Hydrazine Treatment Research Articles

히드록실아민과 히드라진 처리에 의한 폴리아크릴로니트릴 필름의 개질

폴리아크릴로니트릴(PAN) 필름에 히드록실아민(HA)을 반응시켜 히드록시기와 아민기를 생성시키고, 히드라진으로 처리하여 가교결합을 도입시키는 방법을 검토하였다. HA와 히드라진을 각각 처리하거나 2단계 또는 동시 처리하여 개질시킨 PAN 시료들의 반응도, 물 및 N,N'-디메틸포름아미드(DMF) 팽윤도, FTIR 스펙트럼, 원소함량, 열분석 결과들을 분석하여 효율적으로 기능기와 가교결합을 도입시키는 방법을 제시하였다. PAN 필름은 HA와의 반응에 의해 기능기가 도입되고 친수성이 향상되지만 형태안정성이 감소하며, 히드라진 처리에 의해 DMF 팽윤도가 감소한다. 히드라진 및 HA를 2단계로 처리하면 형태안정성은 향상되지만 기능기 도입이 어려워지고, 히드라진과 HA를 동시에 처리하면 형태안정성과 친수성을 효율적으로 향상시킬 수 있다. Modification of polyacrylonitrile (PAN) films by using hydroxylamine (HA) and hydrazine to produce hydroxyl and amine groups, respectively, and to introduce cross-linking of PAN polymers was studied. Modified PAN films obtained by HA and/or hydrazine treatment including a successive or a simultaneous process were analyzed by the degree of conversion, water and N,N'-dimethylformamide (DMF) swelling ratio, FTIR spectra, atom content, and thermal analysis data. PAN films reacted with HA showed increased hydrophilicity and low dimensional stability in water. Hydrazine treatment gave PAN films high dimensional stability of low DMF swelling. Although the DMF swelling ratio of the modified PAN films was dramatically decreased by the successive treatment of hydrazine and HA, the introduction of the hydrophilic functional groups was limited due to the cross-linking. Simultaneous treatment of HA and hydrazine was the most effective method to increase hydrophilicity of PAN films with a high dimensional stability.

(Invited) Tunable Thermoelectric Power Factor in Semiconducting Single-Walled Carbon Nanotube Networks

Single-walled carbon nanotubes (SWCNTs) are a versatile electronic material being explored as cost-effective, high-performance active materials in a variety of renewable energy applications such as transparent conducting or light-harvesting layers in photovoltaics and inclusions in thermoelectric composites. We present a series of experiments focused on understanding the thermoelectric performance of enriched semiconducting SWCNT networks dispersed in a semiconducting polymer matrix. Rational choice of the semiconducting polymer allows us to sensitively tune the s-SWCNT diameter and band gap distributions within the composites. We use a stable charge-transfer dopant to control the density of carriers in the s-SWCNT network, as determined by the bleach of the absorption corresponding to the S11 excitonic transition. The performance of these transparent conducting s-SWCNT composite networks is comparable to neat p-type and n-type s-SWCNT networks doped by either nitric acid or hydrazine treatments. By varying the carrier density we are able to probe the relationship between the electrical conductivity and Seebeck coefficient (thermopower) in the s-SWCNT networks as a function of the carrier density and position of the Fermi energy. Although the electrical conductivity of the s-SWCNT networks is poor at very low carrier densities we have measured a colossal thermopower as high as ~2,500 µV/K, which is more than an order of magnitude larger than has been previously reported for SWCNT-based material systems and is consistent with theoretical calculations that consider the density of electronic states in individual s-SWCNTs. As we tune the carrier density, we are able to maintain a thermopower above 200 µV/K over almost the entire range of hole densities, corresponding to conductivities up to 1885 S/m, resulting in a thermoelectric power factor of ~100 µW/m·K2. These studies suggest that the low dimensionality of the SWCNTs has a stronger impact on the electrical conductivity than the thermopower, implying that they are less strongly coupled in these systems than is observed for compound inorganic semiconductors. These observations demonstrate the ability to exert exquisite control of the thermoelectric performance by tuning the carrier density and/or Fermi energy, and touts SWCNTs as an avenue for realizing thermally stable room temperature thermoelectric devices fashioned from inexpensive and abundant organic constituents.

