Heteroatom-doped Graphene Research Articles

Nitrogen‑sulfur doped graphene-loaded SiO2/Co9S8 composites as anode materials for improved lithium storage

Heteroatom-doped graphene lamellae can effectively modulate the physical and chemical surface activities of Co9S8 materials. The addition of a second dopant atom, such as nitrogen (N) can further improve the composite properties. Herein, novel nitrogen‑sulfur double-doped graphene-loaded SiO2/Co9S8 composites (SiO2/Co9S8@NSG) were prepared by a one-step solvothermal method using polyethylene glycol as the carbon source and cobalt chloride hexahydrate as the cobalt source to yield a Deep Eutectic Solvents (DESs) system. The precursor was then obtained by adding tetraethyl silicate as the silicon source, thiourea as the sulfur source, and urea as the nitrogen source. The uniform distribution of Co9S8 in the N/S-doped graphene matrix formed graphene-coated SiO2 particles SiO2/Co9S8@NSG with high specific surface area, superior ionic conductivity, and elevated theoretical specific capacity. The N/S co-doped graphene matrix not only improved the electrical conductivity and hindered the adhesion of the particles, but also buffered the volume of the Co9S8 change and enhanced the electrochemical performance. The testing of SiO2/Co9S8@NSG composite as an anode for lithium-ion batteries (LIBs) revealed an impressive specific capacity with reversible capacity of 850 mA h/g after 900 cycles at a current density of 0.5 A/g and multiplicative capacity of 730 mA h/g at a current density of 0.1 A/g, confirming excellent cycling stability and a Coulombic efficiency close to 100 %. Overall, the proposed doping strategy looks promising for the development of high-performance LIBs.

Microwave plasma conversion of food waste using carbon foam: Production of heteroatom-doped graphene and combustible gas

The mass production of food waste (FW) has a terrible impact on the environment, but with proper treatment, FW can be transformed into a new resource. Currently, thermal conversion (especially incineration) has been the most common and efficient means of handling FW, but it also entails negative impacts, such as high carbon emissions and lower added value. In this study, a new high-efficiency thermal conversion process is proposed that uses carbon foams to induce the formation of microwave plasma (MP), which generates very high final temperatures to enable the direct conversion of FW into combustible gases and high-value-added heteroatom-doped microwave plasma graphene (HMPG) in 5–20 s. This work investigated the optimal carbonization temperature of the melamine sponge (carbon foam precursor) and the effect of microwave plasma reaction duration on the distribution of the gas products and the properties of HMPG, and HMPG was characterized in detail by Raman spectroscopy, X-ray diffraction, scanning electron microscope, etc. Ultimately, HMPG was tested in potassium ion battery anodes for evaluation of its energy storage potential, and the results showed that the capacities were able to reach ∼270 mAh g−1 at 50 mA g−1 after 60 cycles.

Pt Nanoparticles Electrochemically Deposited onto Heteroatom-Doped Graphene Supports as Electrocatalysts for ORR in Acid Media

Platinum nanoparticles (PtNPs) are attached to different single heteroatom-doped (N, S, P, and B) and dual heteroatom-doped (N, B and N, P) graphene nanosheets via electrochemical deposition using the chronoamperometric method, which allowed for strong attachment of the PtNPs onto the support surface. The effect of the support material on the electrocatalytic activity of the PtNPs on the oxygen reduction reaction (ORR) in acidic media is examined. The PtNPs supported on boron-doped graphene exhibit the highest specific activity (1.26 mA cm−2), and the PtNPs supported on nitrogen and boron dual heteroatom-doped graphene exhibit the highest mass activity (0.70 A mg−1) at 0.9 V vs reversible hydrogen electrode. The kinetics of the ORR vary significantly depending on the dopants, thus concluding that the heteroatom doping of the graphene support material affects the electrocatalytic activity of PtNPs toward the ORR.

Constructing Reversible Li Deposition Interfaces by Tailoring Lithiophilic Functionalities of a Heteroatom-Doped Graphene Interlayer for Highly Stable Li Metal Anodes.

