Defective Graphene Research Articles

Controlled nucleation of ultrasmall MoO3 nanoparticles on defective graphene for enhanced ammonia efficiency.

Ultrasmall nanoparticles on nanocarbons enhance the electrocatalytic nitrogen reduction (NRR) efficiency. Herein, we demonstrate a novel method for depositing MoO3 nanoparticles on defective graphene, achieving a high faradaic efficiency (FE) of 43.1% at -0.2 V vs. RHE.

Strain engineering for the interfacial thermal resistance of few-layer graphene with porous defects

As electronic devices continue to advance toward higher integration, thermal management issues have become a bottleneck, limiting device performance at the nanoscale. In this study, we reveal the bistable structural characteristics of circular hole defects in few-layer graphene, exhibiting both adhered and separated states, through molecular dynamics simulations. We propose a mechanical model that considers the interplay between the bending energy and cohesive energy to determine the critical size of the hole defect, at which the structure transits between the adhered and separated states. We further demonstrate that strain engineering can adjust the interfacial thermal resistance by more than fivefolds, which drives the structure transit between bistable states. The strain effect on the interfacial thermal resistance of the structure can be accurately described using analytical models. These findings illustrate that strain engineering is an effective method for precisely controlling the interfacial thermal resistance in few-layer graphene and provide new insights into possible thermal switch applications.

Nitrogen-doped modified graphene aerogel enhancing interfacial bonding with lithium aluminium silicate ceramics for broadband microwave absorption

The swift progression of e-communication technology has resulted in significant electromagnetic pollution, necessitating the urgent need for effective microwave-absorbing materials to mitigate this issue. Augmenting heterogeneous phase interfaces and incorporating heteroatoms constitute viable strategies for enhancing the electromagnetic properties of functional materials. In this study, a series of lithium aluminium silicate glass-ceramic/nitrogen-doped graphene (LAS/N-GF) aerogels was synthesised via the hydrothermal and freeze-drying methods. An innovative bonding mechanism for the heterogeneous phase interface was revealed, in which nitrogen doping enabled the formation of lattice defects in LAS ceramic particles and graphene and promoted a closed approach for unsaturated carbon and silicon atoms to form carbon-silicon bonds through the electrostatic force generated by interfacial polarisation. Given that covalent bonds are widely recognized as stable carrier channels, the presence of carbon-silicon bonds at the interface facilitates electron migration, ultimately leading to improved microwave absorption. The maximum absorptivity of the LAS/N-GF aerogels could reach -47.98 dB at 8.96 GHz with a filler loading as low as 10 wt.%. It is noteworthy that the LAS/N-GF aerogel exhibits an effective absorption bandwidth of 8.34 GHz, which fully spans the entire X-band and more than two-thirds of the Ku-band. Such exceptional performance is rarely observed in dielectric loss materials. Finally, the application potential of the LAS/N-GF aerogels in microwave absorbers was simulated and analysed. The unique chemical phenomenon stemming from the bonding at the carbon material-ceramic interface offers a fresh perspective in interface science, enabling a deeper comprehension of the underlying mechanism of microwave absorption.

Carbon defect induced electron transfer promotes electrocatalytic activation of molecular oxygen to selectively generate singlet oxygen for pollutants removal

This study explored the design of heterojunctions incorporating defective graphene and boron nitride (BN) to activate molecular oxygen (O₂) and degrade sulfamethoxazole (SMX) by establishing efficient electron transport channels. These heterojunction catalysts, designed using theoretical predictions, were synthesized by controlling carbon defect concentration and pyrolysis temperature. The optimized GBN cathode achieved a maximum SMX degradation rate of 0.0252min⁻¹, with a total organic carbon (TOC) removal efficiency of 47.31%. Singlet oxygen (¹O₂) was identified as the primary reactive oxygen species, exhibiting a generation rate of 18.66μMmin⁻¹ and contributing 93.5% to SMX degradation. Results demonstrated that an optimal defect concentration enhances electron transfer, promoting the 2-electron reduction of O₂ to H₂O₂ and facilitating further H₂O₂ activation, thereby accelerating SMX degradation. This work advances the development of non-metallic cathodic catalysts and provides valuable insights into electrochemical degradation mechanisms for organic pollutants.

Advancing Graphene Imaging for Clear Identification of Lattice Defects: The Application of Revolve Sphere Levelling to Scanning Tunnelling Microscopy Images.

