Phosphorus and Halogen Co‐Doped Graphene Materials and their Electrochemistry

Doping of graphene materials with heteroatoms is important as it can change their electronic and electrochemical properties. Here, graphene is co‐doped with n‐type dopants such as phosphorus and halogen (Cl, Br, I). Phosphorus and halogen are introduced through the treatment of graphene oxide with PX₃ gas (PCl₃, PBr₃, and PI₃). Graphene oxides are prepared through chlorate and permanganate routes. Detailed chemical and structural characterization demonstrates that the graphene sheets are covered homogeneously by phosphorus and halogen atoms. It is found that the amount of phosphorus and halogen introduced depends on the graphene oxide preparation method. The electrocatalytic effect of the resulting co‐doped materials is demonstrated for industrially relevant electrochemical reactions such as the hydrogen evolution and oxygen reduction reactions.     

Selective Removal of Hydroxyl Groups from Graphene Oxide

Graphene has a wide range of potential applications, thus tremendous efforts have been put into ensuring that the most direct and effective methods for its large‐scale production are developed. The formation of graphene materials from graphene oxide through a chemical reduction method is still one of the most preferred routes. Numerous methods starting from various reducing agents have been developed to obtain near‐pristine graphene sheets. However, most of the reducing agents are not mechanistically supported by classical organic chemistry knowledge and of those that are supported, they are only theoretically capable of, at most, reducing oxygen‐containing groups on graphene oxide to hydroxyl groups. Herein, we present a mechanistically proven method for the selective defunctionalisation of hydroxyl groups from graphene oxide that is based on ethanethiol–aluminium chloride complexes and provides a graphene material with improved properties. The structural, morphological and electrochemical properties of the graphene materials have been fully characterised based on high‐resolution X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses showed that the obtained graphene materials exhibited high heterogeneous electron‐transfer rates, low charge‐transfer resistance and high conductivity as compared to the parent graphene oxide. Moreover, the selective defunctionalisation of hydroxyl groups could potentially allow for the tailoring of graphene properties for various applications.     

Precise Tuning of Surface Composition and Electron‐Transfer Properties of Graphene Oxide Films through Electroreduction

Graphene materials are generally prepared from the exfoliation of graphite oxide (GO) to graphene oxide, followed by subsequent chemical or thermal reduction. These methods, although efficient in removing most of the oxygen functionalities from the GO material, lack control over the extent of the reduction process. We demonstrate here an electrochemical reduction procedure that not only allows for precise control of the reduction process to obtain a graphene material with a well‐defined C/O ratio in the range of 3 to 10, but also one that is able to tune the electrocatalytic properties of the reduced material. A method that is able to precisely control the amount and density of the oxygen functionalities on the graphene material as well as its electrochemical behaviour is very important for several applications such as electronics, bio‐composites and electrochemical devices.     

Phosphorus‐Doped Graphene Oxide Layer as a Highly Efficient Flame Retardant

A simple and easy process has been developed to efficiently dope phosphorus into a graphene oxide surface. Phosphorus‐doped graphene oxide (PGO) is prepared by the treatment of polyphosphoric acid with phosphoric acid followed by addition of a graphene oxide solution while maintaining a pH of around 5 by addition of NaOH solution. The resulting materials are characterized by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The as‐made PGO solution‐coated cloth exhibits excellent flame retardation properties. The PGO‐coated cloth emits some smoke at the beginning without catching fire for more than 120 s and maintains its initial shape with little shrinkage. In contrast, the pristine cloth catches fire within 5 s and is completely burned within 25 s, leaving trace amounts of black residue. The simple technique of direct introduction of phosphorus into the graphene oxide surface to produce phosphorus‐doped oxidized carbon nanoplatelets may be a general approach towards the low‐cost mass production of PGO for many practical applications, including flame retardation.     

