Synthesis, Structure, and Characteristics of the New Host Material [(C3N3)2(NH)3]n

Kawaguchi, Masayuki; Nozaki, Koji

doi:10.1021/cm00050a005

Cited by 114 publications

(96 citation statements)

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“…21,24,25 At higher wavenumbers, another broad set of low intensity peaks between 3000 and 3300 cm À1 can be observed and is attributed to the presence of the stretching vibrational modes of primary (-NH 2 ) and secondary (]N-H) amines suggesting the hydrogenation of some nitrogen atoms in the g-C 3 N 4 material. 19,25,26 These peaks are also associated with amine bridges. Moreover, a small absorption peak at 2157 cm À1 can be noticed, and is assigned to the cyano terminal group (C^N) and cumulated double bond (-N]C]N-and similar species) in the powder.…”

Section: -23mentioning

confidence: 96%

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

et al. 2013

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a Polymeric carbon nitride (g-C 3 N 4 ) films were synthesized on polycrystalline semiconductor CuInS 2 chalcopyrite thin film electrodes by thermal polycondensation and were investigated as photocathodes for the hydrogen evolution reaction (HER) under photoelectrochemical conditions. The composite photocathode materials were compared to g-C 3 N 4 powders and were characterized with grazing incidence X-ray diffraction and X-ray photoemission spectroscopy as well as Fourier transform infrared and Raman spectroscopies. Surface modification of polycrystalline CuInS 2 semiconducting thin films with photocatalytically active g-C 3 N 4 films revealed structural and chemical properties corresponding to the properties of g-C 3 N 4 powders. The g-C 3 N 4 /CuInS 2 composite photocathode material generates a cathodic photocurrent at potentials up to +0.36 V vs. RHE in 0.1 M H 2 SO 4 aqueous solution (pH 1), which corresponds to a +0.15 V higher onset potential of cathodic photocurrent than the unmodified CuInS 2 semiconducting thin film photocathodes. The cathodic photocurrent for the modified composite photocathode materials was reduced by almost 60% at the hydrogen redox potential. However, the photocurrent generated from the g-C 3 N 4 /CuInS 2 composite electrode was stable for 22 h. Therefore, the presence of the polymeric g-C 3 N 4 films composed of a network of nanoporous crystallites strongly protects the CuInS 2 semiconducting substrate from degradation and photocorrosion under acidic conditions. Conversion of visible light to hydrogen by photoelectrochemical water splitting can thus be successfully achieved by g-C 3 N 4 films synthesized on polycrystalline CuInS 2 chalcopyrite electrodes.

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Section: -23mentioning

confidence: 96%

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

et al. 2013

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“…The broad absorption band at 3100 cm -1 is related to modes involving N-H stretching vibrations. As ever mentioned by Kawaguchi and Nozaki [19], it is probable that hydrogen is bonded to nitrogen atoms which do not belong to triazine ring but which are preferably outside the ring (bridging nitrogen). This IR characterization then precises the location of hydrogen in the material and, due to the absence of absorption at 2800 cm -1 , the existence of bonds between carbon and hydrogen tends to be excluded [38].…”

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confidence: 88%

“…Although nitrogen deficiency is common in carbon nitrides because of the stability of the easily-formed N 2 molecules, it was evidenced that mild experimental conditions involved in processes such as solvothermal reactions or thermal decomposition are favorable to retain nitrogen in the material, leading then to nitrogen-rich materials [9,[15][16][17][18]. The presence of hydrogen in raw-sample is not surprising as it is usually evidenced in carbon nitrides [9,[15][16][19][20][21][22][23]. Finally, the presence of oxygen, although in low content, should be noticed as well as the absence of sulfur in raw-sample.…”

mentioning

confidence: 99%

“…While in raw-sample, carbon is only involved in triazine cycles, the XPS N1s spectrum appears much more complex as it can be analyzed on the basis of four components suggesting then an variety of nitrogen environments as shown on Fig. 4b [19,23,28,40,42]. The main component is centered at 398.3 eV and is attributed to sp 2 N involved in C 3 N 3 cycles, the  electrons delocalization in C 3 N 3 heterocycles leading to a peak at 404.1 eV.…”

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confidence: 99%

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Modulation of the crystallinity of hydrogenated nitrogen-rich graphitic carbon nitrides

Foy

Demazeau

Florian

et al. 2009

Journal of Solid State Chemistry

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An hydrogenated nitrogen-rich graphitic carbon nitride, structurally related to the theoretical graphitic phase of C 3 N 4 , has been synthesized in a bulk wellcrystallized form. This new material was prepared by thermal decomposition of thiosemicarbazide up to 600°C at ambient pressure under nitrogen flow. Its composition was determined by elemental combustion analysis. Powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and C 13MAS NMR characterizations were performed. This material can be schematically described with a two-dimensional framework and a composition close to C 3 N 4.17 H 1.12 . In this nitrogen-rich material, C 3 N 3 voids are fully occupied by water molecules which are strongly trapped into the material. A loss of crystallinity associated with a modification of the thermal behaviour is observed when the amount of trapped molecules decreases in the graphitic material, order being damaged both between and in the graphitic planes.

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“…The first examples of structural investigation date back to the early 20 th century. [5][6][7] Since then two main 2D structures have been suggested: a triazine-based ( Figure 1a) [8][9][10][11] and a tri-s-triazine-based one( Figure 1b) [12][13][14][15] . Many investigations have been carried out in order to confirm which of the two structures could describe g-C 3 N 4 .…”

Section: Introductionmentioning

confidence: 99%

Structural Investigation of Graphitic Carbon Nitride via XRD and Neutron Diffraction

et al. 2015

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Graphitic carbon nitride (g-C 3 N 4 ) has, since 2009, attracted great attention for its activity as a visible light-active photocatalyst for hydrogen evolution. Since it was synthesized in 1834, g-C 3 N 4 has been extensively studied both catalytically and structurally. While its 2D structure seems to have been solved, its 3D crystal structure has not yet been confirmed. This study attempts to solve the 3D structure of graphitic carbon nitride by mean of x-ray diffraction and of neutron scattering. Initially, various structural models are considered and their XRD patterns compared to the measured one. After selecting possible candidates as g-C 3 N 4 structure, neutron scattering is employed to identify the best model that describes the 3D structure of graphitic carbon nitride. Parallel chains of tri-s-triazine units organized in layers with an A-B stacking motif are found to describe the structure of the synthesized graphitic carbon nitride well. A misalignment of the layers is favorable because of the decreased π-π repulsive inter-layer interactions.

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Synthesis, Structure, and Characteristics of the New Host Material [(C3N3)2(NH)3]n

Cited by 114 publications

References 0 publications

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

Modulation of the crystallinity of hydrogenated nitrogen-rich graphitic carbon nitrides

Structural Investigation of Graphitic Carbon Nitride via XRD and Neutron Diffraction

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