was estimated to be approximately 4.5 kJ/mol, and elevated temperatures accelerated the reaction, with the removal rate remaining above 85% after five regeneration cycles. Quenching experiments and EPR spectra confirmed that the primary pathway for PMS activation by β/N-rGO was a non-radical process dominated by singlet oxygen. These findings broaden the research and application scope of cyclodextrin–graphene interactions and provide a feasible approach for the removal of trace antibiotics from water. Full article

The efficient mass transport and enhanced accessibility of active sites are crucial for high-performance electrocatalysts in water splitting. Inspired by the hierarchical structure of natural wood, we engineered a monolithic electrocatalyst, cobalt nanoparticles encapsulated in nitrogen-doped carbon layers on carbonized wood (Co@NC/CW), by carbonizing wood to create a three-dimensional framework with vertically aligned macropores. The unique architecture encapsulates cobalt nanoparticles within in situ-grown nitrogen-doped graphene layers on wood-derived microchannels, facilitating ultrafast electrolyte infusion and anisotropic electron transport. As a result, the optimized freestanding Co@NC/CW electrode exhibits remarkable bifunctional activity, achieving overpotentials of 403 mV and 227 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, at a current density of 50 mA cm⁻². Furthermore, the integrated hybrid electrolyzer combining the HER and the OER delivers an impressive 50 A cm⁻² at a cell voltage of 1.72 V while maintaining a Faradaic efficiency near 99.5% and sustaining long-term stability over 120 h of continuous operation. Co@NC/CW also demonstrates performance in the complete decomposition of alkaline seawater, underscoring its potential for scalable applications. This wood-derived catalyst design not only leverages the natural hierarchical porosity of wood but also offers a sustainable platform for advanced electrochemical systems. Full article

NiFe₂O₄ and TiO₂ are widely studied for photoelectrochemical (PEC) applications due to their unique properties. Nitrogen-doped graphene (NG) and metal–organic frameworks (MOFs), such as MIL-100(Fe) (where MIL stands for Materials of Lavoisier Institute), are commonly incorporated to enhance PEC performance by offering a high surface area and facilitating efficient charge transport. Composite systems are commonly employed to overcome the limitations of individual PEC catalysts. In this study, a highly efficient NiFe₂O₄/NG@MIL-100(Fe)/TiO₂ photoanode was developed to enhance photoelectrochemical water-splitting performance. The composite was synthesized via a hydrothermal method with a two-step heating process. X-ray diffraction confirmed the expected crystal structures, with peak broadening in NiFe₂O₄ indicating reduced crystallite size and increased lattice strain. X-ray photoelectron spectroscopy of the Ni 2p and Fe 2p regions validated the successful integration of NiFe₂O₄ into the composite. Electrochemical analysis demonstrated excellent performance, with linear sweep voltammetry achieving a peak photocurrent density of 3.5 mA cm⁻² at 1.23 V (vs RHE). Electrochemical impedance spectroscopy revealed a reduced charge-transfer resistance of 50 Ω, indicating improved charge transport. Optical and electronic properties were evaluated using UV-Vis spectroscopy and Tauc plots, revealing a direct bandgap of 2.1 eV. The composite exhibited stable photocurrent under amperometric J-t testing for 2000 s, demonstrating its durability. These findings underscore the potential of NiFe₂O₄/NG@MIL-100(Fe)/TiO₂ as a promising material for renewable energy applications, particularly in photoelectrochemical water splitting. Full article

Organophosphorus pesticides (OPs), while pivotal for agricultural productivity, pose severe environmental and health risks due to their persistence and bioaccumulation. Existing detection methods, such as chromatography and spectroscopy, face limitations in field adaptability, cost, and operational complexity. To address these challenges, this study introduces a novel dual-mode photoelectrochemical–electrochemical (PEC-EC) sensor based on a Co,N-TiO₂@ZrO₂/3DGH nanocomposite. The sensor synergistically integrates zirconium oxide (ZrO₂) for selective OP capture via phosphate-Zr coordination, cobalt-nitrogen co-doped titanium dioxide (Co,N-TiO₂) for visible-light responsiveness, and a three-dimensional graphene hydrogel (3DGH) for enhanced conductivity. In the PEC mode under light irradiation, OP adsorption induces charge recombination, yielding a logarithmic photocurrent attenuation with a detection limit of 0.058 ng mL⁻¹. Subsequently, the EC mode via square wave voltammetry (SWV) self-validates the results, achieving a detection limit of 0.716 ng mL⁻¹. The dual-mode system demonstrates exceptional reproducibility, long-term stability, and selectivity against common interferents. Parallel measurements revealed <5% inter-mode discrepancy, validating the intrinsic self-checking capability. This portable platform bridges the gap between laboratory-grade accuracy and field-deployable simplicity, offering transformative potential for environmental monitoring and food safety management. Full article

