RESUMEN
Graphene (Gr) has shown great potential in the field of oxidation protection for metals. However, numerous studies have shown that Gr will suffer structural degradation on metal surface during high-temperature oxidation, which significantly limited the effectiveness of their oxidation protection. Therefore, understanding the degradation mechanism of Gr is of great interest to enhance their structural stability. Here, the effect of copper (Cu) surface roughness on the high-temperature structural stability of single-layer graphene (SLG) was examined using Cu covered with SLG as a model material. SLG/Cu with different roughness values was obtained via high-temperature annealing of the model material. After high-temperature oxidation at 500 °C, Raman spectra analysis showed that the defect density of the oxidized SLG increased from 41% to 81% when the surface roughness varied from 37 nm to 81 nm. Combined with density functional theory calculations, it was found that the lower formation energy of the C-O bond on rough Cu surfaces (0.19 eV) promoted the formation of defects in SLG. This study may provide guidance for improving the effectiveness of SLG for the oxidation protection of metallic materials.
RESUMEN
Grain boundaries (GBs) and twin boundaries (TBs) in copper (Cu) are two major planar defects that influence electrical conductivity due to their complex electron transport characteristics, involving electron scattering and electron concentration. Understanding their local electronic states is crucial for the design of future conductor materials. In this study, we characterized electron behaviors at TBs and GBs within one Cu grain using atomic force microscopy. Our findings revealed that, compared with GBs, TBs exhibit better current transport capability (direct-current mode) and larger electromagnetic loss (high-frequency microwave mode). Both kelvin probe force microscopy and theoretical analysis suggested that TBs with smaller lattice disorder possess lower density of states at the Fermi level. The reduced density of states may result in decreased electron scattering and a lower electron concentration at TBs. The latter can be highlighted by the high-frequency skinning effect, manifested as larger electromagnetic loss and weaker high-frequency conductivity.
RESUMEN
Interfacial bonding that directly influences the functional and mechanical properties of metal/nonmetal composites is commonly estimated by destructive pull-off measurements such as scratch tests, etc. However, these destructive methods may not be applicable under certain extreme environments; it is urgently necessary to develop a nondestructive quantification technique to determine the composite's performance. In this work, the time-domain thermoreflectance (TDTR) technique is applied to study the inter-relationship between interfacial bonding and interface characteristics through thermal boundary conductance (G) measurements. We think that interfacial phonon transmission capability plays a decisive role in influencing interfacial heat transport, especially for scenarios with a large mismatch of phonon density of states (PDOS). Moreover, we demonstrated this method at (100) and (111) cubic boron nitride/copper (c-BN/Cu) interfaces by both experimental and simulation efforts. The results show that the TDTR-measured G of the (100) c-BN/Cu interface (30 MW/m2·K) is about 20% higher than that of the (111) c-BN/Cu (25 MW/m2·K), which is ascribed to that higher interfacial bonding of the (100) c-BN/Cu endows it with better interfacial phonon transmission capability. In addition, detailed comparison of 10+ other metal/nonmetal interfaces exhibits similar positive relationship for interfaces with a large PDOS mismatch but negative relationship for interfaces with a small PDOS mismatch. The latter one is attributed to that extra inelastic phonon scattering and electron transport channels abnormally promoting interfacial heat transport. This work may provide some insights into quantitatively establishing inter-relationship between interfacial bonding and interface characteristics.
RESUMEN
Transition metal phosphates (TMPs) are regarded as efficient co-catalysts for photoanodes, but they are rarely applied in hydrogen production reactions. In this work, iron phosphate (FePi), a co-catalyst for hydrogen production, is introduced onto the Fe2O3 surface by facile surface phosphorization under low-temperature conditions. The surface FePi leads to a shift of the onset potential by +201 mV and an increase in the photocurrent density by more than 10 mA cm-2 at 0 VRHE for the Fe2O3/p-Si photocathode in a strong alkaline electrolyte. The role of FePi stems from the smaller transfer resistance, efficient photogenerated carrier separation and electron injection, and preferable H* adsorption energy, as suggested by Kelvin probe force microscopy and density functional theory (DFT) calculation. The surface phosphorization presents a facile and attractive strategy for the treatment of transition metal oxide catalyzed photocathodes for green hydrogen production.
RESUMEN
As a typical two-dimensional material, graphene (Gr) has shown great potential to be used in thermal management applications due to its ultrahigh in-plane thermal conductivity (k). However, low interface thermal conductance (ITC) between Gr and metals to a large extent limits the effective heat dissipation in Gr-based devices. Therefore, having a deep understanding on heat transport at Gr-metal interfaces is essential. Because of the semimetallic nature of Gr, electrons would possibly play a role in the heat transport across Gr-metal interfaces as heat carriers, whereas, However, how much the electron can participate in this process and how to optimize the total ITC considering both electron and phonon transportations have not yet been revealed yet. Therefore, in this work, hydrogenation-treated Gr (H-Gr) was sandwiched by nickel (Ni) nanofilms to compare with the samples containing pure Gr for investigating the interfacial electron behaviors. Moreover, both Gr and H-Gr sets of the samples were prepared with different layer numbers (N) ranging from 1 to 7, and the corresponding ITC was systematically studied based on both time-domain thermoreflectance measurements and theoretical calculations. We found that a larger ITC can be obtained when N is low, and the ITC may reach a peak value when N is 2 in certain circumstances. The present findings not only provide a comprehensive understanding on heat transport across Gr-metal interfaces byconsidering a combined effect of the interfacial interaction strength, phonon mode mismatch, and electron contributions, but also shed new lights on interface strucure optimiazations of Gr-based devices.
RESUMEN
It is difficult to disperse graphene flakes well in an aqueous solution while maintaining conductivity due to its high hydrophobicity. Herein, we demonstrated that a well-dispersed state of graphene in an aqueous solution was realized by using reduced graphene oxide (rGO) with a suitable content of oxygen-functional groups. A rGO-dispersed graphene (rGO/G) film was fabricated from the graphene dispersion with good conductivity by using rGO with a C/O ratio of 2.48 as the surfactant. Also, the prepared rGO/G aerogel has a broad prospect. Density functional theory calculation revealed that the strong electrostatic repulsion, which was more potent than the van der Waals force and the π-π interaction, was the primary driving force promoting the dispersibility of graphene in an aqueous solution. Furthermore, the repulsion of the rGO/G dispersion decreased with the reduction of the oxygen-functional groups of rGO. Therefore, applying rGO with an appropriate content of oxygen-functional groups is an alternative option to improve the dispersibility of graphene in an aqueous medium while maintaining its original properties, from which many potential applications could be expected.