N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

The Fluorination of Boron-Doped Graphene for CF_(x) Cathode with Ultrahigh Energy Density

The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.

Designing N-doped graphene/ReSe_(2)/Ti_(3)C_(2) MXene heterostructure frameworks as promising anodes for high-rate potassium-ion batteries

Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.

In-situ preparation of TiO_(2)/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO_(2) reduction performance

Photocatalytic CO_(2)conversion efficiency is hampered by the rapid recombination of photogenerated charge carriers.It is effective to suppress the recombination by constructing cocatalysts on photocatalysts with high-quality interfacial contact.Herein,we develop a novel strategy to in-situ grow ultrathin/V-doped graphene(NG)layer on TiO_(2) hollow spheres(HS) with large area and intimate interfacial contact via a chemical vapor deposition(CVD).The optimized TiO^(2)/NG HS nanocomposite achieves total CO_(2)conversion rates(the sum yield of CO,CH_(3)OH and CH_(4))of 18.11μmol·g^(-1)h^(-1),which is about 4.6 times higher than blank T1O_(2)HS.Experimental results demonstrate that intimate interfacial contact and abundant pyridinic N sites can effectively facilitate photogenerated charge carrier separation and transport,realizing enhanced photocatalytic CO_(2)reduction performance.In addition,this work provides an effective strategy for in-situ construction of graphene-based photocatalysts for highly efficient photocatalytic CO_(2)conversion.

Selective glycerol oxidation using platinum nanoparticles supported on multi-walled carbon nanotubes and nitrogen-doped graphene hybrid

Selective oxidation of glycerol is a hot topic.Increased biodiesel production has led to glycerol oxidation over Au- and Pt-based catalysts being widely studied.However,Pt catalysts suffer from deactivation because of weak metal-support interactions.In this study,multi-walled carbon nanotube（MWCNTs）-pillared nitrogen-doped graphene（NG） was prepared by direct pyrolysis of melamine on MWCNTs,and the synthesized NG-MWCNT composite was used as the support for Pt.Characterization results showed that the surface area（173 m^2/g） and pore volume of the NG-MWCNT composite were greater than those of bare MWCNTs and the separated melamine pyrolysis product（CH_x）.Pt（1.4±0.4 nm） dispersion on the NG-MWCNTs was favorable and the Pt/NG-MWCNT catalyst was highly active and selective in the oxidation of glycerol to glyceric acid（GLYA） in base-free aqueous solution.For example,the conversion of glycerol reached 64.4% with a GLYA selectivity of 81.0%,whereas the conversions of glycerol over Pt/MWCNTs and Pt/CN_x were 29.0% and 31.6%,respectively.The unique catalytic activity of the Pt/NG-MWCNTs is attributed to well-dispersed Pt clusters on the NG-MWCNTs and the electron-donating effect of the nitrogen dopant in the NG-MWCNTs.

Nitrogen-doped graphene:Synthesis,characterizations and energy applications

Nitrogen-doped（N-doped） graphene has attracted increasing attentions because of the significantly enhanced properties in physic, chemistry, biology and material science, as compared with those of pristine graphene. By date, N-doped graphene has opened up an exciting new field in the science and technology of two-dimensional materials. From the viewpoints of chemistry and materials, this article presents an overview on the recent progress of N-doped graphene, including the typical synthesis methods, characterization techniques, and various applications in energy fields. The challenges and perspective of Ndoped graphene are also discussed. We expect that this review will provide new insights into the further development and practical applications of N-doped graphene.

Cobalt-based multicomponent nanoparticles supported on N-doped graphene as advanced cathodic catalyst for zinc-air batteries

To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprising Co,Co_(3)O_(4)and CoN,as well as numerous N heteroatoms,on graphene nanosheets(Co/Co_(3)O_(4)/CoN/NG).The Co/Co_(3)O_(4)/CoN nanoparticles with the size of less than 50 nm are homogeneously dispersed on N-doped graphene(NG)substrate,which greatly improve the catalytic behaviors for ORR.The results show that the half-wave potential is as high as 0.80 V vs.RHE and the limiting current density is 4.60 mA·cm^(−2),which are close to those of commercially available platinum/carbon(Pt/C)catalysts.Applying as cathodic catalyst for ZABs,the battery shows large specific capacity and open circuit voltage of 843.0 mAh∙g^(−1) and 1.41 V,respectively.The excellent performance is attributed to the efficient two-dimensional structure with high accessible surface area and the numerous multiple active sites provided by highly scattered Co/Co_(3)O_(4)/CoN particles and doped nitrogen on the carbon matrix.

