scispace - formally typeset
Open AccessJournal ArticleDOI

Facile synthesis of nitrogen-doped graphene via low-temperature pyrolysis: The effects of precursors and annealing ambience on metal-free catalytic oxidation

TLDR
In this article, a green and facile protocol of thermal treatment of graphene oxide (GO) with urea was adopted to synthesize nitrogen-doped graphene (NG-Urea-air) at a low temperature (350°C) in the static air.
About
This article is published in Carbon.The article was published on 2017-05-01 and is currently open access. It has received 299 citations till now. The article focuses on the topics: Graphene & Carbocatalysis.

read more

Citations
More filters
Journal ArticleDOI

Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks.

TL;DR: This Critical Review comparatively examines the activation mechanisms of peroxymonosulfate and peroxydisulfates and the formation pathways of oxidizing species and the impacts of water parameters and constituents such as pH, background organic matter, halide, phosphate, and carbonate on persulfate-driven chemistry.
Journal ArticleDOI

Metal-free carbocatalysis in advanced oxidation reactions

TL;DR: This Account showcases the recent contributions to metal-free catalysis in advanced oxidation, including design of nanocarbon catalysts, exploration of intrinsic active sites, and identification of reactive species and reaction pathways, and offers perspectives on carbocatalysis for future environmental applications.
Journal ArticleDOI

Catalytic removal of aqueous contaminants on N-doped graphitic biochars: inherent roles of adsorption and nonradical mechanisms.

TL;DR: This study not only provides robust and cheap carbonaceous materials for environmental remediation but also enables the first insight into the graphitic biochar-based nonradical catalysis.
Journal ArticleDOI

Identifying the Nonradical Mechanism in the Peroxymonosulfate Activation Process: Singlet Oxygenation Versus Mediated Electron Transfer

TL;DR: This study explored singlet oxygenation and mediated electron transfer as plausible nonradical mechanisms for organic degradation by carbon nanotube (CNT)-activated peroxymonosulfate (PMS) and suggested that CNT-mediated electron transfer from organics to persulfate was primarily responsible for the nonradical degradative route.
Journal ArticleDOI

Nonradical reactions in environmental remediation processes: Uncertainty and challenges

TL;DR: In this article, the authors present state-of-the-art research on nonradical pathways in persulfate-based AOPs, with emphases on the controversial methodologies for identifying the oxygen reactive species (ROS), ambiguous reaction mechanisms, intrinsic impacts of metal/carbon catalysts and organic substrates in the nonradical-based catalytic oxidation reactions.
References
More filters
Journal ArticleDOI

Production of Sulfate Radical and Hydroxyl Radical by Reaction of Ozone with Peroxymonosulfate: A Novel Advanced Oxidation Process

TL;DR: It is demonstrated that the reaction between the anion of PMS and O3 is primarily responsible for driving O3 consumption with a measured second order rate constant of (2.12 ± 0.03) × 10(4) M(-1) s(-1).
Journal ArticleDOI

Proton‐Functionalized Two‐Dimensional Graphitic Carbon Nitride Nanosheet: An Excellent Metal‐/Label‐Free Biosensing Platform

TL;DR: A highly sensitive and highly selective heparin sensing platform based on protonated g-C3N4 nanosheets is established that can reach the lowestHeparin detection limit of 18 ng mL(-1).
Journal ArticleDOI

Low-temperature synthesis of nitrogen/sulfur co-doped three-dimensional graphene frameworks as efficient metal-free electrocatalyst for oxygen reduction reaction

TL;DR: In this paper, a one-pot hydrothermal approach towards three-dimensional nitrogen and sulfur co-doped graphene frameworks (N/S-GFs) employing graphene oxide and ammonium thiocyanate as the precursors is presented.
Journal ArticleDOI

Performance of nano-Co3O4/peroxymonosulfate system: Kinetics and mechanism study using Acid Orange 7 as a model compound

TL;DR: Nano-Co 3 O 4 /PMS was used to activate peroxymonosulfate (PMS) and degrade a model compound Acid Orange 7 (AO7).
Journal ArticleDOI

Nitrogen-Doped Graphene Nanosheets as Metal-Free Catalysts for Aerobic Selective Oxidation of Benzylic Alcohols

TL;DR: In this article, the authors demonstrate the molecular engineering of active sites on a graphene scaffold and demonstrate that the N-doped graphene nanosheets prepared by a high-temperature nitridation procedure represent a novel chemical function of efficiently catalyzing aerobic alcohol oxidation.
Related Papers (5)
Frequently Asked Questions (19)
Q1. What are the contributions in "Facile synthesis of nitrogen-doped graphene via low-temperature pyrolysis: the effects of precursors and annealing ambience on metal-free catalytic oxidation" ?

