Graphitic Shells Research Articles

Fabrication of hafnium-based nanoparticles and nanostructures using picosecond laser ablation

This work presents a unique and straightforward method to synthesise hafnium oxide (HfO2) and hafnium carbide (HfC) nanoparticles (NPs) and to fabricate hafnium nanostructures (NSs) on a Hf surface. Ultrafast picosecond laser ablation of the Hf metal target was performed in three different liquid media, namely, deionised water (DW), toluene, and anisole, to fabricate HfO2 and HfC NPs along with Hf NSs. Spherical HfO2 NPs and nanofibres were formed when Hf was ablated in DW. Hf ablated in toluene and anisole demonstrated the formation of core–shell NPs of HfC with a graphitic shell. All NPs exhibited novel optical reflectance properties. Reflectance measurements revealed that the fabricated NPs had a very high and broad optical absorption throughout the UV–vis–NIR range. The NPs synthesised in toluene exhibited the best absorption. The successful fabrication of Hf NSs with the formation of laser-induced periodic surface structures (LIPSS) with low spatial frequency (LSFL) and high spatial frequency (HSFL) orthogonal to each other was also demonstrated. The LSFL and HSFL both exhibited quasi-periodicity. This work presents a simple way to fabricate HfO2 and HfC NPs and provides insight into their morphological and optical characteristics paving way for their applications in future.

Surface Oxygen Engineering Catalytic Pore Tailoring of Coal-Based Needle Coke toward Capacitive Porous Carbon.

Coal-based needle coke (CNC) is an ideal carbon precursor for capacitive materials due to its layered graphitic structure and high electrical conductivity. However, the pore-rich engineering and graphitic structural inheriting of CNC-derived carbon during the conventional activation process present challenges. Herein, a surface oxygen engineering catalytic pore tailoring strategy is developed to manipulate the porous structures of CNC-derived porous carbon. This synthesis uses air oxidation to form oxygen-rich microregions on the CNC surface, which can effectively tear the graphite protective shell, accelerate the bonding of KOH with oxygen groups, and catalyze the etching reaction between potassium compounds and carbon atoms. Thanks to the low activation temperature of 600 °C and alkali-to-carbon ratio of 1:1, the obtained porous carbon (PC) inherits the long-range graphitic structure from CNC, and its specific surface areas can be adjusted from 182.6 to 855.4 m2 g-1 by adjusting the oxidation temperature, which is far more than that of PC (7.6 m2 g-1) derived from CNC direct activation. The optimized PC shows a high specific capacitance of 308.3 F g-1 at 0.5 A g-1 and a capacitive retention of 212.2 F g-1 at 20 A g-1 with a capacitive retention of 68.8%. The assembled supercapacitor delivers an energy density of 8.12 Wh kg-1 at a power density of 50.0 W kg-1 and ultralong cycle stability with capacitance retention of 99% and Coulombic efficiency of 100% after 50,000 cycles. This study validates the feasibility of pore tailoring by surface oxygen engineering catalysis in soft carbon for enhancing capacitance.

Structurally ordered FeCo@FeCoOx@NC dual-shell nanoparticles synthesized under micro-oxygen conditions: An efficient cocatalyst for BiVO4 photoelectrochemical water oxidation

Electrocatalysts are usually integrated onto light-absorbing semiconductors to form efficient photoelectrochemical water-splitting systems. Transition metal oxide nanoparticles serve as excellent electrocatalysts, but exhibit poor performance as cocatalysts for photoelectrodes. To address this issue, a FeCo@FeCoOx@NC dual-shell nanoparticle (consisting of a FeCo alloy core, an intermediate FeCoOx shell, and an outermost graphitic carbon shell) was prepared under micro-oxygen conditions. The FeCo alloy has the dual functions of rapid hole storage and efficient charge transport, while the FeCoOx layer acts as active sites to accelerate the kinetics of the water oxidation reaction and the graphitic carbon protects the internal structure of the nanoparticles. Under the synergistic effect of FeCo@FeCoOx@NC and NiFeOx cocatalysts, the injection efficiency and separation efficiency of BiVO4 photoanode almost reach 100 %, and the photocurrent density reaches 6.85 mA cm−2 (1.23 VRHE, AM 1.5 G), marking the highest reported value to date.