Heterogeneous single-cluster catalysts(Mn_(3),Fe_(3),Co_(3),and Mo_(3))supported on nitrogen-doped graphene for robust electrochemical nitrogen reduction

Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experimental and theoretical advances on single-cluster catalysts(SCCs),we systematically investigated the catalytic performance of various triple-transition-metal-atom clusters anchored on nitrogen-doped graphene for NRR through density functional theory(DFT)calculation.Among them,Mn_(3)-N4,Fe_(3)-N4,Co_(3)-N4,and Mo_(3)-N4 were screened out as electrocatalysis systems composed of non-noble metal with high activity,selectivity,stability,and feasibility.Particularly,the Co_(3)-N4 possesses the highest activity with a limiting potential of-0.41 V through the enzymatic mechanism.The outstanding performance of Co_(3)-N4 can be attributed to the unique electronic structure leading to strong π backdonation,which is crucial in effective N_(2) activation.This work not only predicts four efficient non-noble metal electrocatalysts for NRR,but also suggest the SCCs can serve as potential candidates for other important electrochemical reactions.

Novel Formaldehyde Sensor based on Hydrogen Peroxide/Melamine Modulated Photoluminescence of Nitrogen-doped Graphene Quantum Dots

A modulated photoluminescence nanosensor was developed for the quantitative detection of formaldehyde with nitrogen-doped graphene quantum dots and melamine. The sensing system was based on the different activated effects of melamine and hydrogen peroxide on the photoluminescence intensity of nitrogendoped graphene quantum dots. Under the optimal conditions, the modulated photoluminescence sensing system can be used to detect formaldehyde with a good linear relationship between the nitrogen-doped graphene quantum dots photoluminescence difference and the concentration of formaldehyde. The novel sensing system provided new directions for the detection of formaldehyde with high selectivity and quick response.

TiN nanocrystal anchored on N-doped graphene as effective sulfur hosts for high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have become prospective candidates for next-generation energy storage owing to the high energy density and low cost.However,the sluggish kinetics of the electrochemical reaction and shuttle effect result in a rapid capacity decay.Herein,a titanium nitride nanocrystal/Ndoped graphene(TiN@NG)composite is developed to host elemental sulfur.The TiN nanoparticles decorated on graphene sheets attract Li polysulfides(LiPSx)and catalyze the electrochemical reduction and oxidation of LiPSx in the discharge and charge processes,respectively.These two effects effectively restrain the dissolution of the LiPSx and accelerate the electrochemical reactions,thereby,alleviating the shuttle effect.As a result,the cathode composed of TiN@NG/S delivers a remarkable reversible capacity(1390 mA h g^(-1) at 0.1 C)and excellent cycling performance(730 mA h g^(-1) after 300 cycles).We believe that this work can bring some inspiration for designing high-performance Li-S batteries.

Zeolitic imidazolate framework-67 derived Al-Co-S hierarchical sheets bridged by nitrogen-doped graphene:Incorporation of PANI derived carbon nanorods for solid-state asymmetric supercapacitors

Metal sulfides have been widely enticed as battery-type electrodes in supercapacitor devices because of their maximal theoretical capacitance.Nevertheless,their lower conductivity and ion transport kinetics can largely restrict their rate performance,hence the practical usage in fields of demanding high power devices.Therefore,the design of new electrodes with higher energy and power densities remains a highly challenging task.To the best of our knowledge,a novel hierarchical composite of Al-CoS_(2) on nitrogendoped graphene(NG)is prepared based on a zeolite imidazole framework using a simple and scalable hydrothermal process.In this hybrid,ultrathin Al-CoS_(2) nanosheet arrays are vertically orientated on the NG framework to limit self-aggregation,hence increasing the electrical property and cycle stability of composite.It is investigated that the Al/Co feeding ratio plays a crucial role in controlling the obtained hierarchical structure of Al-Co-S sheets and their electrode performance.Also,Al^(3+) can influence remarkably the morphology and electrochemical property of the resultant graphene composite.An effective synergism is noticed between the redox Al-CoS_(2) and NG resulting in fast electron transfer and chargingdischarging processes.Surprisingly,when the as-developed composite is utilized as a positive electrode at an applied current density of 1 A/g,a specific capacitance of 1915.8 F/g is attained with ultra-long cycle stability(96%,10,000 cycles)and an excellent retention rate(~89%).As a consequence,when a solid-state asymmetric supercapacitor(ASC)device is made by combining an Al-CoS_(2) @NG hybrid with a negative electrode made of polyaniline(PANI)derived carbon nanorods(PCNRs),it demonstrates remarkable specific capacitance(188 F/g),energy density(66.9 Wh/kg),and cyclic stability of 92%after 10,000 cycles.This may open the pathway for the application of the next-generation supercapacitors in the future.