Studies on LiMn1.5Ni0.4Cr0.1O4 Cathode Spinel Combined with Graphene for Lithium Ion Batteries

The low-cost development of rechargeable lithium ion batteries is of considerable technological importance. In this context, the use of active cathode LiMn1.5Ni0.4Cr0.1O4 material has attracted much attention due to its stable structure while intercalation and de-intercalation of lithium ions. The necessity of such battery material is that the energy density stored electrochemically in the electrodes is quite high. They combine high theoretical energy storage capability with low weight and good mechanical strength. Here we report the development of a rechargeable lithium ion battery with homogeneous mixing of graphene powder (with 10, 15 and 20%) in active cathode materials for high energy applications. The reduced graphene oxide was synthesized using modified Hummers method with high purity concentrated of H2SO4 (50 ml), oriented pyrolytic graphite, KMnO4 (7 g) and H2O2 (30 wt %). The resultant mixture was stirred well and then filtered with the help of a glass filter. The obtained precipitates were dried for 30 h in a vacuum oven at room temperature. Highly conducting reduced graphene powder was obtained using hydrazine treatment. The redox behavior of the cell, which is normally too slow for practical applications, is accelerated with highly conductive powder of the graphene (which itself functions as an active cathode material). Intimate mixing of the two materials is achieved by a slurry maker using an organic solution for a cathode paste. The resulting electrode can be repeatedly charged to near its theoretical limit and discharged. The gravimetric energy density of our composite cathode materials exceeds that of the LiMn1.5Ni0.4Cr0.1O4 oxide electrodes in lithium-ion batteries, a feature that is likely to prove advantageous in applications where weight, rather than volume, is a critical factor. The aforementioned results will be discussed.

Iron pyrite nanocrystal film serves as a copper-free back contact for polycrystalline CdTe thin film solar cells

We report the application of thin film nanocrystalline (NC) FeS2 as the copper-free back contact for CdTe solar cells. The FeS2-NC layer is prepared from solution directly on the CdTe surface using drop-casting coupled with a hydrazine treatment at ambient temperature and pressure, and requires no thermal treatment. Copper-free solar cells based on the CdS/CdTe/FeS2-NC/Au architecture exhibit device efficiencies >90% that of a standard Cu/Au back contact devices. The FeS2-NC back contact solar cells show good thermal stability under initial tests. Devices prepared with untreated FeS2-NC back contacts display a strong “S-kink” behavior which we correlate with a high hole-transport barrier arising from inter-NC organic surfactant molecules.

Origin of 1/ f noise in graphene produced for large‐scale applications in electronics

The authors report a detailed investigation of the flicker noise (1/f noise) in graphene films obtained from chemical vapour deposition (CVD) and chemical reduction of graphene oxide. The authors find that in the case of polycrystalline graphene films grown by CVD, the grain boundaries and other structural defects are the dominant source of noise by acting as charged trap centres resulting in huge increase in noise as compared with that of exfoliated graphene. A study of the kinetics of defects in hydrazine-reduced graphene oxide (RGO) films as a function of the extent of reduction showed that for longer hydrazine treatment time strong localised crystal defects are introduced in RGO, whereas the RGO with shorter hydrazine treatment showed the presence of large number of mobile defects leading to higher noise amplitude.

Electron-doping of graphene-based devices by hydrazine

A facile and effective technique to tune the electronic properties of graphene is essential to facilitate the flexibility of graphene-based device performances. Here, the use of hydrazine as a solution-processable and effective n-type dopant for graphene is described. By dropping hydrazine solutions at different concentrations on a graphene surface, the Dirac point of graphene can be remarkably tuned. The transport behavior of graphene can be changed from p-type to n-type accordingly, demonstrating the controllable and adjustable doping effect of the hydrazine solutions. Accompanying the Dirac point shift is an enhanced hysteretic behavior of the graphene conductance, indicating an increasing trap state density induced by the hydrazine adsorbates. The electron-doping of graphene by the hydrazine solutions can be additionally confirmed with graphene/p-type silicon heterojunctions. The decrease of the junction current after the hydrazine treatment demonstrates an increase of the junction barrier between graphene and silicon, which is essentially due to the electron-doping of graphene and the resultant upshift of the Fermi level. Finally, partially doped graphene is realized and its electrical property is studied to demonstrate the potential of the hydrazine solutions to selectively electron-doping graphene for future electronic applications.

Nitrogen-doped carbon nanotubes with hydrazine treatment as cathode materials for lithium-oxygen batteries

Nitrogen-doped multi-wall carbon nanotubes (N-MWCNTs) were obtained by hydrazine reflux treatment. The introduction of hydrazine leads to successful nitrogen insertion in the form of mostly pyrrolic N. Meanwhile, the intrinsic characteristics of carbon nanotubes were retained. In addition, the N-MWCNTs exhibited superior electrochemical performance to that of pristine multi-wall carbon nanotubes (MWCNTs). The prepared N-MWCNTs delivered an initial discharge capacity of 2,927 mAh g−1 at a current density of 0.05 mA cm−2 and presented better reversibility especially at high rate and better electrocatalytic activity than MWCNTs. The results revealed that nitrogen doping into MWCNTs facilitated the reduction of oxygen and it was beneficial for Li2O2 decomposition as well.