Sonochemical Synthesis of Potassium-Intercalated Carbon Allotropes: Bulk Formation at Ambient Room Temperature.

Intercalation can be used to alter the electronic properties of graphitic materials. Intercalation is, however, a notoriously brute-force process typically carried out at a high temperature in an inert environment for an extended period. As an exception to this, a simple sonication-assisted intercalation of potassium into graphite at ambient room temperature (RT) has been reported. Here we extend this approach to intercalation of potassium into other carbon allotropes, including planar graphene nanoplatelets (GNPs) and curved graphitic tubes and shells, such as multiwalled carbon nanotubes (MWCNTs) and nanodiamond-derived carbon nano-onions (NCNOs). We report the rapid room-temperature sonication-assisted potassium metal intercalation of GNPs, MWCNTs, and NCNOs. Powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), and electron dispersive X-ray spectroscopy (EDS) were used to visualize the location of potassium in the intercalated products.

Impact of Carbides on Surface Finish and Wear Characteristics of Graphitic Roll Shell Materials for Hot Rolling Applications

Impact of Carbides on Surface Finish and Wear Characteristics of Graphitic Roll Shell Materials for Hot Rolling Applications

Correlation study of graphitic shell encapsulated nickel: A multi-spectroscopic approach

Graphite-encapsulated metal nanoparticles hold great potential across various applications due to their unique combination of metal and graphitic properties. While Raman spectroscopy is widely used to assess the graphitic shells, metrics derived from prominent Raman bands often prove unreliable when analyzing such structures with a large number of heterogeneous flakes and are mostly applicable to few-layer graphene. However, researchers continue to face challenges in identifying reliable metrics that accurately reflect two key properties of graphitic shells: thickness and degree of graphitization. In this study, graphitic shells were synthesized via plasma-enhanced chemical vapor deposition (PECVD) at low temperatures (500 °C), seeded by nickel nano-islands. A full-factorial experiment was designed to explore a diverse sample space by varying two key input factors: the initial thickness of the nickel seeding film and the duration of carbon deposition. Using resource-intensive surface characterization techniques (SEM, EDS, XPS, and AFM), we verified encapsulation efficiency and morphology, identifying strong correlations between the input factors and properties of the shells. To gain insights into structural characteristics, we employed conventional spectroscopy techniques (Raman, UV–Vis-nIR transmission, and Transient Absorption Spectroscopy), introducing 107 metrics derived from spectral data. Principal Component Analysis (PCA) aligned the input factors, and their corresponding shell properties, with the first two principal components. Accordingly, we identified the most relevant metrics including new candidates derived from less prominent Raman bands. Additionally, inter-metric correlations enable interchangeable use of spectroscopy techniques. This study marks the first multi-spectroscopic correlation analysis of graphitic shells and provides a novel framework for evaluating their properties.

Ni-based compounds in multiwalled graphitic shell for electrocatalytic oxygen evolution reactions

Here, we report a general strategy for designing a metal/carbon system, via a facile and environmentally friendly one-step approach, from metal acetate as an active electrocatalyst in oxygen evolution reaction (OER) during water decomposition. As a demonstration, a nanostructured Ni/C composite induced from nickel acetate is revealed in great detail. The resulting material is composed of: metallic nickel (Ni), nickel(II) oxide (NiO), and nickel carbide (Ni3C) coated with a graphitic shell and deposited on a carbon platform. Our findings underscore the prominent role of nickel species, including Ni0, Ni2+, and Ni3+, in driving the catalytic activity. Notably, the catalyst exhibits an overpotential of 170 mV, a Tafel slope of 49 mV·dec−1, an electrocatalytic surface area (ECSA) of 964.7 cm2, and a turnover frequency (TOF) value of 52.8 s−1, surpassing RuO2. The Raman spectra also suggest a graphitic "self-healing" phenomenon post-OER, attributed to the reduction of oxygen-containing groups. Carbon in the system (i) facilitates electron transfer, (ii) allows homogeneous distribution of Ni nanoparticles avoiding their agglomeration, and (iii) promotes durability of the electrocatalyst by serving as a protective barrier, shielding the core metal compounds. What is more, density functional theory (DFT) calculations allowed to optimized geometry of the model cluster Ni8O8(OH)8 describing two different sites on the β-NiOOH surface (001) and two different intermediates, (i)L-OOH and (ii)L-OOH. This facilitated to propose the reaction mechanisms involving both hydroxide ions and water molecules as reducers. Therefore, the chemisorption of OH− and H2O molecules at the NiOOH active center accompanied by bond breakage and the formation of a lattice hydroperoxide as an important intermediate is presumed. What is more, the proposed fabrication method for electroactive metal/carbon composites was validated with an iron and iron/nickel mixture.