Modified Nitrogen-Doped Graphene Electrocatalyst for Oxygen Reduction Reaction in Alkaline Fuel Cells

We report modified nitrogen-doped graphene （CN） as electrocatalyst for ORR （oxygen reduction reaction） in alkaline medium. CN was synthesized by a novel procedure based on graphite oxide thermally treated with cyanamide suitable for facile N-doping and large-scale production, whereas cyanamide was used as N-precursor. The structure of the material was characterized by TEM （transmission electron microscopy）, SEM （scanning electron microscopy）, Raman spectroscopy and XPS （X-ray photoelectron spectroscopy）. Structural and electrochemical properties of CN were compared with those of non-modified graphene （TRGO （thermally reduced graphite oxide））. The electrochemical characterization of TRGO and CN in alkaline solution demonstrates enhanced electrocatalytic ORR activity and improved long-term stability for N-doped CN. Voltammetric studies confirmed that, oxygen reduction on CN rather follows four-electron pathway. Compared with commercial 20% PtC catalyst, CN is characterized by exceptional methanol crossover resistance and superb long-term operation stability. Owing to these factors, nitrogen-doped graphene has a great potential to be used as metal-free electrocatalyst in cathodes of alkaline fuel cells.

Absorption and Fluorescence Properties of Oxidized and N-doped Graphene Quantum Dots:A Time-dependent DFT Study

Absorption and emission properties of oxidized graphene quantum dots （GQDs） and amino functionalized GQDs （NG） were explored by B3LYP method combined with 6-31G （d） basis set. The oxygen- and nitrogen-containing groups can tune the intensity as well as the wavelength of absorption and emission. The groups such as hydroxyl, carboxyl, amino, amide, and pyridine-like N can appropriately lengthen the absorption and emission wavelength of GQDs. However, the carbonyl group, graphitic-like N, and pyrrolic-like N obviously decrease the oscillator strength and lengthen the emission wavelength of GQDs out of the visible region. The lowest excited state S_1 of NG has the strongest emission in investigated complexes, which indicates that it is an excellent luminous material. The theoretical investigations verify that the oxygen- and nitrogen-related groups can tune the luminescence of GQDs. The fluorescence quenching of GQDs reduced by ammonia mainly depends on the graphitic-like and pyrrolic-like N.

Characterization of Fe/N-doped graphene as air-cathode catalyst in microbial fuel cells

This work proposed a simple and efficient approach for synthesis of durable and efficient non-precious metal oxygen reduction reaction（ORR） electro-catalysts in MFCs. The rod-like carbon nanotubes（CNTs）were formed on the Fe–N/SLG sheets after a carbonization process. The maximum power density of1210 ± 23 m W·mobtained with Fe–N/SLG catalyst in an MFC was 10.7% higher than that of Pt/C catalyst(1080 ± 20 mW ·m) under the same condition. The results of RDE test show that the ORR electron transfer number of Fe–N/SLG was 3.91 ± 0.02, which suggested that ORR catalysis proceeds through a four-electron pathway. The whole time of the synthesis of electro-catalysts is about 10 h, making the research take a solid step in the MFC expansion due to its low-cost, high efficiency and favorable electrochemical performance. Besides, we compared the electrochemical properties of catalysts using SLG, high conductivity graphene（HCG, a kind of multilayer graphene） and high activity graphene（HAG, a kind of GO） under the same conditions, providing a solution for optimal selection of cathode catalyst in MFCs.The morphology, crystalline structure, elemental composition and ORR activity of these three kinds of Fe–N/C catalysts were characterized. Their ORR activities were compared with commercial Pt/C catalyst.It demonstrates that this kind of Fe–N/SLG can be a type of promising highly efficient catalyst and could enhance ORR performance of MFCs.

Synthesis of Nitrogen-Doped Graphene via Thermal Annealing Graphene with Urea

Chemical doping is an effective method to intrinsically modify the chemical and electronic property of graphene. We propose a novel approach to synthesize the nitrogen-doped graphene via thermal annealing graphene with urea, in which the nitrogen source can be controllably released from the urea by varying the annealed temperature and time. The doped N content and the configuration N as well as the thermal stabilities are also evaluated with X-ray photoelectron spectroscopy and Raman spectra. Electrical measurements indi- cate that the conductivity of doped graphene can be well regulated with the N content. The method is expected to produce large scale and controllable N-doped graphene sheets for a variety of potential applications.

