Phosphorus and nitrogen co-doped graphene for catalytic dehydrochlorination of 1,2-dichloroethane

A phosphorus and nitrogen co-doped graphene(PNG)was developed via a two-step pyrolysis approach through the intermedium of g-C_(3)N_(4) template and glyphosate as the phosphorus source,and was used for the catalytic dehydrochlorination of 1,2-dichloroethane(EDC)to vinyl chloride monomer(VCM)production.The characterization results indicate that a volcano relationship of surface area and surface properties with the usage of phosphorus precursor was observed,and the sample of PNG-900-6 possesses not only the thin film structure with enhanced surface area but also the smaller grain size of PNG attachments.Accordingly,such PNGs show a great improvement of catalytic performance in the dehydrochlorination of EDC,and the PNG-900-6 catalyst behaves the best with a 4-times higher activity than that on the nitrogen doped graphene(NG).It was also proved that the synergetic effect of the unique P-C coordination on the graphene to generate more quaternary nitrogen species was crucial in determining the catalytic performance of EDC conversion.Our results demonstrate that the phosphorus and nitrogen co-doped graphene offers many advantages in physical structure and chemical property,and are also great potential on the catalytic application in the dehydrochlorination of 1,2-dichloroethane.

A study of highly activated hydrogen evolution reaction performance in acidic media by 2D heterostructure of N and S doped graphene on MoO_(x)

Herein,a layer of molybdenum oxide(MoO_(x)),a transition metal oxide(TMO),which has outstanding catalytic properties in combination with a carbonbased thin film,is modified to improve the hydrogen production performance and protect the MoO_(x)in acidic media.A thin film of graphene is transferred onto the MoO_(x)layer,after which the graphene structure is doped with N and S atoms at room temperature using a plasma doping method to modify the electronic structure and intrinsic properties of the material.The oxygen functional groups in graphene increase the interfacial interactions and electrical contacts between graphene and MoO_(x).The appearance of surface defects such as oxygen vacancies can result in vacancies in MoO_(x).This improves the electrical conductivity and electrochemically accessible surface area.Increasing the number of defects in graphene by adding dopants can significantly affect the chemical reaction at the interfaces and improve the electrochemical performance.These defects in graphene play a crucial role in the adsorption of H^(+)ions on the graphene surface and their transport to the MoO_(x)layer underneath.This enables MoO_(x)to participate in the reaction with the doped graphene.N^(‐)and S^(‐)doped graphene(NSGr)on MoO_(x)is active in acidic media and performs well in terms of hydrogen production.The initial overpotential value of 359 mV for the current density of−10 mA/cm^(2)is lowered to 228 mV after activation.

Doped graphene/carbon black hybrid catalyst giving enhanced oxygen reduction reaction activity with high resistance to corrosion in proton exchange membrane fuel cells

Nitrogen doping of the carbon is an important method to improve the performance and durability of catalysts for proton exchange membrane fuel cells by platinum–nitrogen and carbon–nitrogen bonds. This study shows that p-phenyl groups and graphitic N acting bridges linking platinum and the graphene/carbon black(the ratio graphene/carbon black = 2/3) hybrid support materials achieved the average size of platinum nanoparticles with(4.88 ± 1.79) nm. It improved the performance of the lower-temperature hydrogen fuel cell up to 0.934 W cm^(-2) at 0.60 V, which is 1.55 times greater than that of commercial Pt/C. Doping also enhanced the interaction between Pt and the support materials, and the resistance to corrosion, thus improving the durability of the low-temperature hydrogen fuel cell with a much lower decay of 10 mV at 0.80 A cm^(-2) after 30 k cycles of an in-situ accelerated stress test of catalyst degradation than that of 92 mV in Pt/C, which achieves the target of Department of Energy(<30 mV). Meanwhile,Pt/Nr EGO_(2)-CB_(3) remains 78% of initial power density at 1.5 A cm^(-2) after 5 k cycles of in-situ accelerated stress test of carbon corrosion, which is more stable than the power density of commercial Pt/C, keeping only 54% after accelerated stress test.

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.

First-principles study of plasmons in doped graphene nanostructures

The operating frequencies of surface plasmons in pristine graphene lie in the terahertz and infrared spectral range,which limits their utilization.Here,the high-frequency plasmons in doped graphene nanostructures are studied by the time-dependent density functional theory.The doping atoms include boron,nitrogen,aluminum,silicon,phosphorus,and sulfur atoms.The influences of the position and concentration of nitrogen dopants on the collective stimulation are investigated,and the effects of different types of doping atoms on the plasmonic stimulation are discussed.For different positions of nitrogen dopants,it is found that a higher degree of symmetry destruction is correlated with weaker optical absorption.In contrast,a higher concentration of nitrogen dopants is not correlated with a stronger absorption.Regarding different doping atoms,atoms similar to carbon atom in size,such as boron atom and nitrogen atom,result in less spectral attenuation.In systems with other doping atoms,the absorption is significantly weakened compared with the absorption of the pristine graphene nanostructure.Plasmon energy resonance dots of doped graphene lie in the visible and ultraviolet spectral range.The doped graphene nanostructure presents a promising material for nanoscaled plasmonic devices with effective absorption in the visible and ultraviolet range.

Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene

Developing stable and efficient catalysts for the electroreduction of nitrogen remains a huge challenge and single atom catalysts(SACs)are expected to achieve relatively high ammonia selectivity at low applied potential.Based on density functional theory calculations,the potential application of 27 single transition metal(TM=Sc-Zn,Y-Ag,Hf-Au)atoms supported by N(O)-dualdoped graphene(TM-O_(2)N_(2)/G)for the electroreduction of nitrogen is intensively investigated.At low nitrogen coverage,W(Mo,Nb,Ta)-O_(2)N_(2)/G are predicted to yield low ammonia selectivity(<13%)at limiting-potential of-0.58,-0.53,-0.56,and-0.76 V starting from adsorbed nitrogen with side-on mode,respectively.With the increasing N_(2)coverage,the TM-O_(2)N_(2)/G is reconstructed as TM-(N_(2))2N_(2)/graphene.The electroreduction of nitrogen proceeds from end-on adsorbed nitrogen molecule with high ammonia selectivity,and the limiting-potentials are theoretically predicted as-0.20,-0.40,-0.29,and-0.21 V on W(Mo,Nb,Ta)-(N_(2))2N_(2)/G,respectively.It is suggested that utilizing the reorganization of local coordination environments of SACs by high coverage of reactant molecules under reaction condition can not only enhance the activity at lower limiting-potential but also improve the ammonia selectivity.

Heteroatom Doped Multi-Layered Graphene Material for Hydrogen Storage Application

A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a suitable route for the preparation of high volumes of graphene derivatives. P-substituted graphene material is developed for its application in hydrogen sorption in room temperature. Phosphorous doped graphene material with multi-layers of graphene shows a nearly ~2.2 wt% hydrogen sorption capacity at 298 K and 100 bar. This value is higher than that for reduced graphene oxide (RGO without phosphorous).

Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction

Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells,hydrogen production and understanding nitrogen cycle.Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media.In this study,Pt/nitrogen-doped graphene(NDG)and Pt/tungsten monocarbide(WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C.Pt/NDG exhibits a specific activity of 0.472 mA·cm^(-2),which is 44%higher than commercial Pt/C,thus establishing NDG as a more effective support than carbon black.Moreover,it is demonstrated that WC as a support also impacts the activity with further 30%increase in comparison to NDG.Surface modification with Ir resulted in the best electro-catalytic activity with Pt-IrAVC/NDG having almost thrice the current density of commercial Pt/C.This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.

Alloying cobalt with ruthenium in nitrogen doped graphene layers for developing highly active hydrogen evolution electrocatalysts in alkaline media

Subject Code:B01With the support by the National Natural Science Foundation of China,a creative study by the research group led by Prof.Chen Qianwang(陈乾旺)from the University of Science and Technology of China and High Magnetic Field Laboratory,Hefei Institutes of Physical Science,Chinese Academy of

Atomic Layer Coated Al_(2)O_(3) on Nitrogen Doped Vertical Graphene Nanosheets for High Performance Sodium Ion Batteries

Heteroatom doped graphene materials are considered as promising anode for high-performance sodium-ion batteries(SIBs).Defective and porous structure especially with large specific surface area is generally considered as a feasible strategy to boost reaction kinetics;however,the unwanted side reaction at the anode hinders the practical application of SIBs.In this work,a precisely controlled Al_(2)O_(3)coated nitrogen doped vertical graphene nanosheets(NVG)anode material has been proposed,which exhibits excellent sodium storage capacity and cycling stability.The ultrathin Al_(2)O_(3)coating on the NVG is considered to help construct an advantageous interface between electrode and electrolyte,both alleviating the electrolyte decomposition and enhancing sodium adsorption ability.As a result,the optimal Al_(2)O_(3)coated NVG materials delivers a high reversible capacity(835.0 mAh g^(-1))and superior cycling stability(retention of 92.3%after 5000 cycles).This work demonstrates a new way to design graphene-based anode materials for highperformance sodium-ion batteries.

