Graphene Substrate Research Articles

One‐Step Electrodeposition of Iron Oxyhydroxide Onto 3D Porous Graphene Substrates for on Chip Asymmetric Micro‐Supercapacitors

AbstractElectrochemical capacitors based on redox active materials can achieve greater capacitance values than traditional electric double layer composites. Herein, electrodeposition of iron oxyhydroxide from a mildly acidic acetate precursor is reported. The one‐step deposition resulted in a submicron film composed of FeOOH phase, which was confirmed via Raman and x‐ray photoelectron spectroscopy. The capacitance increased linearly with loading amount and achieved a maximum at 1600 mC deposition with 120 mF cm−2 at 25 mV s−1 after which the film became more resistive, limiting electrolyte access to the porous graphene substrate. The deposited FeOOH demonstrated promising rate capability and good cycling stability, without phase changes, retaining 82 % of the initial capacitance after 5000 consecutive charge/discharge cycles. The charge storage mechanism of FeOOH was determined via in situ Raman spectroscopy, which followed reversible iron oxygen vibration changes upon cycling which become more intense upon reduction as a result of sodium ion intercalation. Furthermore, an asymmetric configuration full cell combining FeOOH/MnO2 allowed the working voltage to be extended to 2 V, maintaining an ideal capacitor behaviour, and achieving a maximum energy and power density of 21 μWh cm−2 and 2.5 mW cm−2 respectively.

Adsorption of Hydrogen Cyanide, Cyanogen Fluoride and Cyanogen Chloride on Iron Decorated Graphene Substrates: A DFT-D2 Study

Adsorption of Hydrogen Cyanide, Cyanogen Fluoride and Cyanogen Chloride on Iron Decorated Graphene Substrates: A DFT-D2 Study

Seebeck Coefficient Modulation of Graphene Grown on Faceted Cu Surfaces

The thermoelectric properties of polycrystalline copper (Cu) surfaces partially covered with graphene grown by Joule‐heating chemical vapor deposition using scanning thermoelectric microscopy are investigated. Atomic‐resolution atomic force microscopy topographic images of graphene grown on Cu(100) surfaces showed a 1D stripe pattern of Moiré superlattices, while thermoelectric voltage images clearly distinguish wrinkle defects caused by thermal mismatch between graphene and Cu substrate. Regions of different signs were found in the thermoelectric voltage image of the graphene island, which are attributed to the faceted surface of the Cu substrate. In addition, faceted surfaces consisting of low‐ and high‐index Cu surfaces are formed on the Cu grain to minimize the surface energy. Due to these structural changes, charge transfer and chemical interactions at the interface between the graphene and Cu facets affect the electronic structure of the graphene, which is understood as the observed Seebeck coefficients with different signs in the thermoelectric microscopy measurements, which are sensitive to the local density of states.

Computational Design of the Electronic Response for Volatile Organic Compounds Interacting with Doped Graphene Substrates

Changes in the work function provide a fingerprint to characterize analyte binding in charge transfer-based sensor devices. Hence, a rational sensor design requires a fundamental understanding of the microscopic factors controlling the modification of the work function. In the current investigation, we address the mechanisms behind the work function change (WFC) for the adsorption of four common volatile organic compounds (toluene, ethanol, 2-Furfurylthiol, and guaiacol) on different nitrogen-doped graphene-based 2D materials using density functional theory. We show that competition between the surface dipole moment change induced by spatial charge redistribution, the one induced by the pure adsorbate, and the one caused by the surface deformation can quantitatively predict the work function change. Furthermore, we also show this competition can explain the non-growing work function change behavior in the increasing concentrations of nitrogen-doped graphenes. Finally, we propose possible design principles for WFC of VOCs interacting with N-doped graphene materials.

Electronic and Magnetic Properties of Cobalt Clusters on Pristine and Divacancy Graphene