Nitrogen,Phosphorus, and Fluorine Tri‐doped Graphene as a Multifunctional Catalyst for Self‐Powered Electrochemical Water Splitting

Electrocatalysts are required for clean energy technologies (for example, water‐splitting and metal‐air batteries). The development of a multifunctional electrocatalyst composed of nitrogen, phosphorus, and fluorine tri‐doped graphene is reported, which was obtained by thermal activation of a mixture of polyaniline‐coated graphene oxide and ammonium hexafluorophosphate (AHF). It was found that thermal decomposition of AHF provides nitrogen, phosphorus, and fluorine sources for tri‐doping with N, P, and F, and simultaneously facilitates template‐free formation of porous structures as a result of thermal gas evolution. The resultant N, P, and F tri‐doped graphene exhibited excellent electrocatalytic activities for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The trifunctional metal‐free catalyst was further used as an OER–HER bifunctional catalyst for oxygen and hydrogen gas production in an electrochemical water‐splitting unit, which was powered by an integrated Zn–air battery based on an air electrode made from the same electrocatalyst for ORR. The integrated unit, fabricated from the newly developed N, P, and F tri‐doped graphene multifunctional metal‐free catalyst, can operate in ambient air with a high gas production rate of 0.496 and 0.254 μL s⁻¹ for hydrogen and oxygen gas, respectively, showing great potential for practical applications.     

Nitrogen,Phosphorus, and Fluorine Tri‐doped Graphene as a Multifunctional Catalyst for Self‐Powered Electrochemical Water Splitting

Electrocatalysts are required for clean energy technologies (for example, water‐splitting and metal‐air batteries). The development of a multifunctional electrocatalyst composed of nitrogen, phosphorus, and fluorine tri‐doped graphene is reported, which was obtained by thermal activation of a mixture of polyaniline‐coated graphene oxide and ammonium hexafluorophosphate (AHF). It was found that thermal decomposition of AHF provides nitrogen, phosphorus, and fluorine sources for tri‐doping with N, P, and F, and simultaneously facilitates template‐free formation of porous structures as a result of thermal gas evolution. The resultant N, P, and F tri‐doped graphene exhibited excellent electrocatalytic activities for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The trifunctional metal‐free catalyst was further used as an OER–HER bifunctional catalyst for oxygen and hydrogen gas production in an electrochemical water‐splitting unit, which was powered by an integrated Zn–air battery based on an air electrode made from the same electrocatalyst for ORR. The integrated unit, fabricated from the newly developed N, P, and F tri‐doped graphene multifunctional metal‐free catalyst, can operate in ambient air with a high gas production rate of 0.496 and 0.254 μL s^?1 for hydrogen and oxygen gas, respectively, showing great potential for practical applications.     

Transition Metal (Mn,Fe, Co,Ni)‐Doped Graphene Hybrids for Electrocatalysis

The development of electrocatalysts is crucial for renewable energy applications. Metal‐doped graphene hybrid materials have been explored for this purpose, however, with much focus on noble metals, which are limited by their low availability and high costs. Transition metals may serve as promising alternatives. Here, transition metal‐doped graphene hybrids were synthesized by a simple and scalable method. Metal‐doped graphite oxide precursors were thermally exfoliated in either hydrogen or nitrogen atmosphere; by changing exfoliation atmospheres from inert to reductive, we produced materials with different degrees of oxidation. Effects of the presence of metal nanoparticles and exfoliation atmosphere on the morphology and electrocatalytic activity of the hybrid materials were investigated using electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy, and cyclic voltammetry. Doping of graphene with transition metal nanoparticles of the 4th period significantly influenced the electrocatalysis of compounds important in energy production and storage applications, with hybrid materials exfoliated in nitrogen atmosphere displaying superior performance over those exfoliated in hydrogen atmosphere. Moreover, nickel‐doped graphene hybrids displayed outstanding electrocatalytic activities towards reduction of O₂ when compared to bare graphenes. These findings may be exploited in the research field of renewable energy.     