A nanoporous nitrogen-doped graphene for high performance lithium sulfur batteries

A nanoporous N-doped reduced graphene oxide（p-N-rGO） was prepared through carbothermal reaction between graphene oxide and ammonium-containing oxometalates as sulfur host for Li-S batteries.The p-N-rGO sheets have abundant nanopores with diameters of 10-40 nm and the nitrogen content is 2.65 at%.When used as sulfur cathode,the obtained p-N-rGO/S composite has a high reversible capacity of 1110mAhg^-1 at 1C rate and stable cycling performance with 781.8 mAhg-1 retained after 110 cycles,much better than those of the rGO/S composite.The enhanced electrochemical performance is ascribed to the rational combination of nanopores and N-doping,which provide efficient contact and wetting with the electrolyte,accommodate volume expansion and immobilize polysulfides during cycling.

A Study on the Efficiency Gain of CsSnGeI3 Solar Cells with Graphene Doping

This paper presents a newly designed ultra-thin, lead-free, and all-inorganic solar cell structure. The structure was optimized using the SCAPS-1D simulator, incorporating solid-state layers arranged as n-graphene/CsSnGeI3/p-graphene. The objective was to investigate the potential of utilizing n-graphene as the electron transport layer and p-graphene as the hole transport layer to achieve maximum power conversion efficiency. Various materials for the electron transport layer were evaluated. The optimized cell structure achieved a maximum power conversion efficiency of 20.97%. The proposed solar cell structure demonstrates promising potential as an efficient, inorganic photovoltaic device. These findings provide important insights for developing and optimizing inorganic photovoltaic cells based on CsSnGeI3, with n-graphene electron transport layers and p-graphene hole transport layers.

CO Catalytic Oxide over Cu Atom Supported on Graphene Oxides from the First Principles

Via the first principles calculations, we predict that Cu doped graphene oxide （GO） is a much better nanocatalyst in terms of activity and feasibility. The high activity of Cu doped graphene oxides may be attributed to the charge transfer between the GO and Cu atom, resulting in an activated Cu atom. In the ER mechanism, the CO molecules directly react with the activated O2, then forming a metastable carbonate-like intermediate state （OOCO）. The reaction may proceed via two reaction paths of OOCO → CO2 ＋ O and CO ＋ OOCO → 2CO2, respectively. The calculated results show that the latter path is relatively more thermodynamically favorable with a modest energy barrier, so it should be more preferred. We expect our theoretical predictions to open a new avenue to fabricate carbon-based catalysts for CO oxidation with lower cost and higher activity.

Effect of Chemical Doping on the Electronic Transport Properties of Tailoring Graphene Nanoribbons

The electronic transport properties of a molecular junction based on doping tailoring armchair-type graphene nanoribbons（AGNRs）with different widths are investigated by applying the non-equilibrium Green＇s function formalism combined with first-principles density functional theory.The calculated results show that the width and doping play significant roles in the electronic transport properties of the molecular junction.A higher current can be obtained for the molecular junctions with the tailoring AGNRs with W=11.Furthermore,the current of boron-doped tailoring AGNRs with widths W=7 is nearly four times larger than that of the undoped one,which can be potentially useful for the design of high performance electronic devices.

Electronic Transport Properties of Diblock Co-Oligomer Molecule Devices Sandwiched between Nitrogen Doping Armchair Graphene Nanoribbon Electrodes

We investigate the electronic transport properties of dipyrimidinyl-diphenyl sandwiched between two armchair graphene nanoribbon electrodes using the nonequilibrium Green function formalism combined with a first-principles method based on density functional theory. Among the three models M1–M3, M1 is not doped with a heteroatom. In the left parts of M2 and M3, nitrogen atoms are doped at two edges of the nanoribbon. In the right parts, nitrogen atoms are doped at one center and at the edges of M2 and M3, respectively. Comparisons of M1, M2 and M3 show obvious rectifying characteristics, and the maximum rectification ratios are up to 42.9 in M2. The results show that the rectifying behavior is strongly dependent on the doping position of electrodes. A higher rectification ratio can be found in the dipyrimidinyl-diphenyl molecular device with asymmetric doping of left and right electrodes, which suggests that this system has a broader application in future logic and memory devices.

Combined DFT and experiment:Stabilizing the electrochemical interfaces via boron Lewis acids

The incorporation of boron into carbon material can significantly enhance its capacity performances.However,the origin of the promotion effect of boron doping on electrochemical performances is still unclear,in part due to the inadequate exposure of boron configurations resulting from the complexity of traditional carbon materials.To overcome this issue,herein,a series of boron-doped graphene with highly-exposed boron configurations are prepared by tuning annealing temperature.Then the correlation between boron configurations and the electrochemical performances is investigated.The combination of density-functional theory(DFT)computation and NH3-TPD/Py-FTIR indicates that the BCO_(2)configuration formed on the surface of graphene is easier to accept lone-pair electrons than BC_(2)O and BC_(3)configurations due to the stronger Lewis acidity.Such an electronic structure can effectively reduce the number of unstable electron donors and stabilize the electrochemical interface,which is proved by NMR,and critical for improving the electrochemical performances.Further experiments confirm that the optimized BG800 with the largest amount of BCO_(2)configuration presents ultralow leak current,improved cyclic stability,and better rate performance in SBPBF4/PC.This work would provide an insight into the design of high-performance boron-doped carbon materials towards energy storage.