Lithium (Li) metal has been regarded as the ideal anode for rechargeable batteries due to its low reduction potential and high theoretical capacity. However, the formation of fatal Li dendrites during repeated cycling shortens the battery life and causes serious safety concerns. Functionalized separators with electrically conductive and lithiophilic coating layers potentially inhibit dendrite formation and growth on Li metal anodes by providing nucleation sites for reversible Li deposition/stripping. In this work, we propose functionalized separators incorporating heteroatom-doped (N or B) graphene interlayers to modulate the Li nucleation behavior. The electronegative N-doping and electropositive B-doping were investigated to understand their regulation of the Li deposition behavior. With the heteroatom-doped graphene-coated separators, we observe significantly improved cycling stability along with enhanced charge transfer kinetics and low Li nucleation overpotential. This is attributed to the heteroatom-doped graphene interlayer expanding the surface area of the Li metal anode while providing additional space for uniform Li deposition/stripping, thus preventing undesirable side reactions. As a result, the formation of dendrites and pits on the Li metal anode surface is suppressed, demonstrating the protective effect of the Li metal anode. Interestingly, N-doped graphene-coated separators exhibit lower Li nucleation overpotentials than B-doped graphene-coated separators but rather lower average Coulombic efficiencies and reduced cycling stability. This implies that adequate adsorption on B-based sites, as opposed to the strong adsorption on N-based sites, improves the reversibility. Notably, the Li adsorption strength of the lithiophilic functional groups critically affects the reversibility, as observed by Li nucleation barrier measurements and atomistic simulations. This work suggests that interface engineering using conductive and lithiophilic materials can be a promising strategy for controlling Li deposition in advanced Li metal batteries.

N, S, P tri-doped porous graphene electrocatalyst with excellent oxygen reduction activity for zinc-air battery

The heteroatom-doped graphene has attracted a lot of research due to its excellent physical, chemical and electrochemical properties considered to be the most promising electrocatalytic material for oxygen reduction reaction (ORR). Multi-doping can exert the synergistic effect between different doped heteroatoms and effectively improve the catalytic activity of doped graphene catalysts. N, P, S tri-doped graphene catalysts were prepared by simple and convenient hydrothermal and high-temperature treatment. The experimental results show that different phosphorus sources have a significant impact on the structure and performance of the prepared catalyst materials. The NSP-Gr-1 catalyst shows the high onset potential (1.035 V), half-wave potential (0.79 V) and limiting current density (−5.33 mA cm−2) for ORR. The power density of the zinc-air battery assembled with the NSP-Gr-1 catalyst achieves 163.1 mW cm−2 at 186.7 mA cm−2, which is much higher than the maximum power density of 140.0 mW cm−2 at 190 mA cm−2 for commercial Pt/C. The discharge stability under different current densities is outstanding.

Laser-induced nitrogen and boron co-doped graphene film for dye-sensitized solar cell applications

Heteroatom-doped graphenes play a crucial role in developing metal-free electrocatalysts for dye-sensitized solar cells (DSSCs). This work demonstrates an approach to synthesizing nitrogen and boron dual-doped porous graphene as an efficient DSSC counter electrode (CE) by one-step laser induction technology. The morphologies, crystal structure, and chemical composition of N and/or B-doped laser-induced graphene were characterized and confirmed by SEM, XRD, and XPS measurements. Electrochemical results indicate that the conductivity and electrocalalytic activity of the nitrogen and boron co-doped graphene (BN-LIG) for triiodide reduction were enhanced after B-doping. Hence, the DSSC based on BN-LIG CE achieved a power conversion efficiency of 4.99%, which is 90.9% of a DSSC with Pt CE.