Application of revolve sphere levelling (RSL) as a practical and effective image processing tool for enhancing scanning tunnelling microscopy (STM) images of graphene atomic lattices is presented. Low-cost, ambient, and non-invasive STM methods overcome limitations of traditional imaging methods like scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) that can introduce or alter defects in graphene. Utilizing high-quality graphene synthesized via Paragraf's patented Metal-Organic Chemical Vapor Deposition (MOCVD) method, RSL, which is easily implemented via the Gwyddion software package, effectively highlights the hexagonal lattice structure and specific defect structures. This provides clarity of the atomic structure that traditional methods struggle to achieve. This research emphasizes the utility of RSL in materials science for defect identification in graphene, and points to future research in optimizing RSL for a broader range of defects and applications in other 2D materials.

Recent Research Progress of Porous Graphene and Applications in Molecular Sieve, Sensor, and Supercapacitor.

Porous graphene, including 2D and 3D porous graphene, is widely researched recently. One of the most attractive features is the proper utilization of graphene defects, which combine the advantages of both graphene and porous materials, greatly enriching the applications of porous graphene in biology, chemistry, electronics, and other fields. In this review, the defects of graphene are first discussed to provide a comprehensive understanding of porous graphene. Then, the latest advancements in the preparation of 2D and 3D porous graphene are presented. The pros and cons of these preparation methods are discussed in detail, providing a direction for the fabrication of porous graphene. Moreover, various superior properties of porous graphene are described, laying the foundation for their promising applications. Owing to its abundant morphology, wide distribution of pore size, and remarkable properties benefited from porous structure, porous graphene can not only promote molecular diffusion and electron transfer but also expose more active sites. Consequently, a serious of applications containing gas sieving, liquid separation, sensors, and supercapacitors, are presented. Finally, the challenges confronted during preparation and characterization of porous graphene are discussed, offering guidance for the future development of porous graphene in fabrication, characterization, properties, and applications.

Process Development of a Liquid-Gated Graphene Field-Effect Transistor Gas Sensor for Applications in Smart Agriculture

A compact, multi-channel ionic liquid-gated graphene field-effect transistor (FET) has been proposed and developed in our work for on-field continuous monitoring of nitrate nitrogen and other nitrogen fertilizers to achieve sustainable and efficient farming practices in agriculture. However, fabricating graphene FETs with easy filling of ionic liquids, minimal graphene defects, and high process yields remains challenging, given the sensitivity of these devices to processing conditions and environmental factors. In this work, two approaches for the fabrication of our graphene FETs were presented, evaluated, and compared for high yields and easy filling of ionic liquids. The process difficulties, major obstacles, and improvements are discussed herein in detail. Both devices, those fabricated using a 3 μm-thick CYTOP® layer for position restriction and volume control of the ionic liquid and those using a ~20 nm-thick photosensitive hydrophobic layer for the same purpose, exhibited typical FET characteristics and were applicable to various application environments. The research findings and experiences presented in this paper will provide important references to related societies for the design, fabrication, and application of liquid-gated graphene FETs.

DFT investigation on effectiveness of Beryllium-doped and defective graphene for anode material in lithium-ion batteries

Lithium-ion batteries employing graphite as the anode material are now widely used in powering electronic gadgets like, mobile phones, laptops, electronic watches and calculators and also to provide required power to run engine of electric vehicles. However, storage capacity, open circuit voltage, energy density and battery life are the major considerations on which researchers are trying different alternatives to achieve better performance of the battery. In this research, Beryllium-doped and defective graphenes have been investigated by employing the ab initio DFT method. It has been found that graphene with a defect and Be–doped graphene with defects can serve as an efficient materials for anode in Li-ion batteries.

Lanthanide Atoms Induce Strong Graphene Sheet Distortion When Adsorbed on Stone-Wales Defects.

Local curvature in graphene can enhance its reactivity and catalytic activity and can be induced by the adsorption of certain chemical species. By employing periodic density functional theory (DFT) calculations, we demonstrate that significant local curvature can be systematically observed when lanthanide atoms (the full series from La to Lu) are adsorbed on the Stone-Wales (SW) defect in graphene, contrary to that in defect-free graphene. Despite the typical high coordination numbers of lanthanide species, their hapticity is always η2 (and not η5, η6, or η7), where Ln atoms are adsorbed on the (7,7) junction, forming relatively short Ln···C separations. Contrary to the pristine graphene, the SW region undergoes considerable distortion and results in much stronger Ln bonding. The positive charge acquired by Ln atoms upon adsorption on SW is approximately 1.5 times larger than that on defect-free graphene. The high visibility of electron-rich lanthanide species in scanning tunneling microscopy images provides a means to locate SW defects in graphene samples experimentally.

