Defective/Doped Graphene-Based Materials as Cathodes for Metal-Air Batteries

Graphene,as a proof-of-concept two-dimensional material,has proven to have excellent physical and chemical properties.Its derivatives,such as defective or doped graphene,are also applied as catalytic materials for metal-air batteries(MABs).MABs have been recognized as possible candidates for new-generation energy storage systems due to their ultra-high theoretical energy density.So far,graphene and its derivatives with optimized structures have been widely explored to improve the electrochemical performance in MABs.Generally speaking,perfect graphene crystalline is inert for many catalytic processes,while defects and heteroatoms can endow graphene with high activity for many electrocatalytic reactions.Under this circumstance,recent progress is summarized for defective/doped graphene as air cathodes in aqueous or organic MABs,which are actually different electrochemical systems with distinct requirements for air cathodes.Also,the relationship is clarified between graphene defects/doping and electrocatalytic mechanisms that can be the guidance for catalyst design.Future directions are also prospected for the development of graphene-based MAB cathodes.

Negative Differential Resistance and Spin-Filtering Effects in Zigzag Graphene Nanoribbons with Nitrogen-Vacancy Defects

We explore the electronic and transport properties of zigzag graphene nanoribbons （GNRs） with nitrogen-vacancy defects by performing fully self-consistent spin-polarized density functional theory calculations combined with non-equilibrium Green＇s function technique. We observe robust negative di erential resistance （NDR） effect in all examined molecular junctions. Through analyzing the calculated electronic structures and the bias-dependent transmission coefficients, we find that the narrow density of states of electrodes and the bias-dependent effective coupling between the central molecular orbitals and the electrode subbands are responsible for the observed NDR phenomenon. In addition, the obvious di erence of the transmission spectra of two spin channels is observed in some bias ranges, which leads to the near perfect spin-filtering effect. These theoretical findings imply that GNRs with nitrogenvacancy defects hold great potential for building molecular devices.

Quantum plasmons in the hybrid nanostructures of double vacancy defected graphene and metallic nanoarrays

We study the plasmonic properties of hybrid nanostructures consisting of double vacancy defected graphene(DVDGr)and metallic nanoarrays using the time-dependent density functional theory. It is found that DVDGr with pure and mixed noble/transition-metal nanoarrays can produce a stronger light absorption due to the coherent resonance of plasmons than graphene nanostructures. Comparing with the mixed Au/Pd nanoarrays, pure Au nanoarrays have stronger plasmonic enhancement. Furthermore, harmonics from the hybrid nanostructures exposed to the combination of lasers ranged from ultraviolet to infrared and a controlling pulse are investigated theoretically. The harmonic plateau can be broadened significantly and the energy of harmonic spectra is dramatically extended by the controlling pulse. Thus, it is possible to tune the width and intensity of harmonic spectrum to achieve broadband absorption of radiation. The methodology described here not only improves the understanding of the surface plasmon effect used in a DVDGr-metal optoelectronic device but also may be applicable to different optical technologies.

Coherent resonance of quantum plasmons in Stone-Wales defected graphene-silver nanowire hybrid system

Defected graphene has a more important practical significance than graphene. Silver nanoparticles can modify the optical properties of defected graphene. We present herein a detailed theoretical analysis about the coherent resonance of quantum plasmons in the Stone-Wales （SW） defected graphene-silver nanowire hybrid system by using time-dependent density functional theory. The plasmon coherent effect is mainly attributed to the electromagnetic field coupling between the Stone-Wales defected graphene and silver nanowires. As a result, the optical response of the hybrid system exhibits a remarkable enhancement. Plasmon resonance, which depends on polarization and selectable tuning, is enhanced in wide frequency regions. Moreover, it reveals that the resonance frequency of an optical absorption spectrum depends on the space configuration of the SW defected graphene in the hybrid system. This investigation provides a better understanding of the plasmon enhancement effect used in a graphene-based photoelectric device. The study also offers an effective means of detecting the defects existing in graphene.

Probing the compound effect of spatially varying intrinsic defects and doping on mechanical properties of hybrid graphene monolayers

Doping in pristine 2 D materials brings about the advantage of modulating wide range of mechanical properties simultaneously.However,intrinsic defects(such as Stone-Wales and nanopore) in such hybrid materials are inevitable due to complex manu facturing and synthesis processes.Besides that,de fects and irregularities can be intentionally induced in a pristine nanostructure for multi-synchronous modulation of various multi-functional properties.Whatever the case may be,in order to realistically analyse a doped graphene sheet,it is of utmost importance to investigate the compound effect of doping and defects in such 2 D monolayers.Here we present a molecular dynamics based investigation for probing mechanical properties(such as Young’s modulus,post-elastic behaviour,failure strength and strain)of doped graphene(C14 and Si) coupling the effect of inevitable defects.Spatial sensitivity of defect and doping are systematically analyzed considering different rational instances.The study reveals the effects of individual defects and doping along with their possible compounded influences on the failure stress,failure strain,Young’s modulus and constitutive relations beyond the elastic regime.Such detailed mechanical characterization under the practically relevant compound effects would allow us to access the viability of adopting doped graphene in various multifunctional nanoelectromechanical devices and systems in a realistic situation.

Di-defects synergy boost electrocatalysis hydrogen evolution over two-dimensional heterojunctions

Electronic modulation on the inert basal plane of transition-metal dichalcogenides(TMDs)through vacancy defect excitation,although extremely challenging,is urgent for understanding the factors that impact the hydrogen evolution reaction(HER)catalytic activity.Here,ultrathin WS2 nanosheets with precise quantitative single atomic S-vacancy on the inert basal plane were flexible prepared through hydrogen peroxide etching strategy.The as-synthesized single atomic S-vacancy defect WS2(SVD-WS2)nanoflake with the activated basal plane exhibited an impressive overpotential of 137 mV at a current density of 10 mA·cm^(-2) and a Tafel slope of 53.9 mV dec^(-1).Furthermore,anchoring on the defect graphene matrix,the assembled two-dimensional(2D)stacking heterojunction exhibits further enhanced HER catalytic activity(an overpotential of 108 mV vs.10 mA·cm^(-2) and a Tafel slope of 48.3 mV·dec^(-1))and stability(〜10%decline after 9,000 cycles),which attributed to the electronic structure modulation from the synergetic interactions between SVD-WS_(2) and defect graphene.Our finding provides a smart defects introduce strategy to trigger high-efficiency hydrogen evolution over WS_(2) nanosheets and a general 2D heterojunctions fabricated inspiration based on strong interaction interface.