Hydrazine Doped Graphene and Its Stability

The electronic property of graphene was investigated by hydrazine treatment. Hydrazine (N₂H₄) highly increases electron concentrations and up-shifts Fermi level of graphene based on significant shift of Dirac point to the negative gate voltage. We have observed contact resistance and channel length dependent mobility of graphene in the back-gated device after hydrazine monohydrate treatment and continuously monitored electrical characteristics under Nitrogen or air exposure. The contact resistance increases with hydrazine-treated and subsequent Nitrogen-exposed devices and reduces down in successive Air-exposed device to the similar level of pristine one. The channel conductance curve as a function of gate voltage in hole conduction regime keeps analogous value and shape even after Nitrogen/Air exposure specially whereas, in electron conduction regime change rate of conductance along with the level of conductance with gate voltage are decreased. Hydrazine could be utilized as the highly effective donor without degradation of mobility but the stability issue to be solved for future application.

A Novel Surface Treatment Method and New Insight into Discharge Voltage Deterioration for High‐Performance 0.4Li2MnO3–0.6LiNi1/3Co1/3Mn1/3O2 Cathode Materials

The Li‐rich cathode materials have been considered as one of the most promising cathodes for high energy Li‐ion batteries. However, realization of these materials for use in Li‐ion batteries is currently limited by their intrinsic problems. To overcome this barrier, a new surface treatment concept is proposed in which a hybrid surface layer composed of a reduced graphene oxide (rGO) coating and a chemically activated layer is created. A few layers of GO are first coated on the surface of the Li‐rich cathode material, followed by a hydrazine treatment to produce the reducing agent of GO and the chemical activator of the Li2MnO3 phase. Compared to previous studies, this surface treatment provides substantially improved electrochemical performance in terms of initial Coulombic effiency and retention of discharge voltage. As a result, the surface‐treated 0.4Li­2MnO3–0.6LiNi1/3Co1/3Mn1/3O2 exhibits a high capacity efficiency of 99.5% during the first cycle a the discharge capacity of 250 mAh g−1 (2.0–4.6 V under 0.1C), 94.6% discharge voltage retention during 100 cycles (1C) and the superior capacity retention of 60% at 12C at 24 °C.

Experimental study on the preparation, characterization and conductivity improvement of reduced graphene-oxide papers

In the present study, reduced graphene-oxide (r-GO) papers were prepared by vacuum filtration method using chemically obtained graphene oxide as raw materials. Different reduction methods, chemical, thermal or the combination were designed to investigate the influence of reduction process on the structure and conductivity of r-GO papers. The reducibility of the obtained papers was investigated by XPS and Raman. The structure, morphology and electrical conductivity were examined by XRD, SEM and four point resistivity test system, respectively. Results showed that chemical reduction using hydrazine or annealing in reducing ambinent alone was not sufficient to achieve maximum reduction, the highest C/O ratio and highest conductivity was obtained in paper reduced via a combination of hydrazine and thermal annealing treatment. In order to further improve the conductivity of the paper, Ag nanoparticles have been decorated into the paper.

Enamel proteins mitigate mechanical and structural degradations in mature human enamel during acid attack

A hydrazine deproteination process was used to investigate the role of enamel proteins in the acid erosion of mature human dental enamel. Bright field high resolution transmission electron micrographs and x-ray diffraction analysis show no crystallographic changes after the hydrazine treatment with similar nanoscale hydroxyapatite crystallite size and orientation for sound and de-proteinated enamel. However, the presence of enamel proteins reduces the erosion depth, the loss of hardness and the loss of structural order in enamel, following exposure to citric acid. Nanoindentation creep is larger for sound enamel than for deproteinated enamel but it reduces in sound enamel after acid attack. These novel results are consistent with calcium ion-mediated visco-elasticty in enamel matrix proteins as described previously for nacre, bone and dental proteins. They are also in good agreement with a previous double layer force spectroscopy study by the authors which found that the proteins electrochemically buffer enamel against acid attack. Finally, this suggests that acid attack, and more specifically dental erosion, is influenced by ionic permeation through the enamel layer and that it is mitigated by the enamel protein matrix.