Porous Nitrogen‐doped Reduced Graphene Oxide Gels as Efficient Supercapacitor Electrodes and Oxygen Reduction Reaction Electrocatalysts

Heteroatom‐doped carbon materials have been widely used in energy storage and conversion such as supercapacitors and electrocatalysts. In this work, L‐asparagine (Asn), an amino acid derivative, has been used as a doping agent to prepare nitrogen‐ doped reduced graphene oxide gels (N‐GAs). The 3D interconnected structure gives rise to the superior electrochemical properties for supercapacitor and electrocatalytic oxygen reduction reaction (ORR). The N‐GA‐4 (the mass ratio of Asn to graphene oxide (GO) is 4 : 1 by hydrothermal method) electrode shows the capacitance of 291.6 F·g^–1 at 0.5 A·g^–1. Meanwhile, the assembled symmetric supercapacitor achieves a maximum energy density of 23.8 Wh· kg^–1 when the power density is 451.2 W·kg^–1, and demonstrates an ultralong cycling life that the retention of capacitance is 99.3% after 80000 cycles. What's more, the annealed aerogel N‐GA‐4‐900 exhibits an onset potential (E_onset) of 0.95 V, half wave potential (E_1/2) of 0.84 V (vs. RHE) and the oxygen reduction current density of 5.5 mA·cm^–2 at 0.1 V with nearly four‐electron transfer, which are superior to commercial Pt/C. This work offers a new insight into the synthesis and applications of N‐GAs materials towards high performance in supercapacitors and ORR.     

Heavily Doped and Highly Conductive Hierarchical Nanoporous Graphene for Electrochemical Hydrogen Production

Heavy chemical doping and high electrical conductivity are two key factors for metal‐free graphene electrocatalysts to realize superior catalytic performance toward hydrogen evolution. However, heavy chemical doping usually leads to the reduction of electrical conductivity because the catalytically active dopants give rise to additional electron scattering and hence increased electrical resistance. A hierarchical nanoporous graphene, which is comprised of heavily chemical doped domains and a highly conductive pure graphene substrate, is reported. The hierarchical nanoporous graphene can host a remarkably high concentration of N and S dopants up to 9.0 at % without sacrificing the excellent electrical conductivity of graphene. The combination of heavy chemical doping and high conductivity results in high catalytic activity toward electrochemical hydrogen production. This study has an important implication in developing multi‐functional electrocatalysts by 3D nanoarchitecture design.     

Synthesis of Phosphorus‐Doped Graphene and its Wide Potential Window in Aqueous Supercapacitors

Phosphorus‐doped (P‐doped) graphene with the P doping level of 1.30 at % was synthesized by annealing the mixture of graphene and phosphoric acid. The presence of P was confirmed by elemental mapping and X‐ray photoelectron spectroscopy, while the morphology of P‐doped graphene was revealed by using scanning electron microscopy and transmission electron microscopy. To investigate the effect of P doping, the electrochemical properties of P‐doped graphene were tested as a supercapacitor electrode in an aqueous electrolyte of 1 M H₂SO₄. The results showed that doping of P in graphene exhibited significant improvement in terms of specific capacitance and cycling stability, compared with undoped graphene electrode. More interestingly, the P‐doped graphene electrode can survive at a wide voltage window of 1.7 V with only 3 % performance degradation after 5000 cycles at a current density of 5 A g^?1, providing a high energy density of 11.64 Wh kg^?1 and a high power density of 831 W kg^?1.     

Electrochemistry at chemically modified graphenes

Electrochemical applications of graphene are of great interest to many researchers as they can potentially lead to crucial technological advancements in fabrication of electrochemical devices for energy production and storage, and highly sensitive sensors. There are many routes towards fabrication of bulk quantities of chemically modified graphenes (CMG) for applications such as electrode materials. Each of them yields different graphene materials with different functionalities and structural defects. Here, we compare the electrochemical properties of five different chemically modified graphenes: graphite oxide, graphene oxide, thermally reduced graphene oxide, chemically reduced graphene oxide, and electrochemically reduced graphene oxide. We characterized these materials using transmission electron microscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, which allowed us to correlate the electrochemical properties with the structural and chemical features of the CMGs. We found that thermally reduced graphene oxide offers the most favorable electrochemical performance among the different materials studied. Our findings have a profound impact for the applications of chemically modified graphenes in electrochemical devices.     

