Vol. 6, №1, 2014

SERGEY PAVLOVICH GUBIN - 75

SUPERCRITICAL ISOPROPANOL AS REAGENT IN ORGANIC, ORGANOMETALLIC, INORGANIC CHEMISTRY AND NANOTECHNOLOGY
Buslaeva Elena Yu.
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, http://www.igic.ras.ru
31, Leninsky prosp., 117991 Moscow, Russian Federation
eyubuslaeva@inbox.ru

There is a short review of experimental results, obtained by Prof. S.P. Gubin and his colleagues in chemistry of supercritical fluids. It was found, that isopropanol under supercritical conditions (SCI) changes its hydrogenating capacity in the following order: (CH₃)₂CHOH>C₂H₅OH>CH₃OH. The multiple bonds of different types as С=С, С=О, C=S, C=N, C=P were hydrogenated by SCI. Ordinary bonds C-S, C-Hal, C-M were exposed to effective hydrogenolysis. Reactions were conducted without catalysts; the yields and selectivity of the reactions were high. It was shown, that supercritical isopropanol is universal hydrogenating reagent, which reacts with wide series of organic and organometallic substrates. The preparative procedures of ordinary oxides reduction by SCI were developed in the Laboratory of nanomaterial chemistry IGIC RAS, leading by S.P. Gubin. The methods, allowing working with SCI under normal laboratory conditions were developed. The optimal conditions (temperature, pressure) of the reactions and also the ratios of reactants for working with inorganic oxides were found. The procedure of complex oxides reduction by SCI was developed. The simple method of stabilized in polyethylene matrices nanoparticles metal oxides reduction by SCI to obtain metal nanoparticles was developed in situ. The procedure of SCI reduction of metal oxides, localized in matrices of synthetic SiO₂, without extraction of nanoparticles from matrices was found. The simple method of the reducing graphene oxide fabrication was found in the Laboratory of nanomaterial chemistry IGIC RAS, leading by Prof. S.P.Gubin. This method allows obtaining of appreciable amounts of graphene (grams). At present novel procedures for nanomateriales on the basis of graphene are developed. It was found, that SCI is universal, nontoxic, applicable in mild conditions reducing agent, which can be used in inorganic chemistry, nanotechnology and chemistry of graphene.

Keywords: supercritical isopropanol, hydrogenation, inorganic oxides, reduction, nanotechnologies, grapheme