Zinc Vaporization Induced Formation of Desired Ni Nanoparticles Coated with Ultrathin Carbon Shells for Efficient Electrocatalytic H2 Production Coupling with Methanol Upgrading.

The integration of the hydrogen evolution reaction (HER) with the methanol oxidation reaction (MOR) has been demonstrated to be a viable strategy for the energy-saving generation of H2 and value-added formate, which relies primarily on highly active and cost-effective bifunctional electrocatalysts. Herein, an efficient electrocatalyst consisting of controllable Ni nanoparticles (NPs) coated with ultrathin graphitic carbon shells was obtained by the pyrolysis of a Ni-Zn metal-organic framework. Intriguingly, we found that zinc vaporization not only resulted in the relatively small Ni NPs but also ultrathin carbon shells (≤3 layers). The density functional theory simulations confirmed that these ultrathin carbon shells significantly influenced electrocatalytic activity by facilitating electron transfer from the Ni core to the carbon shell. The optimized Ni1(Zn)@C demonstrated high catalytic activity for both HER and MOR, and only a low potential of 97 mV at 10 mA cm-2 was required for HER and 1.48 V at 30 mA cm-2 for MOR. In a two-electrode electrocatalytic cell measurement, a cell voltage of 1.63 V was observed at 10 mA cm-2 in the presence of methanol, 240 mV lower than that without methanol.

Iron-Catalyzed Laser-Induced Graphitization - Multiscale Analysis of the Structural Evolution and Underlying Mechanism.

The transition to sustainable materials and eco-efficient processes in commercial electronics is a driving force in developing green electronics. Iron-catalyzed laser-induced graphitization (IC-LIG) has been demonstrated as a promising approach for rendering biomaterials electrically conductive. To optimize the IC-LIG process and fully exploit its potential for future green electronics, it is crucial to gain deeper insights into its catalyzation mechanism and structural evolution. However, this is challenging due to the rapid nature of the laser-induced graphitization process. Therefore, multiscale preparation techniques, including ultramicrotomy of the cross-sectional transition zone from precursor to fully graphitized IC-LIG electrode, are employed to virtually freeze the IC-LIG process in time. Complementary characterization is performed to generate a 3D model that integrates nanoscale findings within a mesoscopic framework. This enabled tracing the growth and migration behavior of catalytic iron nanoparticles and their role during the catalytic laser-graphitization process. A three-layered arrangement of the IC-LIG electrode is identified including a highly graphitized top layer with an interplanar spacing of 0.343nm. The middle layer contained γ-iron nanoparticles encapsulated in graphitic shells. A comparison with catalyst-free laser graphitization approaches highlights the unique opportunities that IC-LIG offers and discuss potential applications in energy storage devices, catalysts, sensors, and beyond.

Fast diffusion and stable topotactic reaction in single crystal conversion anode

Conversion electrodes typically have high theoretical specific capacity, but mostly suffer large structural changes during charge/discharge and result in poor cycling stability. The optimization of the polycrystalline materials is the mostly used strategy, however, these polycrystalline materials are intrinsically vulnerable to grain-boundary (intergranular) fracture caused by the anisotropic volume change during sodiation/desodiation, resulting in rapid impedance growth and capacity decay. Herein, we propose an alternative pathway to design single-crystal materials as potential conversion anodes. As an example, SnO2 with different crystallinities is successfully synthesized via solvothermal methods and compared to determine the implications of different crystallinity for the electrochemical properties of conversion anodes. It is demonstrated that the single-crystal SnO2 not only has faster Na+ diffusion dynamics but also maintains structural stability via topotactic reaction. Further optimization of the electron conduction and structural robustness is realized by uniformly covering a graphitic carbon shell on the surface of single-crystal SnO2 nanosheets. The modified single-crystal SnO2 exhibits a high reversible capacity of 436.2 mA h g–1 and maintains a high capacity of 257.1 mA h g-1 and remarkable capacity retention of about 98.9% after 9000 cycles at 5000 mA g-1. The deep understandings of the topotactic reaction in single crystal conversion anode in this work provide a theoretical foundation and new direction for further developing electrode materials with excellent electrochemical performance, especially high rate capabilities, and long cyclability.