Strongly Veined Carbon Nanoleaves as a Highly Efficient Metal‐Free Electrocatalyst

Effective integration of one‐dimensional carbon nanofibers (CNF) and two‐dimensional carbon sheets into three‐dimensional (3D) conductive frameworks is essential for their practical applications as electrode materials. Herein, a novel “vein‐leaf”‐type 3D complex of carbon nanofibers with nitrogen‐doped graphene (NG) was prepared through a simple thermal condensation of urea and bacterial cellulose. During the formation of the 3D complex CNF@NG, the graphene species was tethered to CNF via carbon–carbon bonds. Such an interconnected 3D network facilitates both the electron transfer and mass diffusion for electrochemical reactions.     

Rules of Boron–Nitrogen Doping in Defect Graphene Sheets: A First‐Principles Investigation of Band‐Gap Tuning and Oxygen Reduction Reaction Catalysis Capabilities

Introduction of defects and nitrogen doping are two of the most pursued methods to tailor the properties of graphene for better suitability to applications such as catalysis and energy conversion. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B?N bonding. Systematic exploration of the possible doping/codoping configurations reflecting defect regions of graphene presents a prevalent doping site for nitrogen‐rich BN clusters and they are also highly suitable for modulating (0.2–0.9 eV) the band gap of defect graphene. Such codoped systems perform significantly better than the platinum surface, undoped defect graphene, and the single nitrogen or boron atom doped defect graphene system for dioxygen adsorption. Significant stretching of the O?O bond indicates a lowering of the bond breakage barrier, which is advantageous for applications in the oxygen reduction reaction.     

Chemical Preparation of Graphene Materials Results in Extensive Unintentional Doping with Heteroatoms and Metals

Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at %), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.     

Germanium Quantum Dots Embedded in N‐Doping Graphene Matrix with Sponge‐Like Architecture for Enhanced Performance in Lithium‐Ion Batteries

Germanium quantum dots embedded in a nitrogen‐doped graphene matrix with a sponge‐like architecture (Ge/GN sponge) are prepared through a simple and scalable synthetic method, involving freeze drying to obtain the Ge(OH)₄/graphene oxide (GO) precursor and subsequent heat reduction treatment. Upon application as an anode for the lithium‐ion battery (LIB), the Ge/GN sponge exhibits a high discharge capacity compared with previously reported N‐doped graphene. The electrode with the as‐synthesized Ge/GN sponge can deliver a capacity of 1258 mAh g^?1 even after 50 charge/discharge cycles. This improved electrochemical performance can be attributed to the pore memory effect and highly conductive N‐doping GN matrix from the unique sponge‐like structure.     

Developing Graphene‐Based Nanohybrids for Electrochemical Sensing

Graphene‐based nanohybrid is considered to be the most promising nanomaterial for electrochemical sensing applications due to the defects created on the graphene oxide layers. These defects provide graphene oxide unique properties, such as excellent conductivity, large specific surface area, and electrocatalytic activity. These unique properties encourage scientists to develop novel graphene‐based nanohybrids and improve the sensing efficiency. This review, therefore, addresses this topic by comprehensively discussing the strategies to fabricate novel graphene based nanohybrids with high sensitivity. The combinations of graphene with various nanomaterials, such as metal nanoclusters, metal compound nanoparticles, carbon materials, polymers and peptides, in the direction of electrochemical sensing, were systematically analyzed. Meanwhile, the challenges in the functional design and application of graphene‐based nanohybrids were described and the reasonable solutions were proposed.     

Electrochemically Exfoliated Graphene and Graphene Oxide for Energy Storage and Electrochemistry Applications