Heteroatom-doped Graphene to Extend the Life of Sub-nanometer-scale Metal Catalysts

Heteroatom-doped Graphene to Extend the Life of Sub-nanometer-scale Metal Catalysts

One-pot synthesis of phosphorous, iodine atoms co-functionalized graphene for high-performance supercapacitor and flame-retardant applications

There has been extensive research on heteroatom-doped graphene for electrochemical energy storage and flame-retardant (FR) applications. Herein, we used a one-pot method for developing phosphorous, iodine co-doped reduced graphene oxide (PI@rGO) from red phosphorus and iodine via in situ graphene oxide (GO) reduction for supercapacitor and FR applications. In a symmetrical two-electrode cell device, the as-prepared PI@rGO demonstrated good super capacitive performance of 178 F g−1 at a current density of 1.0 A g−1, along with an exceptional energy density of 20 Wh kg−1 and power density of 1791 W kg−1. The as-synthesized PI@rGO demonstrated outstanding cyclic stability at a high current density of 10 A g−1, retaining up to 84 % of its initial capacitance after more than 6000 recurrent charge–discharge cycles. The synthesized PI@rGO showed excellent FR properties toward cotton fabric and sustained cotton fabric up to 337 s with continuous flame exposure. The control cotton fabric was completely burned in 16 s. The synthesized PI@rGO coated cotton fabric showed an excellent value of 39 % limiting oxygen index and residual char length of 2 cm. With the excellent super capacitive performance and FR properties, PI@rGO can be a promising candidate for different applications including supercapacitors and FR products.

Synthesis of graphene oxide and nitrogen-doped graphene oxide by nanosecond pulsed laser ablation of graphene in liquid for fiber optic gas sensing application

Heteroatom-doped graphene oxide has a wide range of applications in bio-imaging and sensing. In this work, Graphene Oxide (GO) and Nitrogen-doped GO (NG) were synthesized by laser ablation of Graphene in ethanol. The dopant Diethylenetriamine (DETA) is used in different amounts for different nitrogen concentrations. Optical, morphological, structural, and elemental composition studies were done by UV–vis spectroscopy, FT-IR, FE-SEM, XRD, Raman, and EDAX analysis, respectively. The nitrogen doping on the surface of GO was confirmed by FT-IR and EDAX studies. Upon laser ablation with fundamental wavelength, the graphene is converted to spherical GO nanoparticles, and nitrogen doping is done to produce porous nano coral structured NG nanoparticles. The sensitivity and selectivity of GO and NG for ammonia, ethanol, and acetone target gaseous were investigated and compared. NG sample shows excellent sensitivity and selectivity towards acetone gas. And the Nitrogen-doped graphene oxide can be considered an ideal material for gas-sensing applications.

Hetero-atom doped graphene for marvellous hydrogen storage: unveiling recent advances and future pathways

This review outlines the role of heteroatom-doped graphene in hydrogen storage. It covers storage mechanisms, critical research findings, current challenges, future research directions, and commercial implications in detail.

Investigation of Heteroatom Doped Graphene Anode for High-Capacity Alkali Metal-Ion Batteries