Nitrogen-doped graphene quantum dots (NGQDs) are made by heating a mixture of GQDs and ammonia using a thermochemical method. The optical properties of the samples were studied. Here, the role of the temperature used in the annealing process is investigated. It is found that with the increase in heating temperature, the sp² fraction content continuously increases, and the photoluminescence (PL) blue shift continuously increases. The 550 nm peak of GQDs shifts from 550 nm to 513 nm NGQDs synthesized at 300 °C. The normalized PL intensity shows a significant blue shift in the emission peak of the NGQD samples compared to the GQDs. The peak position of the GQDs is 555 nm, while the peak positions of the NGQDs are 511 nm for NGQDs-250, 488 nm for NGQDs-300, and 480 nm for NGQDs-350. Using a simple thermochemical method, we can effectively dope N into GQDs, and it is evident from the electron energy loss spectra that N doping induces the emergence of a new energy level in the electronic structure, which alters the optical properties of NGQDs. Full article

Li-ion batteries (LIBs) are one of the most deployed energy storage technologies worldwide, providing power for a wide range of applications—from portable electronic devices to electric vehicles (EVs). The growing demand for LIBs, coupled with a shortage of critical battery materials, has prompted the scientific community to seek ways to improve material utilization through the recycling of end-of-life LIBs. While valuable battery metals are already being recycled on an industrial scale, graphite—a material classified as a critical resource—continues to be discarded. In this study, graphite waste recovered from the recycling of LIBs was successfully upcycled into an active graphite/rGO (reduced graphene oxide) composite oxygen electrocatalyst. The precursor graphite for rGO synthesis was also extracted from LIBs. Incorporating rGO into the graphite significantly enhanced the specific surface area and porosity of the resulting composite, facilitating effective doping with residual metals during subsequent nitrogen doping via pyrolysis. These composite catalysts enhanced both the oxygen reduction and oxygen evolution reactions, enabling their use as air electrode catalyst materials in zinc–air batteries (ZABs). The best-performing composite catalyst demonstrated an impressive power density of 100 mW cm⁻² and exceptional cycling stability for 137 h. This research further demonstrates the utilization of waste fractions from LIB recycling to drive advancements in energy conversion technologies. Full article

We investigated the electrochemical performance of undoped artificial graphene-based material (UAG) and N-doped graphene-based material (NAG, ~3.5% nitrogen doping), synthesized by the arc-discharge method, for sodium-ion battery anodes. The NAG demonstrated slightly superior fast-charging capability compared to UAG, achieving a specific capacity of 46.8 mAh g⁻¹ at 30 A g⁻¹, compared to UAG’s capacity of 36.7 mAh g⁻¹, representing an enhancement of approximately 28%. It also showed high cycle stability, retaining a capacity of 100 mAh g⁻¹ (retention ratio ~99.9%) after 2500 cycles at 5 A g⁻¹, compared to UAG’s retention of 90 mAh g⁻¹ (retention ratio ~95%). The diffusion behavior of the UAG and NAG samples was significantly higher than that of graphite. The improvement in electrochemical properties is attributed to the successful doping of nitrogen in NAG, which results in enhanced electrical conductivity and structural disordering. Full article

A supercapacitor’s energy storage capability is greatly dependent on electrode materials. Layered double hydroxides (LDHs) were extensively studied as battery-type electrodes because of their 2D structure and quick intercalation/deintercalation of electrolyte ions. However, the energy storage capability for pristine LDHs is limited by their large aggregation tendency and poor electrical conductivity. Herein, a novel NiCoMn-LDH/SWCNTs (single-walled carbon nanotubes) composite electrode material, with ultrathin NiCoMn-LDH nanosheets dispersedly grown among the highly conductive networks of SWCNTs, was prepared via a facile zeolitic imidazolate framework-67 (ZIF-67)-derived in situ etching and deposition procedure. The NiCoMn-LDH/SWCNTs electrode demonstrates a specific capacitance as large as 1704.3 F g⁻¹ at 1 A g⁻¹, which is ascribed to its exposure of more active sites than NiCoMn-LDH. Moreover, the assembled NiCoMn-LDH/SWCNTs//BGA (boron-doped graphene aerogel) hybrid supercapacitor exhibits a superior capacitance of 167.9 F g⁻¹ at 1.0 A g⁻¹, an excellent energy density of 45.7 Wh kg⁻¹ with a power density of 700 W kg⁻¹, and an outstanding cyclic stability with 82.3% incipient capacitance maintained when subjected to 5000 charge and discharge cycles at the current density of 10 A g⁻¹, suggesting the significant potential of NiCoMn-LDH/SWCNTs as the electrode material applicable in supercapacitors. Full article