Selective Electrochemical CO2 Reduction tuned by N Configuration on graphitic Shells of Nickel Particles

AbstractDespite of high conductivity and reducing ability, transition metal nanoparticles tend to aggregate and unavoidably impact the selectivity during the proton‐coupled reduction process of CO2RR. New strategy to regulate and utilize the electronic property of transition‐metal particles allows for effective tuning of eCO2RR activity. Through simple creation of N‐doped carbon shells surrounding Ni nanoparticles and controlling the amount and arrangement of the N atoms, successful and long‐lasting electrochemical reduction of CO2 was accomplished. The inherent HER activity was almost completely suppressed. It exhibited FECO above 90 % in a 500 mV potential window, with the optimal up to 96.5 % at −0.78 V vs RHE. In flow cell electrolysis, a current density of 289.4 mA/cm2 was achieved with Faradic efficiency of 96.4 % towards CO. The results of control experiments using different catalysts imply that electron transfer between Ni core and shells was significantly influenced by the property of N atoms. High content of graphitic nitrogen is crucial for the catalytic performance.

Bimetallic Ni–Fe nanoparticles encapsulated with biomass-derived N-doped graphitic carbon core-shell nanostructures an efficient bifunctional electrocatalyst for enhanced overall seawater splitting and human urine electrolysis

Producing green hydrogen from abundant natural resources such as seawater and human urine is a viable solution for energy and industrial applications. However, the field of electrocatalysis faces challenges in developing cost-effective metal catalysts for efficient electrolysis of seawater and urea sewage. Here, we reported bimetallic NiFe nanoparticles encapsulated in a biomass derived N-doped graphitic carbon core shell structure (NiFe@BNGC-700) as a stable and effective catalyst for seawater and human urine electrolysis. NiFe@BNGC-700 exhibits remarkable electrocatalytic performance, with a low overpotential requiring 300 mV for OER and 297 mV for HER in alkaline 1.0 M KOH + seawater and 1.36 V for UOR in alkaline 1.0 M KOH + human urine at 50 mA cm−2 current density, respectively. The active bifunctional NiFe@BNGC-700 electrocatalyst symmetry pair facilitates the construction of a seawater electrolyser, achieving a cell voltage of 1.74 V at 50 mA cm−2 current density. Furthermore, the human urine-mediated electrolyser employing NiFe@BNGC-700//NiFe@BNGC-700 achieves a cell voltage of 1.64 V at the same current density, maintaining stability over 12 h with negligible potential deviation. Continual evolution of hydrogen and oxygen is feasible in a solar seawater a cell assembled with NiFe@BNGC-700 electrocatalyst, delivering at cell voltage of 1.74 V, enabling sustained and effective green hydrogen delivery on a large scale. This study proposes a sustainable strategy for fabricating electrodes consisting of non-precious metals, thereby permitting the economical and extensive generation of green hydrogen on a large scale.

Amorphous/Graphitic carbon phase engineering of Corrosion-Resistant Fe@C Core-Shell nanowires for optimized dipole polarization and enhanced microwave absorption