The drastic growth of Li-ion batteries (LIBs) in global electronic market and low crustal abundance of Li demands for more abundant alternatives such as sodium and potassium having similar electrochemical properties. Sodium-ion battery (SIB) and potassium-ion battery (PIB) can be used “side-by-side” to LIB which can help battery technology progress efficiently. 1Graphite has been a commercial anode in LIB due to its low cost, high abundance, high electrical conductivity, with a theoretical storage capacity (LiC6) of 372 mAh g-1. In contrast the utilization of graphite in SIBs and PIBs is challenging. This is due to the large radius and unstable graphite-intercalation compounds (NaC64) giving very low theoretical capacity of 30 mAh g-1. In PIBs, graphite exhibits a theoretical capacity of 279 mAh g-1 but suffers from poor stability due to huge volume expansion (60%) in fully potassiated state (KC8). Thus, focus is now shifted on to class of amorphous carbon materials such as hard carbon, soft carbon, graphene etc. with variations in micro-structures, larger interlayer spacing, and defect rich sites promoting enhanced capacity and stability even at high current densities. 2 In my presentation I will be discussing about the synthesis of heteroatom doped graphene with high charge storage and stability for LIB, SIB and PIB compared to graphite. The heteroatom doped graphene exhibits nearly 1000 mAh g-1 (LIB), 380 mAh g-1 (SIB) and 379 mAh g-1 (PIB) at a low current density of 25 mAg-1. Additionally, the elastic nature of ultrathin graphene nanosheets aids in attaining long term cyclability at 1 A g-1 with high-capacity retention of 83% for 300 cycles (LIB), 73% for 400 cycles (SIB) and 91% for 600 cycles (PIB). The enhanced stability in case of PIB, is attributed to optimizing solid electrolyte interphase (SEI) components and improving interfacial reaction kinetics at high current densities. Choice of high concentrated electrolyte (HCE) over conventional KPF6 in EC:DEC determines the nature of SEI and thereby helps in achieving cycling stability. The stability in SEI is characterized via voltage profile and understanding chemical composition by ex-situ X-ray photoelectron spectroscopy. Robust SEI in HCE is due to difference in anion structure studied by Raman spectroscopy.Furthermore, the charge-discharge mechanism, alkali ion diffusion kinetics and structure-activity relationship of electrode materials was investigated using various techniques like cyclic voltammetry profiles at different scan rates and Galvanostatic intermittent titration technique (GITT). Additionally, deeper insights into the fundamental understanding of interfacial and bulk behavior were provided with the help of in-situ Raman spectroscopy and in-situ potentiostatic electrochemical impedance spectroscopy (PEIS) analysis. The investigation of peak area and shift in D (defect) and G (graphitic) band analyzed from in-situ Raman studies helped in understanding the evolution and reversibility of alkali ion storage behavior during charging and discharging. PEIS analysis gave us a thorough understanding of the evolution of stable SEI on charging-discharging and after cycling, which helps us to understand the long-term stability in LIB, SIB and PIB.

Screening for the adsorption-activated H2O2 and peroxymonosulfate for high-performance heteroatom-doped graphene: Molecular dynamics simulation and DFT

As an green and efficient metal-free catalyst, heteroatom-doped graphene has gradually become a research topic in the catalytic field, but the active sites and mechanisms of the catalytic reactions are still not thorough enough. In this paper, the adsorption-activation properties of two activated molecules, H2O2 and peroxymonosulfate (PMS), on graphene (GR) and heteroatom (N, P, B, Si, F) doped graphene were investigated by means of computational methods. Molecular dynamics (MD) simulation results showed that the adsorption activation process of activated molecules on the surface of the six catalysts occurs in their first adsorption layer, in which B-doped graphene (BGR) has better catalytic activation performance for H2O2, while N-doped graphene (NGR) has better catalytic activation performance for PMS. Density function theory (DFT) revealed that the lowest molecular orbital gap of H2O2 at -BCO2 (0.691 eV), PMS at -NC2 has the lowest gap (0.432 eV). It is inferred that -BCO2 and -NC2 functional groups are the main functional regions of H2O2 activation by BGR and PMS activation by NGR, respectively. This work provides useful guidance for the design and optimization of high-performance metal-free catalysts, and the realization of green remediation for wastewater in the electrocatalytic oxidation process.

Synergistic effects of nitrogen-doped carbon and praseodymium oxide in electrochemical water splitting

Hybrid materials featuring perovskite-type metal oxide in conjunction with heteroatom-doped graphene hold immense promise as alternatives to costly noble metal catalysts for electrochemical water splitting, facilitating the generation of environmentally friendly hydrogen. In this study, perovskite-type oxide containing praseodymium, barium, strontium, cobalt, and iron atoms dispersed in a carbon matrix as a catalyst is synthesized via annealing of the carbon material with substrates for the preparation of perovskite oxide. The mass ratio of reagents regulates the porous structure and elemental composition. The result of the hydrogen evolution reaction (HER), suggests that the hybrid catalysts exhibit intermediate HER kinetics compared to the commercial Pt/C and the catalyst without carbon. The Tafel slope for HER is lower for materials containing carbon, because of the improved reaction kinetics, facilitated proton transfer, and enhanced electrochemical surface area. Therefore, the study provides an effective strategy for the preparation of catalyst and their use as the active catalyst of water splitting.