The process of directly using atmospheric H₂ for the catalytic semi-hydrogenation of alkynes to alkenes has significant applications in the polyolefin industry. Herein, we report a facile approach to synthesize a hierarchical carbon-encapsulated Pd catalyst for the highly selective semi-hydrogenation of nitrophenylacetylene. The catalyst featured a structure of (Pd@NG)/(Pd@C), which demonstrated that an oligo-layer of nitrogen-doped graphene (NG)-encapsulated Pd particles are supported on the carbon matrix, semi-embedded by another type of Pd particle. The catalyst, named Pd@NC, achieved 99% selectivity for nitrostyrene at 97% nitrophenylacetylene conversion and demonstrated an excellent stability. A good selectivity arose from the bridging effect of hierarchical porous carbon, where hydrogen activation and alkyne hemihydrogenation took place on palladium particles and NG, respectively. The NG layer provided excellent protection against the over-hydrogenation of the reaction. Full article

Carcinoembryonic antigen (CEA) is an important tumor biomarker for the early clinical diagnosis of various cancers, and, therefore, the accurate and sensitive quantitative determination of CEA is of vital significance. In this study, we demonstrated the in situ growth of Au nanoparticles (AuNPs) on nitrogen-doped graphene quantum dots (N-GQDs) decorated reduced graphene oxide (rGO) nanocomposites by using simple drop-coating and electrochemical deposition methods. N-GQDs@rGO can be formed through the π–π stacking interaction and possesses a high specific surface area and many functional groups, providing lots of anchor sites (amino moieties in NGQDs) for the in situ electrochemical growth of AuNPs without the addition of reductants and protective agents. Such AuNPs/N-GQDs@rGO ternary nanocomposites combine the characteristics of three nanomaterials, showing a large surface area, excellent solubility, good conductivity, catalytic activity, a simple fabrication process, and notable stability, which are further used to construct a label-free electrochemical immunosensor for the determination of CEA. Under the optimized experimental conditions, the AuNPs/N-GQDs@rGO-based electrochemical immunosensor achieves a broad linear response, ranging from 1 pg/mL to 0.5 μg/mL and a low detection limit of 0.13 pg/mL. Moreover, the AuNPs/N-GQDs@rGO-based electrochemical immunosensor shows exceptional selectivity, anti-interference, and anti-fouling capabilities for the direct analysis of CEA amounts in fetal bovine serum samples, showing vast potential in the clinical screening of cancer. Full article

Graphene quantum dots (GQDs) represent a class of promising nanomaterials characterized by adjustable optical properties, making them well suited for applications in biosensing and chemical detection. However, challenges persist in achieving scalable, cost-effective synthesis and enhancing detection sensitivity. In this study, we have developed a simple and environmentally friendly method to prepare blue graphene quantum dots, c-GQDs, using nitronaphthalene as a precursor, and yellow graphene quantum dots, y-GQDs, using nitronaphthalene doped acid. The quantum yield is 29.75%, and the average thickness is 2.08 nm and 3.95 nm, respectively. The synthesized c-GQDs exhibit a prominent cyan fluorescence at a wavelength of 490 nm under excitation at 380 nm, while the y-GQDs show a distinct yellow fluorescence at a wavelength of 540 nm under excitation at 494 nm. The introduction of p-aminobenzoic acid (PABA) introduced a marked red shift in fluorescence, attributed to the electron-withdrawing effect of the carboxyl groups on PABA. This key finding significantly enhanced the sensitivity of GQDs for detecting trace copper(II) ions (Cu²⁺), a heavy metal contaminant posing serious environmental risks. The fluorescence of the GQDs was selectively quenched in the presence of Cu²⁺, facilitating accurate and sensitive detection even in complex ion matrices. Mechanistic studies revealed that the quenching effect is driven by strong static quenching interactions, which inhibit non-radiative transitions. This work not only introduces a scalable method for producing high-performance GQDs but also highlights their potential as effective fluorescent probes for environmental monitoring and heavy metal ion detection. Full article

Detecting low nitrogen dioxide concentrations (NO₂) is crucial for environmental monitoring. In this paper, we report the synergistic effect of decorating nitrogen-doped reduced graphene oxide (N-rGO) with nickel oxide (NiO) nanoparticles for developing highly selective and sensitive chemiresistive NO₂ gas sensors. The N-rGO/NiO sensor was synthesized straightforwardly, ensuring uniform decoration of NiO nanoparticles on the N-rGO surface. Comprehensive characterization using SEM, TEM, XRD, and Raman spectroscopy confirmed the successful integration of NiO nanoparticles with N-rGO and revealed key structural and morphological features contributing to its enhanced sensing performance. As a result, the NiO/N-rGO nanohybrids demonstrate a significantly enhanced response five orders of magnitude higher than that of N-rGO toward low NO₂ concentrations (<1 ppm) at 100 °C. Moreover, the present device has an outstanding performance, high sensitivity, and low limit of detection (<1 ppb). The findings pave the way for integrating these sensors into advanced applications, including environmental monitoring and IoT-enabled air quality management systems. Full article