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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.
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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.

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Nitrogen-doped carbon nanotubes derived from carbonized polyaniline as a robust peroxydisulfate activator for the oxidation removal of organic pollutants: Singlet oxygen dominated mechanism and structure-activity relationship

TL;DR: In this article , a nitrogen-doped carbon nanotube catalyst (CPNT-10) was developed using the low-cost polyaniline (PANI) nanotubes as the precursor, which exhibited excellent peroxydisulfate (PDS) catalytic activity to degrade 2,4-dichlorophenol (2, 4-DCP).
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Heteroatom-Doped Graphene for Efficient NO Decomposition by Metal-Free Catalysis.

TL;DR: The feasibility for heteroatom-doped graphene to be effectively used for decomposing NO was experimentally confirmed and the effect of pyridinic N and thiophene S on the reaction mechanism was proposed.
Journal ArticleDOI

Selective production of singlet oxygen from zinc-etching hierarchically porous biochar for sulfamethoxazole degradation.

TL;DR: In this paper, a family of porous biochar catalysts (ZnBCs) with different porous structures and surface functionalities are synthesized using a chemical activation agent, and the functional biochars are used to activate persulfate for sulfamethoxazole (SMX) degradation.
Journal ArticleDOI

Bamboo-like nitrogen-doped carbon nanotubes on iron mesh for electrochemically-assisted catalytic oxidation

TL;DR: According to the quenching tests, both radical and non-radical processes are present for PMS activation, thus obtaining enhanced organics removal efficiency and the electrochemically assistant could enhance the PMS adsorption on the electrode as well as electrons transfer between Fen+ and PMS, thus increasing thePMS activation efficiency.
Journal ArticleDOI

Recent advances in applications of nonradical oxidation in water treatment: Mechanisms, catalysts and environmental effects

TL;DR: In this paper, the intrinsic impacts of carbon-based, metal-based materials are clarified, with emphasis on reactive oxygen species, pivotal functional groups and specific mechanism, and the applications, opportunities and challenges of non-radical oxidation.
References
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Journal ArticleDOI

Electric Field Effect in Atomically Thin Carbon Films

TL;DR: Monocrystalline graphitic films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands and they exhibit a strong ambipolar electric field effect.
Journal ArticleDOI

The rise of graphene

TL;DR: Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena can now be mimicked and tested in table-top experiments.
Journal ArticleDOI

Raman spectrum of graphene and graphene layers.

TL;DR: This work shows that graphene's electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers, and allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area.
Journal ArticleDOI

Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide

TL;DR: In this paper, a colloidal suspension of exfoliated graphene oxide sheets in water with hydrazine hydrate results in their aggregation and subsequent formation of a high surface area carbon material which consists of thin graphene-based sheets.
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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.%).