Exploring the Potential of Heteroatom-Doped Graphene Nanoribbons as a Catalyst for Oxygen Reduction

In this study, we created a series of N, S, and P-doped and co-doped carbon catalysts using a single graphene nanoribbon (GNR) matrix and thoroughly evaluated the impact of doping on ORR activity and selectivity in acidic, neutral, and alkaline conditions. The results obtained showed no significant changes in the GNR structure after the doping process, though changes were observed in the surface chemistry in view of the heteroatom insertion and oxygen depletion. Of all the dopants investigated, nitrogen (mainly in the form of pyrrolic-N and graphitic-N) was the most easily inserted and detected in the carbon matrix. The electrochemical analyses conducted showed that doping impacted the performance of the catalyst in ORR through changes in the chemical composition of the catalyst, as well as in the double-layer capacitance and electrochemically accessible surface area. In terms of selectivity, GNR doped with phosphorus and sulfur favored the 2e− ORR pathway, while nitrogen favored the 4e− ORR pathway. These findings can provide useful insights into the design of more efficient and versatile catalytic materials for ORR in different electrolyte solutions, based on functionalized carbon.

A colorimetric sensor array based on nanoceria crosslinked and heteroatom-doped graphene oxide nanoribbons for the detection and discrimination of multiple pesticides

Nanozymes have demonstrated high potential in constructing colorimetric sensor array for pesticides. However, rarely array for pesticides constructed without bio-enzyme were reported. Herein, nanoceria crosslinked graphene oxide nanoribbons (Ce-GONRs) and heteroatom-doped graphene oxide nanoribbons (Ce-BGONRs and Ce-NGONRs) were prepared, demonstrating excellent peroxidase-like activities. A colorimetric sensor array was developed based on directly inhibiting the peroxidase-like activities of the above three nanozymes, which realized the discrimination and quantitative analysis of six pesticides. In the presence of pesticides including carbaryl (Car), fluroxypyr-mepthyl (Flu), thiophanate-methyl (Thio), thiram (Thir), diafenthiuron (Dia) and fomesafen (Fom), the peroxidase-like activities of three nanozymes were inhibited to different degrees, resulting in different fingerprint responses. The six pesticides in the concentration range of 0.1–50 μg/mL and two pesticides mixtures at varied ratios could be detected and discriminated, and minimum detection limit for pesticides was 0.022 μg/mL. In addition, this sensor array has been successfully applied for pesticides discrimination in lake water and apple samples. This work provided a new strategy of constructing simple and sensitive colorimetric sensor array for pesticides based on directly inhibiting the catalytic activities of nanozymes.

The Effect of Heteroatom-Doped Graphene Supports on the PtNPs Electrocatalytic Activity for ORR

There has been a global shift in energy production emphasizing the reduction of fossil fuels by the augmentation of more renewable energy. Proton-exchange membrane fuel cells (PEMFC) and anion-exchange membrane fuel cells (AEMFC) can mitigate a need for fossil fuels and provide an alternative route of hydrogen-based energy production. Fuel cells utilize a catalyst at both the cathode and anode to increase the overall kinetics of the redox reactions and enhance the cell performance.1 Current fuel cell technology employs a platinum based catalyst due to its efficiency and robust performance in both alkaline and acidic environments.1,2 The drawbacks associated with Pt-based catalysts are centered around its economic viability and its affinity towards surface poisoning.1 A catalyst using platinum nanoparticles (PtNPs) loaded onto a graphene support can address some of the aforementioned drawbacks.1 To maximize the electrocatalytic activity of the PtNPs – all aspects of the PtNPs catalyst must be optimized, which includes the optimization of the support material. The effect that the different commercially available heteroatom-doped graphene had on the activity of the PtNPs was investigated during this study. The PtNPs were synthesized using the citrate method, which produces ≤ 5 nm size particles. Our study confirmed that the choice of doped graphene support has an effect on the overall activity of PtNPs. The results were confirmed via a comparison with PtNPs supported on Vulcan XC-72R carbon. All Pt catalysts supported on the doped graphene showed an improvement in the oxygen reduction reaction (ORR) half-wave potentials (E 1/2) over PtNPs on Vulcan XC-72R carbon (Fig. 1A); with the nitrogen-doped graphene exhibiting the greatest improvements in the half-wave potential with the E 1/2 value of 0.85 V vs. RHE as compared to the 0.77 V of the Pt/C. A comparison of the Tafel slopes (Fig. 1B) confirmed that the transfer of the first electron was the rate-determining step for all of the Pt catalysts supported on doped graphene as all Tafel slopes were around -120 mV per decade. This has been confirmed in literature with Pt on various carbon supports.2 Figure 1. A) Comparison of RDE polarization curves for oxygen reduction on Pt/NGr (pink), Pt/SGr (green) and Pt/N-PGr (blue) with Pt/C (black) at 1900 rpm in a O2-saturated 0.1 M HClO4 solution (v= 10 mV s−1). B) Mass transfer corrected Tafel plots derived from A