The study of designing and developing ferromagnetic nanocomposites with both microwave absorption (MA) and corrosion protection properties through microscopic heterogeneous interfacial engineering and crystal phase engineering remains challenging. In this study, Fe@C core–shell nanowires (FCNWs) are obtained by magnetic field-controlled in situ reduction method and annealing process to de-regulate the carbon shell thickness and carbon morphology. The enhancement of Fe-C heterogeneous relative interfacial effects and dielectric/magnetic response is revealed using density functional theory and simulated electromagnetic field distribution, and the modulation of the amorphous carbon/graphitic carbon ratio achieves the enhancement of dipole polarization in the low-frequency region. The FCNWs absorber had a minimum reflection loss (RLmin) of −47.6 dB at a thickness of 4.9 mm, and the maximum effective absorption bandwidth (EABmax) was achieved at 5.5 mm up to 4.0 GHz. In addition, the shielding effect of the graphitic carbon shell on the corrosion medium and the addition of additional electron conduction pathways allow the FCNWs absorber to obtain smaller corrosion currents and larger polarization resistances compared to Fe nanowires. Thus, modulation of atomic-scale heterogeneous interfaces and crystal phases has great potential in modulating the dielectric response.

Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C3N4 catalysts with ultra-low Ni loading

Selective hydrogenolysis of biomass-based platform compounds is of great importance for the production of chemicals and fuels. Herein, we reported that the catalyst of Ni-C3N4 supported on H2 activated carbon (HC) synthesized by a simple coordination-impregnation-pyrolysis method is efficient for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); the yield of 94.2% can be obtained in a batch reactor and the lifetime of greater than 120 h can be achieved in fixed-bed experiment. It is demonstrated that Ni nanoparticles coated by graphitic C3N4 shell were highly dispersed on the surface of HC and the Ni loading is as low as 0.86 wt%, beneficial to the anti-sintering of Ni nanoparticles during the reaction. Both XPS characterizations and theoretical calculations reveal that Ni3N is the intrinsic active component for the hydrogenolysis, which exhibits efficient activity for the dissociation of C–O bond. This work opens up a new avenue to develop catalysts with single non-noble metal component for the efficient conversion of biomass-based chemicals.

Exceptional performance of Fe@carbon-rich nanoparticles prepared via hydrothermal carbonization of oil mill wastes for H2S removal

Carbon-encapsulated iron oxide nanoparticles (CE-nFe) have been obtained from an industrial waste (oil mill wastewater-OMW, as a carbonaceous source), and using iron sulfate as metallic precursor. In an initial step, the hydrochar obtained has been thermally activated under an inert atmosphere at three different temperatures (600 °C, 800 °C and 1000 °C). The thermal treatment promotes the development of core-shell nanoparticles, with an inner core of α-Fe/Fe3O4, surrounded by a well-defined graphite shell. Temperatures above 800 °C are needed to promote the graphitization of the carbonaceous species, a process promoted by iron nanoparticles through the dissolution, diffusion and growth of the carbon nanostructures on the outer shell. Breakthrough column tests show that CE-nFe exhibit an exceptional performance for H2S removal with a breakthrough capacity larger than 0.5–0.6 g H2S/gcatalyst after 3 days experiment. Experimental results anticipate the crucial role of humidity and oxygen in the adsorption/catalytic performance. Compared to some commercial samples, these results constitute a three-fold increase in the catalytic performance under similar experimental conditions.

The construction of iron-based catalysts encapsulated by graphite for CO2 hydrogenation to light olefins

Developing efficient catalytic materials and unveiling the active factors are significant for selective hydrogenation of CO2 to light olefins (C2–4=). Herein, Fe3O4-FeCx nanoparticles coated by graphite without other doped elements were synthesized successfully. The optimal catalyst exhibited CO2 conversion of 48.0%, C2–4= space–time yield of 29.0 mmol·g−1·h−1, and a stability of 100 h (3.0 MPa, 320 °C, and GHSV = 12000 mL·g−1·h−1). The core–shell structure derived from the strong interaction between the phenolic hydroxyl group of resin and iron ions, as well as the encapsulation of the copolymer P123. The characterization results revealed that the size of core–shell particles and thickness of graphite layers could be regulated by P123, which affected the conversion of CO2 and products distribution significantly. Moreover, the combined results of quasi in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) and Raman spectra suggested small particle size and thin graphite shell strengthen the adsorption and conversion of CO2, playing an important role in the formation of light olefins. This work proposes a simple and feasible synthesis strategy to construct Fe3O4-FeCx particles encapsulated by graphite shell, which provides insights into catalysts design and the reaction mechanism of CO2 conversion to light olefins.