Nitrogen-doped pyrogenic carbonaceous matter facilitates azo dye decolorization by sulfide: The important role of graphitic nitrogen

Pyrogenic carbonaceous matter(PCM) catalyzes azo dye decolorization by sulfide, but the nitrogen doping catalytic mechanisms are poorly understood. In this study, we found that stagnate time of azo dye methyl orange(MO) decolorization was reduced to 0.54-18.28 min in the presence of various nitrogen-doped graphenes(NGs), remarkably lower compared to graphene itself. Particularly, graphitic nitrogen played a critical role in NGs-catalyzed MO decolorization by sulfide. Gas chromatography-mass spectrometry and in-situ surface Raman analysis demonstrated that doping nitrogen, especially graphite one facilitated reactive intermediate polysulfides formation. This is attributed to the improved electron conductivity through graphitic nitrogen doping, and the enhanced interactions between sulfide and carbon atoms bonded to graphitic nitrogen. This study not only provides a better understanding of PCM impact on transformations and fates of organic pollutants in natural environments, but also offer a new regulation strategy for more efficient wastewater treatment processes in PCM-catalyzed engineering systems.

Chemically doped macroscopic graphene fibers with significantly enhanced thermoelectric properties

Flexible wearable electronics, when combined with outstanding thermoelectric properties, are promising candidates for future energy harvesting systems. Graphene and its macroscopic assemblies （e.g., graphene-based fibers and films） have thus been the subject of numerous studies because of their extraordinary electrical and mechanical properties. However, these assemblies have not been considered suitable for thermoelectric applications owing to their high intrinsic thermal conductivity. In this study, bromine doping is demonstrated to be an effective method for significantly enhancing the thermoelectric properties of graphene fibers. Doping enhances phonon scattering due to the increased defects and thus decreases the thermal conductivity, while the electrical conductivity and Seebeck coefficient are increased by the Fermi level downshift. As a result, the maximum figure of merit is 2.76 ~ 10~, which is approximately four orders of magnitude larger than that of the undoped fibers throughout the temperature range. Moreover, the room temperature power factor is shown to increase up to 624 btW.m-l.K-2, which is higher than that of any other material solely composed of carbon nanotubes and graphene. The enhanced thermoelectric properties indicate the promising potential for graphene fibers in wearable energy harvesting systems.

Enhanced thermal and pyroelectric properties in 0-3 TGS:PVDF composites doped with graphene for infrared application

Pyroelectric composites of triglycine sulfate(TGS)-polyvinylidene difluoride(PVDF)doped with graphene are studied.It is found that the graphene can effectively improve the polling efficiency and thermal property of the composites so that the infrared detective performance can be significantly improved.For example,by adding about 0.83 wt.%of graphene,the infrared detective property can be improved by more than 30%.It is also found that the size of the graphene plays a critical role on the property improvement.For example,the small-sized graphene prepared by ultrasonic exfoliation(UE)method is more effective than the big-sized graphene prepared by electrochemical exfoliation(EE)method.

Study of Graphene Doped Zinc Oxide Nanocomposite as Transparent Conducting Oxide Electrodes for Solar Cell Applications

The graphite oxide(GO) was prepared based on the modified Hummers method, then reacted with zinc acetate aqueous, sodium hydroxide aqueous and hydrazine hydrate, and was doped into ZnO eventually to form graphene doped ZnO, an alternative transparent conducting oxide(TCO) for solar cell applications. The samples were characterized by Raman spectrometer, X-ray diffractometer, Fourier transform infrared spectroscopy and scanning electron microscope, and compared with widely used aluminum doped ZnO(AZO) in resistivity and transmissivity. The results show that the transmissivity of graphene doped ZnO reaches the same level as that of AZO in visible light band. In ultraviolet light wave band, the transmissivity of graphene doped ZnO reaches as high as 50%, exceeding that of AZO which is only 20%. The resistivity of optimized graphene doped ZnO is1.03 × 10-5Ω· m, approaching AZO resistivity which is about 10-4—10-6Ω· m. As a result, graphene doped ZnO may have potential applications in the area of TCO due to its low cost and high performance.