Hypergolic Materials Synthesis through Reaction of Fuming Nitric Acid with Certain Cyclopentadienyl Compounds

Nikolaos Chalmpes; Athanasios B. Bourlinos; Veronika Šedajová; Vojtěch Kupka; Dimitrios Moschovas; Apostolos Avgeropoulos; Michael A. Karakassides; Dimitrios Gournis

doi:10.3390/c6040061

Hypergolic Materials Synthesis through Reaction of Fuming Nitric Acid with Certain Cyclopentadienyl Compounds

C – Journal of Carbon Research ◽

10.3390/c6040061 ◽

2020 ◽

Vol 6 (4) ◽

pp. 61 ◽

Cited By ~ 1

Author(s):

Nikolaos Chalmpes ◽

Athanasios B. Bourlinos ◽

Veronika Šedajová ◽

Vojtěch Kupka ◽

Dimitrios Moschovas ◽

...

Keyword(s):

Nitric Acid ◽

Organometallic Chemistry ◽

Carbon Materials ◽

Materials Science ◽

Inorganic Materials ◽

Materials Synthesis ◽

Fuming Nitric Acid

Recently we have shown the importance of hypergolic reactions in carbon materials synthesis. However, hypergolic reactions could be certainly expanded beyond carbon synthesis, offering a general preparative pathway towards a larger variety of materials. Cyclopentadienyls are one of the most common ligands in organometallic chemistry that react hypergolicly on contact with strong oxidizers. By also considering the plethora of cyclopentadienyl compounds existing today, herein we demonstrate the potential of such compounds in hypergolic materials synthesis in general (carbon or inorganic). In a first example, we show that cyclopentadienyllithium reacts hypergolicly with fuming nitric acid to produce carbon. In a second one, we show that ferrocene and cobaltocene also react hypergolicly with the concentrated acid to afford magnetic inorganic materials, such as γ-Fe2O3 and metallic Co, respectively. The present results further emphasize the importance and universal character of hypergolic reactions in materials science synthesis, as an interesting new alternative to other existing and well-established preparative methods.

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Hypergolic Synthesis of Inorganic Materials by the Reaction of Metallocene Dichlorides With Fuming Nitric Acid At Ambient Conditions: The Case of Photocatalytic Titania

10.20944/preprints202105.0584.v1 ◽

2021 ◽

Author(s):

Nikolaos Chalmpes ◽

Georgios Asimakopoulos ◽

Maria Baikousi ◽

Athanasios B. Bourlinos ◽

Michael A. Karakassides ◽

...

Keyword(s):

Nitric Acid ◽

Materials Science ◽

Organometallic Compounds ◽

Inorganic Materials ◽

Titania Nanoparticles ◽

Titanocene Dichloride ◽

Ambient Conditions ◽

Materials Synthesis ◽

Wide Range ◽

Fuming Nitric Acid

Hypergolic materials synthesis is a new preparative technique in materials science that allows a wide range of carbon or inorganic solids with useful properties to be obtained. Previously we have demonstrated that metallocenes are versatile reagents in the hypergolic synthesis of inorganic materials, such as γ-Fe2O3, Cr2O3, Co, Ni and alloy CoNi. Here, we take one step further by using metallocene dichlorides as precursors for the hypergolic synthesis of additional inorganic phases, such as photocatalytic titania. Metallocene dichlorides are closely related to metallocenes, thus expanding the arsenal of organometallic compounds that can be used in hypergolic materials synthesis. In the present case, we show that hypergolic ignition of the titanocene dichloride-fuming nitric acid pair results in the fast and spontaneous formation of titania nanoparticles at ambient conditions in the form of anatase-rutile mixed phases. The obtained titania shows good photocatalytic activity towards Cr(VI) removal (100 % within 9 h), the latter being dramatically enhanced after calcination of the powder at 500 °C (100 % within 3 h). Worth noting, this performance was found to be comparable to that of commercially available P25 TiO2 under identical conditions. The cases of zirconocene, hafnocene and molybdocene dichlorides are complementary discussed in this work, aiming to show the wider applicability of metallocene dichlorides in the hypergolic synthesis of inorganic materials (ZrO2, HfO2, MoO2).

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Hypergolic Synthesis of Inorganic Materials by the Reaction of Metallocene Dichlorides with Fuming Nitric Acid at Ambient Conditions: The Case of Photocatalytic Titania

Sci ◽

10.3390/sci3040046 ◽

2021 ◽

Vol 3 (4) ◽

pp. 46

Author(s):

Nikolaos Chalmpes ◽

Georgios Asimakopoulos ◽

Maria Baikousi ◽

Athanasios B. Bourlinos ◽

Michael A. Karakassides ◽

...