Precise structural analysis of O-linked oligosaccharides in human serum

O-glycans are suitable targets as novel and useful tumor markers. The structures of O-glycans in human sera from four healthy controls were precisely analyzed to obtain the reference O-glycan database. O-glycans were prepared from sera by hydrazine treatment followed by fluorescent labeling with aminopyridine and identified using two-dimensional mapping, enzymatic digestion and mass spectrometry (MS) together with methanolysis and the use of newly synthesized sulfated oligosaccharides as standards. O-glycans, present at more than 0.01% of the total O-glycans, were analyzed, and 18 kinds of acidic and 2 kinds of neutral glycans were identified. NeuAcα2-3Galβ1-3N-acetylgalactosamine (GalNAc) (61-64%), NeuAcα2-3Galβ1-3(NeuAcα2-6)GalNAc (15-26%) and Galβ1-3GalNAc (6-14%) were major components while other sialylated glycans, Galβ1-3(NeuAcα2-6)GalNAc, Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-3)GalNAc and NeuAcα2-3Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-3)GalNAc were relatively minor components, accounting for ∼1-2%. Very minor glycans accounting for ∼0.01-0.1% of the total include (i) the neutral glycan, Galβ1-4GlcNAcβ1-6(Galβ1-3)GalNAc, (ii) sialylated glycans, having sialyl Tn antigen, agalacto and trisialylated structures, (iii) fucosylated glycans forming blood type H antigen, blood type A antigen, blood type B antigen, Lewis X antigen and sialyl Lewis X antigen and (iv) sulfated glycans, having 6-sulfo and 3'-sulfo structures. Two kinds of clinically applied tumor markers namely sialyl Tn antigen and sialyl Lewis X antigen in healthy controls sera were revealed to be present at ∼0.1-0.2% of the total. However, other markers such as CA19-9 and DU-PAN-2 were not found, suggesting the relative amounts of these glycans to be <0.01%. These detailed O-glycan profiles will help to find novel carbohydrate tumor markers.

Upgrading non-oxidized carbon nanotubes by thermally decomposed hydrazine

We found that the electrical properties of conductive thin films based on non-oxidized carbon nanotubes (CNTs) could be further improved when the CNTs consecutively underwent a mild hydrazine adsorption treatment and then a sufficiently effective thermal desorption treatment. We also found that, after several rounds of vapor-phase hydrazine treatments and baking treatments were applied to an inferior single-CNT field-effect transistor device, the device showed improvement in Ion/Ioff ratio and reduction in the extent of gate-sweeping hysteresis. Our experimental results indicate that, even though hydrazine is a well-known reducing agent, the characteristics of our hydrazine-exposed CNT samples subject to certain treatment conditions could become more graphenic than graphanic, suggesting that the improvement in the electrical and electronic properties of CNT samples could be related to the transient bonding and chemical scavenging of thermally decomposed hydrazine on the surface of CNTs.

X-ray absorption spectroscopy study on the thermal and hydrazine reduction of graphene oxide

X-ray absorption spectroscopy (XAS) was applied to systemically investigate the deoxygenation of graphene oxide (GO) via annealing and hydrazine treatment. Detailed evolution of the electronic structures and chemical bonding of GO was presented. The enhanced intensity of π* resonance and the appearance of splitting σ* resonance in C K-edge XAS spectra suggest high extents of recoveries of π-conjugation upon reduction using thermal annealing or hydrazine. Experimental results revealed that the carboxyl as well as epoxide and hydroxyl groups on the surface of GO were thermally reduced first, followed by the more difficult removal of carbonyl and cyclic ether groups at higher temperatures. The hydrazine reduction could remove epoxide, hydroxyl and carboxyl groups effectively, whereas the carbonyl groups were partially reduced with the incorporation of nitrogen species simultaneously. The residual oxygen functional groups on hydrazine-reduced GO could be further removed after modest thermal annealing. It was proposed that a combination of both types of reductions would give the best deoxygenation efficiency for the production of graphene.

Nitrogen-Doped Pt/C Electrocatalysts with Enhanced Activity and Stability toward the Oxygen Reduction Reaction.

Recently, nitrogen-doped carbon materials have proved to be effective catalytic platforms for the oxygen reduction reaction (ORR). Despite the recent synthetic advances for the preparation of nitrogen-incorporated carbon materials, the low-temperature and water-based synthesis of nitrogen-doped carbon materials has rarely been explored due to the difficulties in nitrogen-doping under such mild conditions. Here, nitrogen-doped Pt/C (Pt/NC) catalysts are prepared using a facile, low-temperature, aqueous-phase method. Hydrazine treatment of a Pt/C catalyst successfully yields Pt/NC with controlled nitrogen content. The as-prepared Pt/NC catalysts exhibit enhanced electrocatalytic activity and stability toward ORR in comparison to nitrogen-free Pt/C, and their ORR activities are highly dependent on the level of nitrogen-doping. The Pt/NC catalyst containing 2.0 at % nitrogen results in the largest improvement of ORR activity.