Top‐down methods are of key importance for large‐scale graphene and graphene oxide preparation. Electrochemical exfoliation of graphite has lately gained much interest because of the simplicity of execution, the short process time, and the good quality of graphene that can be obtained. Here, we test three different electrolytes, that is, H₂SO₄, Na₂SO₄, and LiClO₄, with a common exfoliation procedure to evaluate the difference in structural and chemical properties that result for the graphene. The properties are analyzed by means of scanning transmission electron microscopy (STEM), Raman spectroscopy, and X‐ray photoelectron spectroscopy. We then tested the graphene materials for electrochemical applications, measuring the heterogeneous electron transfer (HET) rates with a Fe(CN)₆^3?/4? redox probe, and their capacitive behavior in alkaline solutions. We correlate the electrochemical features with the presence of structural defects and oxygen functionalities on the graphene materials. In particular, the use of LiClO₄ during the electrochemical exfoliation of graphite allowed the formation of highly oxidized graphene with a C/O ratio close to 4.0 and represents a possible avenue for the mass production of graphene oxide as valid alternative to the current laborious and dangerous chemical procedures, which also have limited scalability.     

n‐Type Reduced Graphene Oxide Field‐Effect Transistors (FETs) from Photoactive Metal Oxides

Graphene is of considerable interest as a next‐generation semiconductor material to serve as a possible substitute for silicon. For real device applications with complete circuits, effective n‐type graphene field effect transistors (FETs) capable of operating even under atmospheric conditions are necessary. In this study, we investigated n‐type reduced graphene oxide (rGO) FETs of photoactive metal oxides, such as TiO₂ and ZnO. These metal oxide doped FETs showed slight n‐type electric properties without irradiation. Under UV light these photoactive materials readily generated electrons and holes, and the generated electrons easily transferred to graphene channels. As a result, the graphene FET showed strong n‐type electric behavior and its drain current was increased. These n‐doping effects showed saturation curves and slowly returned back to their original state in darkness. Finally, the n‐type rGO FET was also highly stable in air due to the use of highly resistant metal oxides and robust graphene as a channel.     

Experimental and Theoretical Study of Enhanced Photocatalytic Activity of Mg‐Doped ZnO NPs and ZnO/rGO Nanocomposites

A systematic experimental and theoretical study of the origin of the enhanced photocatalytic performance of Mg‐doped ZnO nanoparticles (NPs) and Mg‐doped ZnO/reduced graphene oxide (rGO) nanocomposites has been performed. In addition to Mg, Cd was chosen as a doping material for the bandgap engineering of ZnO NPs, and its effects were compared with that of Mg in the photocatalytic performance of ZnO nanostructures. The experimental results revealed that Mg, as a doping material, recognizably ameliorates the photocatalytic performance of ZnO NPs and ZnO/graphene nanocomposites. Transmission electron microscopy (TEM) images showed that the Mg‐doped and Cd‐doped ZnO NPs had the same size. The optical properties of the samples indicated that Cd narrowed the bandgap, whereas Mg widened the bandgap of the ZnO NPs and the oxygen vacancy concentration was similar for both samples. Based on the experimental results, the narrowing of the bandgap, the particle size, and the oxygen vacancy did not enhance the photocatalytic performance. However, Brunauer–Emmett–Teller (BET) and Barret–Joyner–Halenda (BJH) models showed that Mg caused increased textural properties of the samples, whereas rGO played an opposite role. A theoretical study, conducted by using DFT methods, showed that the improvement in the photocatalytic performance of Mg‐doped ZnO NPs was due to a higher electron transfer from the Mg‐doped ZnO NPs to the dye molecules compared with pristine ZnO and Cd‐doped ZnO NPs. Moreover, according to the experimental results, along with Mg, graphene also played an important role in the photocatalytic performance of ZnO.     

氮掺杂石墨烯的制备及其在化学储能中的研究进展

石墨烯独特的二维空间结构使其具有优异的导电性能、力学性能以及超大的比表面积,被认为是颇具潜力的新型储能材料,是目前储能研究的热点之一。 但是石墨烯易团聚、表面光滑且呈惰性而不利于与其它材料的复合,导致其应用受到限制。 石墨烯掺氮可改变其电子结构,增加表面的活性位,从而提高其应用于储能器件时的电化学性能。 本文综述了近几年氮掺杂石墨烯的制备方法以及其在超级电容器、锂离子电池、锂空电池以及锂硫电池等化学储能领域中的应用,指出了目前氮掺杂石墨烯在制备和储能应用中关注的核心问题,并对氮掺杂石墨烯的发展前景进行了展望。