Keyword(s):

Nitric Acid ◽

Materials Science ◽

Organometallic Compounds ◽

Inorganic Materials ◽

Titania Nanoparticles ◽

Titanocene Dichloride ◽

Ambient Conditions ◽

Materials Synthesis ◽

Wide Range ◽

Fuming Nitric Acid

Hypergolic materials synthesis is a new preparative technique in materials science that allows a wide range of carbon or inorganic solids with useful properties to be obtained. Previously we have demonstrated that metallocenes are versatile reagents in the hypergolic synthesis of inorganic materials, such as γ-Fe2O3, Cr2O3, Co, Ni and alloy CoNi. Here, we go one step further by using metallocene dichlorides as precursors for the hypergolic synthesis of additional inorganic phases, such as photocatalytic titania. Metallocene dichlorides are closely related to metallocenes, thus expanding the arsenal of organometallic compounds that can be used in hypergolic materials synthesis. In the present case, we show that hypergolic ignition of the titanocene dichloride–fuming nitric acid pair results in the fast and spontaneous formation of titania nanoparticles at ambient conditions in the form of anatase–rutile mixed phases. The obtained titania shows good photocatalytic activity towards Cr(VI) removal (100% within 9 h), with the latter being dramatically enhanced after calcination of the powder at 500 °C (100% within 3 h). Notably, this performance was found to be comparable to that of commercially available P25 TiO2 under identical conditions. The cases of zirconocene, hafnocene and molybdocene dichlorides are discussed in this work, which aims to show the wider applicability of metallocene dichlorides in the hypergolic synthesis of inorganic materials (ZrO2, HfO2, MoO2).

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Nanocarbon from Rocket Fuel Waste: The Case of Furfuryl Alcohol-Fuming Nitric Acid Hypergolic Pair

Nanomaterials ◽

10.3390/nano11010001 ◽

2020 ◽

Vol 11 (1) ◽

pp. 1

Author(s):

Nikolaos Chalmpes ◽

Athanasios B. Bourlinos ◽

Smita Talande ◽

Aristides Bakandritsos ◽

Dimitrios Moschovas ◽

...

Keyword(s):

Nitric Acid ◽

Furfuryl Alcohol ◽

Materials Science ◽

Ambient Conditions ◽

Materials Synthesis ◽

Rocket Fuel ◽

Carbon Nanosheets ◽

New Synthesis ◽

Fuming Nitric Acid ◽

Liquid Rocket

In hypergolics two substances ignite spontaneously upon contact without external aid. Although the concept mostly applies to rocket fuels and propellants, it is only recently that hypergolics has been recognized from our group as a radically new methodology towards carbon materials synthesis. Comparatively to other preparative methods, hypergolics allows the rapid and spontaneous formation of carbon at ambient conditions in an exothermic manner (e.g., the method releases both carbon and energy at room temperature and atmospheric pressure). In an effort to further build upon the idea of hypergolic synthesis, herein we exploit a classic liquid rocket bipropellant composed of furfuryl alcohol and fuming nitric acid to prepare carbon nanosheets by simply mixing the two reagents at ambient conditions. Furfuryl alcohol served as the carbon source while fuming nitric acid as a strong oxidizer. On ignition the temperature is raised high enough to induce carbonization in a sort of in-situ pyrolytic process. Simultaneously, the released energy was directly converted into useful work, such as heating a liquid to boiling or placing Crookes radiometer into motion. Apart from its value as a new synthesis approach in materials science, carbon from rocket fuel additionally provides a practical way in processing rocket fuel waste or disposed rocket fuels.

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Gallium Arsenide Integrated Circuits Decapsulation Technique Using Mixed Acid Chemistry For Die-Level Failure Analysis

10.31399/asm.cp.istfa2018p0496 ◽

2018 ◽

Author(s):

Harold Jeffrey M. Consigo ◽

Ricardo S. Calanog ◽

Melissa O. Caseria

Keyword(s):

Gallium Arsenide ◽

Sulfuric Acid ◽

Nitric Acid ◽

Integrated Circuits ◽

Failure Analysis ◽

Mixed Acid ◽

Optimum Parameters ◽

Plastic Package ◽

Fuming Nitric Acid ◽

Concentrated Sulfuric Acid

Abstract Gallium Arsenide (GaAs) integrated circuits have become popular these days with superior speed/power products that permit the development of systems that otherwise would have made it impossible or impractical to construct using silicon semiconductors. However, failure analysis remains to be very challenging as GaAs material is easily dissolved when it is reacted with fuming nitric acid used during standard decapsulation process. By utilizing enhanced chemical decapsulation technique with mixture of fuming nitric acid and concentrated sulfuric acid at a low temperature backed with statistical analysis, successful plastic package decapsulation happens to be reproducible mainly for die level failure analysis purposes. The paper aims to develop a chemical decapsulation process with optimum parameters needed to successfully decapsulate plastic molded GaAs integrated circuits for die level failure analysis.

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Synthesis and properties of 1,3-bis(4-nitrophenyl)-1-butene

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19802120 ◽

1980 ◽

Vol 45 (7) ◽

pp. 2120-2124 ◽

Cited By ~ 1

Author(s):

Gabriel Čík ◽

Anton Blažej ◽

Kamil Antoš ◽

Igor Hrušovský

Keyword(s):

Acetic Acid ◽

Nitric Acid ◽

Double Bond ◽

Fuming Nitric Acid

1,3-Bis(4-nitrophenyl)-1-butene was prepared by nitration of 1,3-diphenyl-1-butene (I) with fuming nitric acid in acetic acid. The double bond in I was protected by addition of bromine which was eliminated after the nitration. The UV, IR and 1H- spectra of the synthesized compounds are interpreted.

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