Using ab initio calculations we investigate the adsorption of Co atoms, dimers and small cobalt clusters of 5 and 13 atoms on pristine graphene and graphene with a double vacancy. We report the atomic, electronic, magnetic and energetic properties of these systems. Stable adsorption configurations tend to maximize the number of cobalt-carbon bonds. On graphene, the adsorption energy of the clusters is only about 0.4 to 1 eV, and the clusters are relatively mobile on graphene. Interestingly, for different adsorbed Co13 isomers on graphene it is found that they converge to the same atomic structure. On graphene with a divacancy, the Co clusters bind in the divacancy site and isomerisation also occurs for the Co5 cluster system as well as for Co13. Co atoms and clusters can be effectively immobilized on the divacancy with corresponding adsorption energy being significantly enhanced by about 5 to 7 eV. All clusters act as electron donors in the interaction with the graphene/divacancy systems, and the amount of electron charge transfer increases with cluster size. Finite magnetic moments occur for all systems, where upon adsorption, the magnetic moment of the isolated Co atom (3μB) is significantly reduced due to electron transfer and bonding, resulting in values varying from ≈0.9-2.2 μB per Co atom. For the pristine graphene substrate, the total induced magnetic moments on the carbon atoms are negligible, while on the divacancy system, they are of the order of 0.1-0.3 μB. The attractive physical properties of these hybrid systems could find applications in catalysis and materials science.

Theoretical study on the isomerization mechanism of azobenzene derivatives on graphene substrate

Theoretical study on the isomerization mechanism of azobenzene derivatives on graphene substrate

Exploring Metal‐Organic Molecular Beam Epitaxy as an Alternative Pathway towards 2D Transition Metal Dichalcogenides WSe2 and WS2

A new approach for the growth of vertical 2D van‐der‐Waals heterostructures is reported: Using metal‐organic molecular beam epitaxy (MOMBE), aspects of chemical and physical vapor deposition are combined to grow ultrathin films of WX2 (X = Se, S) on epitaxial graphene on SiC(0001). Thorough investigation of the films using a variety of spectroscopy, diffraction, and microscopy techniques reveals an island‐like growth of predominantly mono‐ and bilayer regions with crystallite size up to 300 nm, which show a preferred epitaxial alignment with the graphene substrate. Angle‐resolved photoemission reveals a well‐developed band structure of the heterostructure, with the growth process showing minimal effect on the electronic structure of the graphene sheet.

Giant Enhancement of Negative Friction by Resonant Coupling Between Localized Surface Phonon Polaritons and Graphene Plasmonics

Abstract Negative friction refers to a frictional force that acts in the same direction as the motion of an object, which has been predicted in terahertz (THz) gain systems [Phys. Rev. B 108 (4), 045406(2023)]. In this work, we investigate the enhancement of the negative friction experienced by nanospheres placed near a graphene substrate. We find that the magnitude of negative friction is related to the resonant coupling between the surface plasmon polaritons (SPPs) of the graphene and localized surface phonon-polaritons (LSPhP) of nanospheres. We exam nanospheres consisted of several different materials, including SiO2, SiC, ZnSe, NaCl, lnSb. Our results suggest that the LSPhP of NaCl nanospheres match effectively with the amplified SPPs of graphene sheets. The negative friction for NaCl nanospheres can be enhanced about one-to-two orders of magnitude compared to that of silica (SiO2) nanospheres. At the resonant peak of negative friction, the required quasi-Fermi energy of graphene is lower for NaCl nanospheres. Our finds hold great prospects for the mechanical manipulations of nanoscale particles.

Unraveling the multistage phase transformations in monolayer MoTe2−x

Monolayer MoTe2 exhibits a variety of derivative structural phases and associated intriguing electronic properties that enable a wealth of potential applications in future electronic and optoelectronic devices. However, a comprehensive study focusing on the complexities of the controllable phase evolution in this atomically thin film has yet to be performed. This work aims to address this issue by systematically investigating molecular beam epitaxial growth of monolayer Mo–Te compounds on bilayer graphene substrates. By utilizing scanning tunneling microscopy, we explored a series of thermally driven structural phase evolutions, including distinct T′-MoTe2, H-MoTe2, Mo6Te6 nanowires, and multistoichiometric MoTe2−x. Furthermore, we carefully investigated the critical effects of the growth parameters—annealing temperature and time and tellurium concentration—on the controllable and reversible phase transformation within monolayer MoTe2−x. The findings have significant implications for understanding the thin film synthesis and phase transformation engineering inherent to two-dimensional crystals, which can foster further development of high-performance devices.