Micrometer-Scale Graphene-Based Liquid Cells of Highly Concentrated Salt Solutions for In Situ Liquid-Cell Transmission Electron Microscopy.

In situ liquid-cell transmission microscopy has attracted much attention as a method for the direct observations of the dynamics of soft matter. A graphene liquid cell (GLC) has previously been investigated as an alternative to a conventional SiN x liquid cell. Although GLCs are capable of scavenging radicals and providing high spatial resolutions, their production is fundamentally stochastic, and a significant compositional change in liquids encapsulated in GLCs has recently been pointed out. We found that graphene-based liquid cells were formed in nano- to micrometer sizes with high reproducibility when the concentration of the encapsulated aqueous salt solution was high. In contrast, when we revisited conventional fabrication methods, water-encapsulated GLC was formed with low yield, and any electron diffraction spots from ice were not confirmed by a cooling experiment. The reason for this was the presence of intrinsic defects in the graphene, the presence of which we confirmed by the etch-pit method. The shrinkage of a water-encapsulated cell and a decrease in the bubble area in an aqueous (NH4)2SO4 solution cell suggested that volatile water molecules and gas molecules can leak from the cells during the fabrication and observation processes. Further revision of the conditions for the formation of liquid cells and a reduction in the number of intrinsic graphene defects are expected to lead to the provision of graphene-based liquid cells capable of encapsulating dilute aqueous solutions or pure water.

The etching effect of oxygen during the cooling process of graphene CVD synthesis

Chemical vapor deposition provides a promising approach for the growth of large-area, high-quality graphene on Cu substrates. Oxygen plays either positive or negative roles for graphene synthesis, which have been extensively investigated predominantly focusing on graphene nucleation and growth stages. This study investigates the influence of oxygen during the cooling phase and demonstrates that graphene is more resistant to oxygen at higher temperatures but becomes susceptible to etching as the temperature decreases, unless it is too low. Thermodynamic simulations reveal that at elevated temperatures, oxygen is consumed by methane in the gas phase, leading to the generation of reactive carbon species that promote graphene growth and inhibit etching. Additionally, the etching reactivity of graphene is found to be correlated with the surface orientation of the underlying Cu grains. These findings suggest that defects in graphene can arise during the cooling stage if oxidant impurities in the atmosphere are not adequately controlled. Strategies to suppress graphene etching during cooling, such as reducing oxidant impurities and increasing cooling rates, are also presented.

Formation, Structure, Electronic, and Transport Properties of Nitrogen Defects in Graphene and Carbon Nanotubes.

The substitutional doping of nitrogen is an efficient way to modulate the electronic properties of graphene and carbon nanotubes (CNTs). Therefore, it could enhance their physical and chemical properties as well as offer potential applications. This paper provides an overview of the experimental and theoretical investigations regarding nitrogen-doped graphene and CNTs. The formation of various nitrogen defects in nitrogen-doped graphene and CNTs, which are identified by several observations, is reviewed. The electronic properties and transport characteristics for nitrogen-doped graphene and CNTs are also reviewed for the development of high-performance electronic device applications.

A First Principles Study of Lithium Adsorption in Nanoporous Graphene

Recently, nanoporous graphene has attracted great interest in the scientific community. It possesses nano-sized holes; thus, it has a highly accessible surface area for lithium adsorption for energy storage applications. Defective graphene has been extensively studied. However, the lithium adsorption mechanism of nanoporous graphene is not clearly understood yet. Here, we present theoretical investigations on the lithium-ion adsorption mechanism in nanoporous graphene. We perform ab initio electronic structure calculations based on density functional theory. Lithium adsorption in a graphene nanopore is studied and adsorption sites are determined. We also study different lithium-ion distributions in graphene nanopores to determine the best lithium–nanoporous graphene structures for lithium-ion batteries. We show that lithium ions can be adsorbed in a graphene nanopore, even in a single layer of graphene. It is also shown that adding more nanopores to multilayer nanoporous graphene can result in higher Li storage capacity for new-generation lithium-ion batteries.