UDC 547.56;547.261; 535,343; 543,51; 546,711; 538,214; 546.26;549.211

Bibliography – 23 references
Received 30.11.2012

RENSIT, 2012, 4(2):38-49
REFERENCES

Kirilets VM, Men’shov VI, Rykov EM, Plopsky EYa, Gubin SP. O superkriticheskom rastvorenii ugley Kansko-Achinskogo basseyna [On the supercritical dissolution of the coals Kansk-Achinsk basin]. DAN SSSR, 1983, 268(5):1129-1131(in Russ.).
Gubin SP, Kirilets VM, Men’shov VI et al. Gidrirovanie kratnykh svyasey izopropilovym spirtom bez katalizatora [Hydrogenation of the double bonds with isopropyl alcohol without catalyst]. Izv. AN SSSR, ser.khim., 1983, 12:2853-2856(in Russ.).
Gubin SP, Kirilets VM, Men’shov VI et al. Alkilirovanie fenolov metanolom bez katalizatora [Alkylation of phenol with methanol without a catalyst]. Izv. AN SSSR, ser.khim., 1985, 9:2159-2160 (in Russ.).
Gubin SP. Superkriticheskoe gidrirovanie bez vodoroda i katalisatorov [Supercritical hydrogenation without hydrogen and catalysts]. DAN SSSR, 1995, 345(4):490-492 (in Russ.).
Kajimoto O. Solvation in supercritical fluids: its effects on energy transfer and chemical reactions. Chem. Rev., 1999, 99:355-389.
Timashev SF, Solov’eva AB, Buslaeva EYu, Gubin SP. Kontsertnye protsessy v srede superkriticheskikh fluidov [Concert processes in the environment of supercritical fluids]. Zh.fizich.khimii, 2013, 1:(in print) (in Russ.).
Buslaeva EYu. Primenenie superkriticheskogo izopropanola kak reagenta v organicheskoy, metalloorganicheskoy i neorganicheskoy khimii [The use of supercritical isopropanol as a reagent in organic, organometallic and inorganic chemistry]. Tez.dokl. I mezhd. nauchno-praktich.konf. «Sverkhkriticheskie fluidnye tekhnologii: innovatsionny potentsial Rossii». Rostov-na Donu, 29.06-1.07 2004, p. 25-26.
Gubin S.P., Buslaeva E.Yu.. SCF-isopropanol as a reagent in organic, organometallic and inorganic chemistry. Proc. 6th Intern. Sympos. on Supercritical Fluids. Versailles, France, April 28-30, 2003, 2:1133-1138.
Buslaeva EYu, Kargin YuF, Kravchuk KG, Sigachev SA, Gubin SP. Vzaimideystvie α-Bi₂O₃ s izopropilovym spirtom, nakhodyaschemsya v nadkriticheskom sostoyanii [Interaction α-Bi2O3 with isopropyl alcohol, being in a supercritical state]. Zh.neorgan.khimii, 2001, 46(3):380-383 (in Russ.).
Buslaeva EYu, Kravchuk KG, Kargin YuF, Gubin SP. Vzaimodeystvie MnО₂, Mn₂О₃ , α-Bi₂О₃ и Bi₁₂Ti_1-xMn_xО₂₀ so sverkhkriticheskim izopropanolom kak metod ozmeneniya kislorodnoy stekhiometrii oksidov [MnО₂, Mn₂О₃ , α-Bi₂О₃ и Bi₁₂Ti_1-xMn_xО₂₀ interaction with supercritical isopropanol as a method of changing the oxygen stoichiometry oxides]. Zh.neorgan.mater., 2002, 38(6):706-710 (in Russ.).
Kargin YuF, Buslaeva EYu, Kravchuk KG, Gubin SP. Vzaimodeystvie oksidov s superkriticheskim izopropilovym spirtom [The interaction of oxides with supercritical isopropyl alcohol]. Zh.neorgan.khimii, 2003, 48(1):111-114 (in Russ.).
Gubin SP, Kargin YuF, Buslaeva EYu, Kravchuk KG. Gidrirovanie oksidov RZE SKF izopropanolom [Hydrogenation of REE oxides SCF isopropanol]. Zh.neorgan.khimii, 2003, 48(5):810-811 (in Russ.).
Kargin YuF, Buslaeva EYu, Egorysheva AV, Kravchuk KG, Gubin SP. Vzaimodeystvie slozhnykh oksidov s superkriticheskim izopropilovym spirtom [The interaction of complex oxides with supercritical isopropyl alcohol].Zh.neorgan.khimii, 2003, 48(11):1765-1768 (in Russ.).
Yurkov GYu, Astaf’ev DA, Gorkovenko MYu, Buslaeva EYu, Kargin YuF, Gubin SP. Modifikatsiya sostava vismutsoderzhaschikh nanochastits vnutri polietilenovoy matritsy [Modification of bismuth-containing nanoparticles inside polyethylene matrix]. Zh.neorgan.khimii, 2005, 50(9):1402-1407 (in Russ.).
Gorkovenko MYu, Yurkov GYu, Buslaeva EYu, Gubin SP. Reaktsii nanochastits oksidov svintsa (II) i rtuti (II) vnutri polietilenovoy matritsy: ikh vosstanovlenie sverkhkriticheskim izopropilovym spirtom [Reaction of plumbum (II) and mercury (II) oxide nanoparticles in a polyethylene matrix: their recovery supercritical isopropyl alcohol]. Zh.neorgan.khimii, 2006, 51(1):1-6 (in Russ.).
Buslaeva E.Yu., Astafiev D.A., Koksharov Yu.A., Yurkov G.Yu. Interaction of Rhenium and Manganese Nanoparticles, Stabilised in polimer matrices, with Supercritical Isopropanol. Abstracts of 8th Intern. Symposium on Supercritical Fluids (ISSF2006), Kyoto(Japan), Novem. 5-8, 2006, PB-2-38.
Kargin YuF, Ivicheva SN, Buslaeva EYu, Kuvshinova TB, Volodin VD, Yurkov GYu. Poluchenie nanochastits vismuta v opalovoy matritse vosstanovleniem soedineniy vismuta izopropanolom v sverkhkriticheskom sostoyanii [Obtaining of bismuth nanoparticles in opal matrix restoration of bismuth compounds with isopropanol in supercritical state]. Neorg.materialy, 2006, 42(5):547-550 (in Russ.).
Kargin YuF, Ivicheva SN, Buslaeva EYu, Volodin VD, Yurkov GYu. Vosstanovlenie soley razlichnykh metallov v opalovoy matritse isopropanolom v sverkhkriticheskom sostoyanii [Reduction of salts of various metals in the opal matrix with isopropanol in the supercritical state]. Neorg.materialy, 2006, 42 (9):1065-1069 (in Russ.).
Egorysheva AV, Burkov VI, Buslaeva EYu, Kargin YuF, Kravchuk KG, Gubin SP, Skorikov VM Izmenenie spektroskopicheskikh kharakteristik kristallov sillenita pri ikh vzaimodeistvii s superkriticheskimi fluidami [Change the spectroscopic characteristics of sillenite crystals in their interaction with supercritical fluids]. Zh.neorgan.khimii, 2002, 47(6):992-998 (in Russ.).
Tkachev SV, Buslaeva EYu, Naumkin AV, Laure IV, Gubin SP. Vosstanovlenny okcid grfena [Refurbished graphene oxide]. Neorg.materialy,, 2012, 48(8):1-7 (in Russ.).
Ioni YuV, Lubimov SE, Gubin SP. Poluchenie vosstanovlennogo oksida grafena s nanochastitsami palladiya i rodiya na ego poverkhnosti [Getting reduced graphene oxide with palladium and rhodium nanoparticles on its surface]. Тez. dokl. 14 mezhd. nauchno-tekhn.konf. «Naukoemkie khimicheskie tekhnologii-2012», 21-25 mai 2012, Tula, Rossiya, s. 909–915.
Shalyapina AYa, Solov’eva AYu, Zaporozhets MA, Khokhlov EM, Fatyushina EV, Buslaeva EYu, Gubin SP. Kompozitsionnye materialy na osnove grafena s nanochastitsami oksida zinka [Composite materials based on graphene with nanoparticles of zinc oxide]. Tez. dokl. 11 mezhd. konf.. «Khimiya tverdogo tela: nanomaterialy, nanotekhnologii». 22-27 apr. 2012, Stavropol, Rossiya, s. 280-282.
Gubim SP, Buslaeva EYu. Sverkhkriticheskiy izopropanol kak vosstanovitel’ neorganicheskikh oksidov [Supercritical isopropanol as a reducing inorganic oxides]. Sverkhkriticheskie fluidy. Teoriya i praktika. 2009, 4(4):73-96 (in Russ.).

Full-text electronic version of this article - web site http://elibrary.ru