Investigating the role of graphene in the formation and stability of [formula omitted]-phase antimonene islands

Two-dimensional materials have shown tremendous potential for various technological applications. Particularly, 2D antimony exhibits high applicability in electronics, sensors, and batteries. This 2D material, known as antimonene, presents two stable phases: α (rectangular lattice) and β (honeycomb lattice), whose formation depends on the substrate where antimony is deposited. In this study, we investigated the growth of antimonene islands on graphene, forming an antimonene/graphene heterostructure. To demonstrate the significance of graphene in the synthesis of antimonene, we also studied antimony deposited on a bare copper foil similar to the one used for the graphene substrate. Antimony deposition exhibits the β phase antimonene structure when deposited on top of monolayer graphene, but not when deposited on a bare copper foil, nor on top of multilayer graphene. Additionally, we investigated the stability of the heterostructure after exposure to air. Pure antimony islands are formed when evaporated in high vacuum on top of graphene and copper substrates, and antimony atoms oxidize upon exposure to air. After annealing the sample in ultra-high-vacuum at temperatures lower than 200 °C, more than half of pure antimony is recovered and almost all oxidized antimony is desorbed from the graphene substrate. In contrast, almost none of the oxidized antimony is desorbed from the bare copper substrate, highlighting the key role of the heterostructure on the formation and preservation of the physical and chemical properties of the deposited 2D material.

Droplet bouncing electricity generation on graphene substrate

Abstract Since the discovery of the phenomenon of droplets bouncing on hydrophobic surfaces, researchers have been dedicated to studying the underlying physical mechanisms of this phenomenon. Particularly, in recent years, researchers have focused on the observation that droplet bouncing can generate electrical signals. Inspired by this, we explore the potential applications of electrical signals generated by droplets (water droplets) bouncing in sensors and other relevant fields. In this study, we chose a well-established reduced graphene oxide (rGO) film, typical in the sensor field, as a substrate to investigate the bouncing electricity generation performance of water droplets on it. Three variable factors were considered, including droplet bouncing on rGO substrates with different inclinations, bouncing of droplets of different sizes at the same inclination on rGO substrates, and droplet dropping frequency, to investigate their effects on the electrical signals.

Investigating Molecular Adsorption on Graphene-Supported Platinum Subnanoclusters: Insights from DFT + D3 Calculations.

Platinum (Pt) subnanoclusters have become pivotal in nanocatalysis, yet their molecular adsorption mechanisms, particularly on supported versus unsupported systems, remain poorly understood. Our study employs detailed density functional theory (DFT) calculations with D3 corrections to investigate molecular adsorption on Pt subnanoclusters, focusing on CO, NO, N2, and O2 species. Gas-phase and graphene-supported scenarios are systematically characterized to elucidate adsorption mechanisms and catalytic potential. Gas-phase Pt n clusters are first analyzed to identify stable configurations and assess size-dependent reactivity. Transitioning to graphene-supported Pt n clusters, both periodic and nonperiodic models are employed to study interactions with graphene substrates. Strong adsorbate interactions predominantly occur at single top sites, revealing distinct adsorption geometries and stabilization effects for specific molecules on Pt6 clusters. Energy decomposition analysis highlights the paramount role of graphene substrates in enhancing stability and modulating cluster-adsorbate interactions. The interaction energy emerges as a critical criterion within the Sabatier principle, crucial for distinguishing between physisorption and chemisorption. Hybridization indices and charge density flow tendencies establish direct relationships with stabilization processes, underscoring graphene's influence in stabilizing highly reactive subnanoclusters. This comprehensive investigation provides critical insights into molecular adsorption mechanisms and the catalytic potential of graphene-supported Pt nanoclusters. Our findings contribute to a deeper understanding of nanocatalysis, emphasizing the essential role of substrates in optimizing catalytic performance for industrial applications.

High-Yield Large-Scale Suspended Graphene Membranes over Closed Cavities for Sensor Applications.

Suspended membranes of monatomic graphene exhibit great potential for applications in electronic and nanoelectromechanical devices. In this work, a "hot and dry" transfer process is demonstrated to address the fabrication and patterning challenges of large-area graphene membranes on top of closed, sealed cavities. Here, "hot" refers to the use of high temperature during transfer, promoting the adhesion. Additionally, "dry" refers to the absence of liquids when graphene and target substrate are brought into contact. The method leads to higher yields of intact suspended monolayer chemical vapor deposition (CVD) graphene and artificially stacked double-layer CVD graphene membranes than previously reported. The yield evaluation is performed using neural-network-based object detection in scanning electron microscopy (SEM) images, ascertaining high yields of intact membranes with large statistical accuracy. The suspended membranes are examined by Raman tomography and atomic force microscopy (AFM). The method is verified by applying the suspended graphene devices as piezoresistive pressure sensors. Our technology advances the application of suspended graphene membranes and can be extended to other two-dimensional materials.