Double Tips for In-Plane Polarized Near-Field Microscopy and Spectroscopy.

Near-field optical microscopy and spectroscopy provide high-resolution imaging below the diffraction limit, crucial in physics, chemistry, and biology for studying molecules, nanoparticles, and viruses. These techniques use a sharp metallic tip of an atomic force microscope (AFM) to enhance incoming and scattered light by excited near-fields at the tip apex, leading to high sensitivity and a spatial resolution of a few nanometers. However, this restricts the near-field orientation to out-of-plane polarization, limiting optical polarization choices. We introduce double tips that offer in-plane polarization for enhanced imaging and spectroscopy. These double tips provide superior enhancement over single tips, although with a slightly lower spatial resolution (∼30 nm). They enable advanced studies of nanotubes, graphene defects, and transition metal dichalcogenides, benefiting from polarization control. The double tips allow varied polarization in tip-enhanced Raman scattering and selective excitation of transverse-electric and -magnetic polaritons, expanding the range of nanoscale samples that can be studied.

The Adsorption Behavior of Gas Molecules on Mn/N- and Mn-Doped Graphene.

By using density functional theory (DFT), the adsorption behavior of gas molecules on defective graphene doped with manganese and nitrogen were investigated. The geometric structure, electronic structure, and magnetic properties of two substrates were calculated and the sensing mechanism was also analyzed. The results indicate that the MnSV-GP and MnN3-GP have stronger structural stability, in which Mn atoms and their coordination atoms will become the adsorption point for five gas molecules (CH2O, CO, N2O, SO2, and NH3), respectively. Moreover, at room temperature (298 K), the recovery time of the MnSV-GP sensor for N2O gas molecules is approximately 1.1 s. Therefore, it can be concluded that the MnSV-GP matrix as a magnetic gas sensor has a promising potential for detecting N2O. These results also provide a new pathway for the potential application of Mn-doped graphene in the field of gas sensors.

Microscopic insights into the aggregation dynamics behavior and tribological properties of graphene

The stable dispersion mechanism of graphene nanoparticles in solid-liquid two-phase lubrication systems still lacks in-depth insights into the dynamic aggregation process at the microscale. Herein, the effects of size difference and defect degree on the agglomeration dynamics behavior and tribological properties of graphene nanosheets were revealed by aggregation, pull-out, and friction molecular dynamics simulations. The results showed that for suspended graphene smaller than 100 nm, the increase in size and defect degree effectively improved the dispersion stability of nanosheets in base oil. Attributed to the rise in size improved solid-liquid chemical affinity and promoted out-of-plane deformation of nanosheets to enhance the steric hindrance effect. The increase in defect degree induced spontaneous wrinkling of nanosheets, leading to enhanced interlayer sliding resistance and thus inhibiting agglomeration behavior. Meanwhile, the rise in nanosheet size and degree of defects sufficiently bear the normal load, effectively avoiding the direct contact of asperities and thus improving the wear and temperature rise at the friction interface. However, friction-induced defective graphene curled to form a “carbon nanotube-like” structure, which reduced the oil film strength and led to deterioration of lubrication performance. The research results will provide certain microscale insights into the dispersion and friction of graphene in base oil.

Understanding of Anion Effect on Iron Redox Behavior and Oxygen Reduction Activity of Fe-N-C Electrocatalysts