P-DSSCs with BiOCl and BiOBr semiconductor and polybromide electrolyte

BiOCl and BiOBr nanodiscs (100–150 nm in diameter, 15–25 nm in thickness) are prepared via water-based nucleation and purified by a phase-transfer reaction, including oleylamine-induced transfer of the as-prepared nanodiscs from the polar water phase to the non-polar toluene phase. The oleylamine-capping is then removed by hydrazine treatment, and the BiOCl/BiOBr nanodiscs are redispersed in 2-propanol. The as-prepared nanodiscs are finally deposited as a porous, p-type semiconductor layer to obtain dye-sensitized solar cells (DSSCs). Herein, coumarin 343 is applied as sensitizer together with BiOCl as p-type semiconductor and a KI–I2 electrolyte. In addition, eosin Y is applied as sensitizer together with BiOBr as p-type semiconductor and a [C4MPyr]2[Br20] polybromide electrolyte (C4MPyr: N-butyl-N-methylpyrrolidinium). Such polybromide electrolyte is firstly applied in a DSSC and allows for a higher redox potential. Both here established p-DSSCs show the characteristic features and function of a solar cell (BiOCl/coumarin 343/KI–I2: Voc = 120 mV, Jsc = 57 μA cm−2, FF = 40.6%, η = 0.003; BiOBr/eosin Y/[C4MPyr]2[Br20]: Voc = 78 mV, Jsc = 3.1 μA cm−2, FF = 28.6%, η = 0.0005) as a result of this conceptual study.

Enhanced transport properties of assembled CdSe quantum dot through slow evaporation with mixed solvents

CdSe quantum dots (QDs) were assembled into uniform aligned packed sheets over large area in a mixture of toluene/acetonitrile solvents through slow evaporation, and preferential evaporation of the solvent led to self-assembly under conditions of continuously decreasing solvent quality. Depending on the volume ratio of acetonitrile, the CdSe QDs formed different packing type and coverage. This simple method of depositing assembled CdSe QDs makes it possible to study the novel transport properties of CdSe QDs. The related transport results showed that the increase in photocurrent with hydrazine and post annealing treatment are due to increased QDs surface passivation and decreased QDs spacing.

Preparation of Nanocrystalline Nitrogen-doped Mesoporous Titanium Dioxide

Nanocrystalline (4–5 nm) N-doped mesoporous TiO 2 (anatase and brookite) with N atoms in interstitial positions and a high specific surface area was prepared using hydrazine treatment and calcination in a flow of N 2 .

Myoblast differentiation on graphene oxide

Graphene-based nanomaterials have received much attention in biomedical applications for drug/gene delivery, cancer therapy, imaging, and tissue engineering. Despite the capacity of 2D carbon materials as a nontoxic and implantable platform, their effect on myogenic differentiation has been rarely studied. We investigated the myotube formation on graphene-based nanomaterials, particularly graphene oxide (GO) and reduced graphene oxide (rGO). GO sheets were immobilized on amine-modified glass to prepare GO-modified glass, which was further reduced by hydrazine treatment for the synthesis of rGO-modified substrate. We studied the behavior, including adhesion, proliferation, and differentiation, of mouse myoblast C2C12 on unmodified, GO-, and rGO-modified glass substrates. According to our analyses of myogenic protein expression, multinucleate myotube formation, and expression of differentiation-specific genes (MyoD, myogenin, Troponin T, and MHC), myogenic differentiation was remarkably enhanced on GO, which resulted from serum protein adsorption and nanotopographical cues. Our results demonstrate the ability of GO to stimulate myogenic differentiation, showing a potential for skeletal tissue engineering applications.

Electrical and spectroscopic investigations on the reduction mechanism of graphene oxide

Ultra-large graphene oxide sheets of monolayer thickness were obtained by removing ultrasonication during the conventional oxidation process of graphite. In situ electrical conductivity measurement during the reduction by hydrazine monohydrate vapor and thermal annealing revealed the existence of an onset temperature at which electrical conduction started to occur. Corresponding X-ray photoelectron spectra indicated that an approximately 65% restoration of the sp2 network led to the occurrence of electrical conduction. Reduction by ring-opening of epoxide group by hydrazine treatment seemed to restore the sp2 network, while thermal annealing left a considerable number of defects in the graphene sheet through the formation of volatile gases.