Defect-Free Nanowelding of Bilayer SnSe Nanoplates.

Nanowelding is a bottom-up technique to create custom-designed nanostructures and devices beyond the precision of lithographic methods. Here, a new technique is reported based on anisotropic lubricity at the van der Waals interface between monolayer and bilayer SnSe nanoplates and a graphene substrate to achieve precise control of the crystal orientation and the interface during the welding process. As-grown SnSe monolayer and bilayer nanoplates are commensurate with graphene's armchair direction but lack commensuration along graphene's zigzag direction, resulting in a reduced friction along that direction and a rail-like, 1D movement that permits joining nanoplates with high precision. This way, molecular beam epitaxially grown SnSe nanoplates of lateral sizes 30-100nm are manipulated by the tip of a scanning tunneling microscope at room temperature. In situ annealing is applied afterward to weld contacting nanoplates without atomic defects at the interface. This technique can be generalized to any van der Waals interfaces with anisotropic lubricity and is highly promising for the construction of complex quantum devices, such as field effect transistors, quantum interference devices, lateral tunneling junctions, and solid-state qubits.

Role of graphene substrate in the formation of MoS2-based nanoparticles with improved sensitivity to NO2 gas

MoS2 coatings were formed on surface-oxidized silicon, chemical vapor deposition (CVD)-grown graphene, and reduced fluorinated graphene (rFG) from ammonium tetrathiomolybdate. The samples were annealed under ultra-high vacuum conditions at a temperature of 1000 °C. Analysis of X-ray photoelectron and X-ray absorption spectra revealed a bonding between MoS2 and the supporting material that was particularly strong for CVD-graphene. Uniform covering of the flat CVD-graphene surface with MoS2 nanoparticles and numerous contacts between them promoted the removal of sulfur and the formation of exposed molybdenum edges. A cracked MoS2 coating consisting of dense domains was formed on the wrinkled rFG surface. The study of samples as NO2 gas sensors revealed the best performance of MoS2/CVD-graphene. The sensor detected NO2 in air below 50 ppb at room temperature, had good response and recovery, operated in humid air, and demonstrated excellent NO2 selectivity. The other two sensors gave signals at elevated temperatures. The advantage of MoS2/CVD-graphene is due to improved electron transport in the hybrid, accessibility of small MoS2 nanoparticles to the analyte, and passivation of high-energy molybdenum sites by oxygen, which improves NO2 desorption.

Metal–Organic Frameworks with Axial Cobalt–Oxygen Coordination Modulate Polysulfide Redox for Lithium–Sulfur Batteries

AbstractAlthough the ultrahigh theoretical energy density and cost‐effectiveness, lithium–sulfur (Li‐S) batteries suffer from sluggish conversion kinetics and the shuttling effect of soluble lithium polysulfides (LiPSs). Herein, conductive hexagonal cobalt‐organic framework (Co‐HTP) nanosheets are anchored in situ on carboxyl graphene (CG) substrates and serve as host catalysts to modulate the polysulfide redox. Substantial characterizations identify that the local coordination environment of the quadrilateral Co–N4 units transforms into an asymmetric penta‐coordinated O–Co–N4 with axial Co─O coordination, which triggers spin polarization and remarkable electron delocalization of Co 3d orbital. The higher spin state and lower local electron density of the O–Co–N4 sites induce more active electronic states in Co‐HTP/CG and facilitate orbital hybridization with polysulfides to form more stable bond orders. Such optimized electronic structure significantly accelerates redox kinetics and enhances the adsorption strength of polysulfides. These merit the lithium–sulfur battery based on Co‐HTP/CG with a high reversible capacity, impressive rate capability, and prolonged cycling performance over 500 cycles. This work will enrich the design philosophy of modulating the spintronic structure of electrocatalysts for advanced Li–S batteries and beyond.