Fe-N-C catalysts are the most promising platinum group metal (PGM) free electrocatalysts for oxygen reduction reaction (ORR). Significant progress has been made in understanding the active site structure and activity and improving the ORR performance. It is generally accepted that the Fe-N-C sites are associated with FeNx centers embedded in a defective nitrogen-doped graphene. As reported in literature, both pyrrolic N and pyridinic N can support Fe single site; however, it is difficult to distinguish between the two. Furthermore, experimental characterization, such as in-situ X-ray absorption spectroscopy (XAS) and Mössbaruer, has elucidated the redox behavior of Fe2+ to Fe3+ during the reaction. Interestingly, in different acidic environments, the ORR activity exhibits differently. For instance, in comparison between H2SO4 and HClO4 solutions at the same pH value, the Fe redox happens at lower potential in H2SO4; however, the right shift of half-wave potential (E1/2) of ORR in H2SO4, compared with HClO4, indicates higher ORR activity. This indicates that the electrolyte systems have a significant impact on ORR activity. To further understand the active site structure and their ORR activity, density functional theory (DFT) calculations utilizing explicit solvation effect are carried out. XANES simulation using FDMNES suggests that as prepared catalysts could consist of Fe single atom sites supported by both pyrrolic and pyridinic N atoms; however, the pyrrolic species are not as stable as pyridinic species in solution. As presented by DFT simulation, the anions in solutions can interact with FeN4 site differently. SO4 2- binds strongly with the FeN4 center, while HSO4- and ClO4- interact rather weakly. Furthermore, the redox potential and limiting potential are evaluated via mechanistic study. By focusing on more stable Fe center supported by pyridinic N, the results suggest that the transformation of Fe2+ to Fe3+ happens at 0.52 V in H2SO4, which is lower than that in HClO4, 0.69V. More interestingly, the limiting potential (activity) of ORR in H2SO4 is higher than that in HClO4 (0.94 vs 0.68 V). DFT simulation indicated that the anions in electrolyte can impact the Fe redox behavior and ORR performance, which agrees well with the experimental investigation. This work also provides significant guidance to further improve ORR activity of Fe-N-C catalysts.

Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction

The electrocatalytic CO2 reduction reaction (CO2RR) represents an effective way to address energy crises and environmental issues by converting CO2 into valuable chemicals. Single-atom catalysts (SACs) can achieve excellent catalytic activity in CO2RR. However, the study of CO2RR on SACs still poses significant challenges, especially in terms of controlling the selectivity towards the deep product such as CH4 and CH3OH. Herein, we employ density functional theory (DFT) calculations to investigate the CO2RR on Cu SAC supported on N-doped graphene (Cu-N/C) and explore the role of N dopants on the CO2RR performance. Compared to Cu SACs supported on N-doped defective graphene with double vacancy (Cu-N/C-DV), Cu SACs supported on N-doped defective graphene with single vacancy (Cu-N/C-SV) can effectively convert CO2 into the deeply reduced C1 products, including CH4 and CH3OH, thus further indicating that Cu-N/C-SV has a stronger interaction with ∗CO, which is conducive to the deep reduction of ∗CO. Increasing the coordination number of N atoms or the proximity of doping site to the Cu active site can effectively enhance the stability of catalyst and promote the adsorption of ∗CO on Cu-N/C-SV. However, this also increases the free energy of the formation of ∗CHO intermediate. The results suggest that CuC3-Nm, which contains a N atom in the second coordination shell (meta-position) of Cu SACs, has the best electrocatalytic performance of CO2RR in terms of both selectivity and catalytic activity, not only contributing to an in-depth understanding of the reaction mechanism of CO2RR on SACs but also providing insights into the design of SACs for efficient CO2RR.

Micro-Raman spectroscopy of graphene defects and tracing the oxidation process caused by UV exposure

Micro-Raman spectroscopy of graphene defects and tracing the oxidation process caused by UV exposure

Interface Characterization of Graphene‐Silicon Heterojunction Using Hg Probe Capacitance–Voltage Measurement

AbstractInvestigating the intrinsic properties of the Schottky interface between graphene and 3D bulk silicon is crucial. However, the semiconductor technology introduces extra doping and defects in graphene, which significantly disturbs the property of the graphene‐silicon interface. Here, the interface parameters of graphene/n‐Si heterojunction are derived by the damage‐free Hg‐probe capacitance–voltage measurement. Due to its low‐density states, the Fermi level of graphene can be pushed upward, which results in a lower Schottky barrier height (ΦB0) of Hg/graphene/n‐Si (HGS) heterostructure than that of Hg/n‐Si (HS) structure. Additionally, the series resistance (Rs) of HGS becomes lower than that of HS, which can be attributed to the narrowed depletion layer width (WD) and the decreased interface state density (Nit). Furthermore, the frequency characteristic is also investigated. Because of the weak interface state charge trapping–detrapping process and the decreased Nit at high frequency, electrons will accumulate in graphene, and the Fermi level will be pushed up. Hence, the ΦB0 and Rs will decrease with increasing frequency. This study contributes to a deep understanding of the graphene/silicon heterojunction interfaces, which is crucial for designing and optimizing the new electronic and optoelectronic devices based on 2D/3D heterostructure.