PdNi/N-doped graphene aerogel with over wide potential activity for formic acid electrooxidation

Anti-CO poisoning ability is significant in formic acid oxidation in the fuel cell technique.Herein,Pd Ni alloy supported on N-doped graphene aerogel(Pd Ni/GA-N)was found to have catalytic ability toward formic acid electrooxidation over a wide potential range because of the improved anti-CO poisoning ability.This catalyst was fabricated by simple freeze-drying of mixture solution of graphene aerogel,polyvinylpyrrolidone,Pd^(2+)and Ni^(2+)and the subsequent thermal annealing reduction approach in the N2/H2 atmosphere.Pd-Ni alloy particles anchored over the folding N-doped graphene surface with a porous hierarchical architecture structure in the 3 D directions.It showed the catalytic performance of its maximum mass activity of 836 m A mg^(-1)in a broad potential range(0.2-0.6 V)for formic acid oxidation.The CO stripping experiment demonstrated its largely improved anti-CO poisoning ability with the peak potential of 0.67 V,approximately 60 and 40 m V less compared to those of Pd/GA-N and Pd/C samples.The high anti-CO poisoning ability and strong electronic effect resulting from the interaction between the3 D GA-N support and the Pd-Ni alloy makes it a promising catalyst for application in direct formic acid fuel cells.

High efficient catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under benign conditions with nitrogen-doped graphene encapsulated Cu nanoparticles

Selective oxidation of 5-hydroxymethylfurfual(HMF) to 2,5-furandicarboxylic acid(FDCA) as a bioplastics monomer is efficiently promoted by a simple system without noble-metal and base additives. In this work, graphene oxide(GO) was first synthesised by an electrochemical method with flexible graphite paper(FGP) as start carbon material, then, nitrogen-doped graphene(NG) layers encapsulated Cu nanoparticles(NPs) was prepared by one-step thermal treatment of GO supported Cu2+ in flowing NH3 atmosphere. Compared with NG supported Cu NPs prepared by the traditional impregnation method, enhanced catalytic activity was achieved over Cu/NG and an FDCA yield of 95.2% was achieved under mild reaction conditions with tert-butylhydroperoxide(t-BuOOH) as the oxidant. Control experiments with different catalysts and different addition procedure of t-BuOOH showed the yield of HMF and various intermediates during reaction. From the changing of intermediates concentrations and reaction rates, a reaction pathway through HMF-DFF-FFCA-FDCA was proposed. This work gives a more convenient, more green,more economical and effective method in encapsulated metal NPs preparation and high selectivity in HMF oxidation to FDCA under mild conditions.

Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

A series of N-doped carbon materials(NCs)were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile onestep pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C_3N_4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6,show the highest N content of ~6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of ~66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal–air batteries.

A quantum explanation of the magnetic properties of Mn-doped graphene

Mn-doped graphene is investigated using first-principles calculations based on the density functional theory （DFT）. The magnetic moment is calculated for systems of various sizes, and the atomic populations and the density of states （DOS） are analyzed in detail. It is found that Mn doped graphene-based diluted magnetic semiconductors （DMS） have strong ferromagnetic properties, the impurity concentration influences the value of the magnetic moment, and the magnetic moment of the 8×8 supercell is greatest for a single impurity. The graphene containing two Mn atoms together is more stable in the 7×7 supercell. The analysis of the total DOS and partial density of states （PDOS） indicates that the magnetic properties of doped graphene originate from the p–d exchange, and the magnetism is given a simple quantum explanation using the Ruderman–Kittel–Kasuya–Yosida （RKKY） exchange theory.

Atomically Dispersed Ni Single-Atoms Anchored on N-Doped Graphene Aerogels for Highly Efficient Electromagnetic Wave Absorption

Uniformly dispersed nickel single atoms(SAs)are experimentally prepared on ultralight N-doped graphene aerogels(Ni-SA@NRGA).The experimental results show that Ni-SAs in graphene aerogels can improve the conduction,polarization losses,and impedance matching properties of the Ni-SA@NRGA.As a result,the minimum reflection loss(R_(L,min))of Ni-SA@NRGA is-49.46 d B with a matching thickness of 2.0 mm and the broadest efficient absorption bandwidth is 3.12 GHz at a low thickness of 1.5 mm.Meanwhile,even with a matching thickness of 1.2–2.0 mm,the RL,min value of Ni-SA@NRGA can reach-20 d B.The current study demonstrates the significance of incorporating metal single atoms into graphene aerogel for electromagnetic wave absorption.