Novel synthesis of FeF3·0.33H2O@hollow acetylene black nanosphere and its long-life electrochemical properties as a cathode for lithium-ion batteries

Iron (III) fluoride (FeF3), characterized by high voltage and high specific capacity and emerges as a promising candidate for the forthcoming generation of cathode materials in lithium-ion batteries. This study employs a novel methodology by introducing Fe3+ sources into hollow acetylene black particles through a vacuum impregnation method. This innovative approach results in the synthesis of a composite material comprising FeF3∙0.33H2O encapsulated within hollow acetylene black nanospheres, denoted as the FeF3∙0.33H2O @hollow acetylene black nanosphere composite material (FF@HCN). The composite exhibits a shell composed of highly graphitized carbon and a core containing FeF3∙0.33H2O particles in the range of 10–20 nm. The proportion of active materials is 75.56 %. The acetylene black has chain-like structure and high specific surface area, significantly enhances the material's conductivity, contributing 74.4 % to the pseudocapacitance at a scan rate of 1 mV s−1. The cavity graphite shell plays a crucial role in restricting the expansion and pulverization decay of FeF3∙0.33H2O nanoparticles, thereby markedly improving the cycle stability. The initial capacity of the FF@HCN composite is 224.4 mAh g−1, and after 1000 cycles at 0.1 C, it maintains a capacity of 162.3 mAh g−1, resulting in a capacity retention rate of 72.3 % and decay per cycle of 0.027 %.

Core-shell diamond-graphene needles with silicon-vacancy color centers

Color centers in diamond nanostructures open new horizons in biomedicine, offering a biocompatible material platform for sensing temperature, pH, and magnetic field. Covering of the color centers enriched diamonds with graphene shell can essentially extend their application potential. Specifically, under irradiation with ultrashort laser pulses, the highly absorptive graphene shell can be used for excitation of a shock acoustic wave which can be used for cancer cell destruction or drug photoactivation through the Joule heating. In this study, we present a novel method for creating diamond-graphite core-shell structures. Through precise control of the growth of the graphitic layer on Single Crystal Diamond Needles (SCDNs) via vacuum annealing at 900°C for 30 minutes, we preserved 57% of the light emission from silicon-vacancy (SiV-) centers while maintaining their spectral peaks. Contrary to our expectations of reduced SiV- luminescence due to the presence of the graphitic shell, we observed that the initial high brightness of SiV- in the diamond needles persisted. This enabled us to detect SiV- luminescence spectrally, even within the core-shell structures. Our results underscore the tunability of these structures’ properties through temperature and duration control, suggesting promising prospects for their application in advanced biomedical tools with sensing capabilities.

Nitrogen-doped carbon nanostructures embedded with Fe-Co-Cr alloy based nanoparticles as robust electrocatalysts for Zn-air batteries

Two types of nitrogen-doped carbon nanomaterials embedded with novel transition metal-based medium entropy alloy nanoparticles are synthesized via a simple, scalable, and cost-effective single-step pyrolysis route, by varying the stoichiometric ratio of iron and cobalt. The samples predominantly have bamboo-shaped nanotube morphology with some globular structures. The globules are core-shell type nanoparticles, i.e., containing the metallic-alloy nanoparticles encapsulated by the graphitic shell and embedded within defective amorphous-type carbon matrix. The electrochemical studies using these samples are conducted in basic medium to explore their potential for Zn-air batteries. Electrochemical measurements are carried out in 1 M and 0.1 M KOH, respectively, on a rotating disk electrode setup. The sample with higher cobalt content performs better for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) with regards to lower onset potential, lower Tafel slope and lower activation energy. However, the stability towards OER is better for the sample with higher iron content. The sample with higher cobalt content shows a better overall oxygen electrochemistry compared to the one with higher iron content, is at par with several state-of art electrocatalysts and is utilized for fabrication of a prototype Zn-air battery demonstrating its practical applicability.

Efficient thermal energy conversion and storage enabled by hybrid graphite nanoparticles/silica-encapsulated phase-change microcapsules

A novel graphite nanoparticles-decorated hybrid shell phase change microcapsule was developed, which exhibits enhanced thermophysical properties and efficient photothermal conversion performance, indicating great potential for application in DASCs.