In this paper, the authors applied a facile strategy by direct treatment of GO and urea at a moderate temperature ( 350 °C ). 

The annealing process with a slowheating rate (5 °C/min) also effectively inhibited the polycondensation of urea as the process only occurs during the rapidly thermal polymerization in the presence of large amounts of urea. 

the acidic/basic condition of the reaction solutions can impact the catalytic performance of metal catalysts as the strong acidic condition can destroy the metal crystalline structure and lead to severe metal leaching. 

Introducing heteroatoms (B, N, O, P, S, and so forth) into the carbon lattice can effectively disorientate the homogeneously conjugated electron network and modulate the surface properties by tweaking the charge distribution and spinning culture of the doped domains [13, 14]. 

Their pioneering studies integrating with material design and theoretical calculations revealed that, due to a greater electronegativity (χN = 3.04) compared with the carbon atom (χC = 2.55), N-doping can effectivtly interrupt the highly-conjugated carbon network of graphene and induce the electron transport from the neighbouring carbon to nitrogen atoms, giving rise to positively charged carbon atoms [37, 38]. 

Many studies have reported that N-doping can effectively break the inertness of sp2 hybridized carbon lattice and dramatically tailor the electron density and spin culture of the adjacent carbon, giving rise to the superb catalytic performances in electrochemistry, hydrocarbon conversion, and superoxide activation [34-36]. 

Their previous study also indicated raising the annealing temperature in inert atmosphere would result in a lower N-doping level due to the breakup of C-N bond while affording a higher proportion of quaternary N benefiting from the better thermal stability of graphitic N, which is simultaneously bonded with three carbon atoms with substitutional doping in the carbon framework [26]. 

The mild annealing and doping processes favored the oxidative atmosphere due to the induced structure defects such as edging sites and vacancies which enabled carbon reconstruction for N-doping. 

the rGO can be used as a better carbon precursor to prepare nitrogen-doped graphene with a desirable SSA, N-doping level, defective degree, and stunning catalytic activity. 

With respect to rGO, the re-constructing of graphene boundaries (edging sites) and lattice during annealing may also help attain certain amounts of N-doping as shown in this study. 

The green and efficient carbocatalysts have demonstrated extraordinary potentials for activating various superoxides (e.g. peroxymonosulfate, persulfate, hydrogen peroxide, and ozone) for the oxidative removal of toxic pollutants in wastewater without any secondary contamination [18-21]. 

Both organic substances and inorganic salts were applied as the nitrogen precursors for nitrogen doping and urea was discovered to be the best precursor with a high doping level and better reducibility without any polycondensation. 

The experimental results indicated that the nitrogen-doped graphene with a higher proportion of graphitic N at a similar doping level exhibited a better catalytic activity for phenol oxidation, and the densities functional theory (DFT) calculations further evidenced that the adsorption of PMS molecules at the adjacent carbon of graphitic N exhibited the lowest adsorption energy and greatest tendency for electron transfer from carbon lattice to PMS for the activation of superoxide O-O bond [26]. 

The proportion of graphitic N of NG-Urea-air and N-rGO-air in total nitrogen was low due to the fact that the mild annealing temperature cannot produce high contents of substitutional N-doping into the carbon lattice. 

The outstanding efficiency of PMS activation on nitrogen-doped graphene is also contributed by the non-radical process, in which the PMS molecules are activated at N-doped domains and followed by readily oxidation of target organics via electron transfer as illustrated in Fig. 

due to the complicated structure and surface chemistry of nanocarbons, the mechanism of carbocatalysis in metal-free oxidation remains ambiguous, leaving more blanks for mechanisticstudy. 

Fig. S8 manifested that the phenol oxidation rate was speeded up with the increased nitrogen amount in graphene, suggesting that the high doping level leads to a promoted catalytic performance for PMS activation. 

The ammonium salts would decompose during the thermal annealing and release NH3 (the doping agent) and other gasses (N2, N2O, or HCl), which facilitate the formation of porous N-doped graphene with larger SSAs, pore size, and pore volume (Fig. S9 and Table S2). 

The XPS surveys in Fig. 3a illustrate that thermal annealing effectively eliminated the oxygen groups of the graphene oxide (31.4 at.%, Table 1) to form a more reductive surface of rGO-air (14.3 at.%).