(Invited) Synthesis, Characterization and Quality Control of Heteroatom-Doped Graphene

Heteroatom doped graphene materials have gained attention as promising candidates for a variety of energy-related applications. Addition of heteroatoms in the graphene lattice is a powerful tool to modify their electronic, electrochemical, and catalytic properties. This presentation focusses on N-doped reduced graphene oxide and summarizes strategies to engineer the structure and properties of the material through control of the synthetic conditions. The produced N-doped graphene materials are characterized to determine their chemical composition, nitrogen content, degree of graphitization, surface area, electronic and electro-chemical properties. The scalability and manufacturability of the N-doped graphene materials are assessed and various examples of their current and future applications in batteries and supercapacitors are discussed.

Insights into Heteroatom-Doped Graphene Supercapacitor Data through Manual Data Separation and Statistical Analysis

Insights into Heteroatom-Doped Graphene Supercapacitor Data through Manual Data Separation and Statistical Analysis

From Pristine to Heteroatom-Doped Graphene Quantum Dots: An Essential Review and Prospects for Future Research.

Graphene quantum dots (GQDs) are carbon-based zero-dimensional materials that have received considerable scientific interest due to their exceptional optical, electrical, and optoelectrical properties. Their unique electronic band structures, influenced by quantum confinement and edge effects, differentiate the physical and optical characteristics of GQDs from other carbon nanostructures. Additionally, GQDs can be synthesized using various top-down and bottom-up approaches, distinguishing them from other carbon nanomaterials. This review discusses recent advancements in GQD research, focusing on their synthesis and functionalization for potential applications. Particularly, various methods for synthesizing functionalized GQDs using different doping routes are comprehensively reviewed. Based on previous reports, current challenges and future directions for GQDs research are discussed in detail herein.

Efficient pH-universal aqueous supercapacitors enabled by an azure C-decorated N-doped graphene aerogel

Current aqueous supercapacitors (SCs) possess the relative low energy density, and there is therefore widespread interest in cost-effective fabrication of capacitive materials with promoted specific capacitance and/or broadened voltage window. Here, a redox-active azure C-decorated N-doped graphene aerogel (AC − NGA) is fabricated using a simple hydrothermal self-assembly method through strong noncovalent π-π interaction. AC − NGA highlights an excellent charge storage performance (a high 591F g−1 gravimetric capacitance under a current density of 1.0 A g-1 and ultrahigh voltage window of 2.3 V) under pH-universal conditions. The capacitive contribution of charge storage is 91.7%, exceeding or comparable to those of the best pseudocapacitors known. Furthermore, a symmetric AC − NGA//AC − NGA device realizes high energy and power densities (15.2–60.2 Wh kg−1 at 650–23,000 W kg−1) and excellent cycling stability in acidic, neutral, and basic aqueous solutions. This work offers a cost-effective strategy to combine redox dye molecules with heteroatom-doped graphene aerogel for building green efficient pH-universal aqueous supercapacitors.