Fabrication of Nano-Carbon-Based Sustainable Perovskite Solar Cells

The rising need for sustainable energy solutions has fuelled considerable research into novel technologies that harness solar energy for efficient and scalable energy storage. Carbon nanotubes (CNTs) have emerged as feasible candidates for these applications due to their unique properties, such as high surface area, better electrical conductivity, and chemical stability.This report focuses on the design and fabrication of cost-effective nano-carbon-based perovskite solar cells (PSCs) and discusses their potential for clean energy generation and storage. This experimental study shows a novel technique to increase the sustainability the conventional fluorine-doped tin oxide (FTO) substrate with an Indium Tin Oxide (ITO) derived from electronic waste and incorporating nanocarbon based-graphene with solution-based techniques. This addition serves as a good basis for the ITO coating, aids charge transport in the perovskite solar cell, and promotes uniform covering maximum electrical conductivity, and transparency. Being the transparent conducting electrode, the CNTs is infused with the upcycled ITO coated glass and was included in the perovskite solar cell architecture, which replaces the traditional ITO electrode, lowering material costs, and improving the circular economy for energy storage devices, and a cleaner energy future.The ITO extraction process entails recovering indium and tin from mobile phones using an environmentally friendly and economical chemical etching process using hydrochloric acid (HCl) to remove the ITO layer. To ensure the purity and structural integrity of the ITO nanoparticles, they were rigorously characterized using X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. After depositing a perovskite- CNTs precursor solution on the ITO layer glass substrate, the light-absorbing layer was annealed. Electron transport and hole-blocking layers were then deposited utilizing solution processing techniques using the PEDOT: PSS and metal electrodes were deposited to complete the device manufacturing. The current-voltage (J-V) relationship was used to compute the open-circuit voltage, short-circuit current density, fill factor (FF), and power conversion efficiency (PCE) of a solar cell. Electrical characterization allow for the calculation of solar cell performance metrics such as short-circuit current (Isc), short-circuit current density (Jsc), and open-circuit voltage (Voc). These findings imply that employing e-waste-derived ITO on graphene substrates to create high-efficiency perovskite solar cells is a realistic option. This research provides a sustainable and cost-effective method for producing high-performance perovskite solar cells by eco-friendly upcycling e-waste for ITO extraction, addressing the critical issue of e-trash management. Keywords Perovskite solar cells, CNTs, sustainable energy, energy conversion.

Investigation the behavior of different fullerenes on graphene surface

In the present study, the regime of motion of fullerene molecules on graphene substrate in a specific temperature range is investigated. The potential energy of fullerene molecules is analyzed using classical molecular dynamics methods. Fullerene molecules C36, C50, C60, C76, C80, and C90 are selected due to spherical shapes of different sizes and good motion performance in previous studies. Analysis of the motion regime at different temperatures is one of the main objectives of this study. To achieve this aim, the translational and rotational movements of fullerene molecules are studied independently. In the first step of the investigation, Lennard-Jone's potential energy of fullerene molecules is calculated. Subsequently, the motion regime of different fullerenes is classified based on their displacement and diffusion coefficient. Findings indicate C60 is not appropriate in all conditions. However, C90 and C76 molecules are found to be appropriate candidates in most cases in different conditions. As far as a straight-line movement is considered, the deviation of fullerene molecules is compared by their angular velocities. Although C60 has a lower angular velocity due to its symmetrical shape, it may not move well due to its low diffusion coefficient. Overall, our study helps to understand the performance of different fullerene molecules on graphene substrate and find their possible applications, especially as wheels in nanomachine or nanocarrier structures.

A Theoretical Inquest of Atomically Injected Ni-Atom over Graphene and Analogous Substrates for Hydrogen Evolution Reaction

A Theoretical Inquest of Atomically Injected Ni-Atom over Graphene and Analogous Substrates for Hydrogen Evolution Reaction

Catalytic Potential of Supported Superatoms.

The importance of catalysts in industrial products is a driving factor in the search of efficient and cost-effective catalysts, creating considerable interest in the past decade in single-atom catalysis. One of the first requirements of a good catalyst is that it should bind to the molecules with energies intermediate between physisorption and chemisorption while simultaneously activating them. Herein, it is shown that superatoms, which are atomic clusters with fixed size and composition, can meet this challenge even better than the atoms whose chemistry they mimic. The reactions of molecules such as H2, O2, N2, CO, NO, and CO2 with an atom (Li) and its corresponding superatom (Li3O) are confirmed through study. As these clusters need to be supported on a substrate for practical applications, the study focuses on the reaction of CO2 with Li and Li3O supported on graphene, Au(111), and Cu(111) substrates. Using density functional theory, it is shown that the Li3O superatom can activate CO2 far greater than the Li atom - stretching the CO bond from 1.16 Å to as large as 1.30 Å and bending the O─C─O bond angle from 180° to as low as 120°. Equally interesting, the results are not very sensitive to the substrate.