Iron-phthalocyanine support

Differences in the orientations and polymorphism have been identified on vapor deposited thick films of iron phthalocyanines supported on glassy carbon (129). These "bulk" differences correlated directly with the ability of the film to catalyze... 

Choi, H.J., G. Kwag, and S. Kim (2001). Electrochemical and XAFS investigation of nitrite reduction by heat-treated fi-oxo derivative if iron phthalocyanin supported on high area carbon. J. Electtoanal. Chem. 508, 105-114. 

Yuan Y, Zhao B, Jeon Y, Zhong S, Zhou S, Kim S (2011) Iron phthalocyanine supported on amino-functionalized multi-walled carbon nanotube as an alternative cathodic oxygen catalyst in microbial fuel cells. Biores Technol 102(10) 5849-5854... 

Previous studies by Sorokin with iron phthalocyanine catalysts made use of oxone in the oxidation of 2,3,6-trimethylphenol [134]. Here, 4 equiv. KHSO5 were necessary to achieve full conversion. Otherwise, a hexamethyl-biphenol is observed as minor side-product. Covalently supported iron phthalocyanine complexes also showed activity in the oxidation of phenols bearing functional groups (alcohols, double bonds, benzylic, and allylic positions) [135]. Besides, silica-supported iron phthalocyanine catalysts were reported in the synthesis of menadione [136]. 

The chemical structure of iron-phthalocyanine is shown on Figure 1. PcFe is a planar molecule with a central cavity in which the iron atom is located. Metal phthalocyanines may be sublimated and the deposition of PcFe on the carbon support has been done by vapor phase condensation (16). During the condensation, the carbon supports are kept at 235°C, Condensation rates were in the range 2-4 mg PcFe per hour. Samples with PcFe content ranging from 0.5 to 30 % in weight have been prepared with both carbon substrates. 

The surface properties of carbon play an important role in the dis persion and the sintering behavior of supported catalyst. The study of iron-phthalocyanine is of particularly interest for the investigation of catalyst-carbon support interactions. The coalescence of PcFe particles on graphitized carbon is considerably lowered by the... 

The mass variation calculated from the variation of the quartz crystal vibration frequency for an iron phthalocyanine catalyst supported on caibon is presented in Fig. 43. In the potential domain over 0.5 V vs RHE, the mass increases during the positive going scan and decreases during the negative going scan. This confirms that the change in oxidation state of the central metal ion is accompanied by an adsorption-desorption process. Furthermore,... 

We have prepared the Fe Pc/ zeolite catalyst and used in the aerobic oxidation of 1-octene and cyclohexene. Zeohte-encapsulated iron phthalocyanine proved to be an active and stable catalyst in the oxidation of hydroquinone and in the triple catdytic oxidation of 1-octene and cyclohexene. Product distribution, selectivity and yield were similar to those obtained with free iron phthalocyanine. No decrease in catalytic activity was observed during the catalytic reaction. The zeohte-encapsulated complex is easier to handle than the non-supported one, it can be removed from the reaction mixture by simple filtration and it can be reused in several subsequent catalytic runs with similar catalytic activity. 

A high density of nucleation centers on a substrate can also be achieved by an accordingly dense arrangement of the catalyst particles in a CVD process. Examples include nanoparticles of iron or cobalt that are precipitated from solution on a silicon support or the pretreatment of the catalyst film with ammonia Likewise does the thermal decomposition of iron phthalocyanine generate enough iron particles for the subsequent growing nanotubes to interfere with each other, thus forcing them into a vertical orientation. 

Selective oxidation of alkenes on a zeolite supported iron phthalocyanine catalyst... 

The zeolite-encaped iron phthalocyanine catalyst was used to oxidize hydro-quinone to benzoquinone, 1-decene to 2-decanone and cyclohexene to 1-acetoxy-2-cyclohexene. The free iron phthalocyanine catalyst was also used for the same oxidation reactions, and the results were compared with those obtained employing the supported catalyst. 

The zeolite-encapsulated iron phthalocyanine catalyst was also active in this reaction and the catalytic activity was similar to that of the free complex. After the injection of a new portion of hydroquinone, the catalyst showed almost the same activity as in the first run, indicating that there was no catalyst deactivation during the reaction. The supported catalyst can be filtered off and used in new experiments. 

Morozan A, Campidelli S, Filoramo A, Jousselme B, Palacin S (2011) Catalytic activity of cobalt and iron phthalocyanines or porphyrins supported on different carbon nanotubes towards oxygen reduction reaction. Carbon 49(14) 4839 847... 

Ahmed J, Yuan Y, Zhou L, Kim S (2012) Carbon supported cobalt oxide nanoparticles-iron phthalocyanine as alternative cathode catalyst for oxygen reduction in microbial fuel cells. J Power Sources 208 170-175... 

Rayati S. Sheybanifard Z. Ultrasound promoted green oxidation of alkenes with hydrogen peroxide in the presence of iron porphyrins supported on multi-walled carbon nanotubes. J Porphyrins Phthalocyanines 2015 19 622-30. 

Jiang Y, Eu Y, Ev X, Han D, Zhang Q, Niu L, Chen W (2013) Enhanced catalytic performance of Pt-free iron phthalocyanine by graphene support for efficient oxygen reduction reaction. ACS Catal 3 1263-1271... 

Supporting electrolyte 0.1 M H2SO4. Potential scan rate 100 mV.s [9]. (Reprinted from Electrochimica Acta (forthcoming). Baker R, Wilkinson DP, Zhang J. Eleetrocatalytie activity and stability of substituted iron phthalocyanines towards oxygen reduetion evaluated at different temperatures. 32008, with permission from Elsevier.)... 

Monteleone, F., Cavani, F., Felloni, C., et al (2004). A Redox Process for the Production of Menadione and Use of Polyoxometalates as Oxidizing Agents, International Patent Application WO 2004014832 Strukul, G., Somma, F., BaUarini, N., et al. (2009). The Oxidation of 2-methyl-1-naphthol to Menadione with H2O2, Catalyzed by Nb-based Heterogeneous Systems, Ap/iZ. Catal. A Gen., 356, pp. 162-166 Zalomaeva, O., Ivanchikova, I., Kholdeeva, O., et al (2009). Kinetics and Mechanism of the Oxidation of Alkyl Substituted Phenols and Naph-thols with TBuOOH in the Presence of Supported Iron Phthalocyanine, New J. Chem., 33, pp. 1031-1037. 

Within this field, many basic investigations and proposals for practical application have been made by Shirai et al. l They have investigated tetra- and octa-carboxylic acid derivatives of iron phthalocyanine and cobalt phthalocyanine, and found that catalytic activity is affected by the states of electron spins of metal ions and inactivated by formation of the mu-oxo dimer. Iron and cobalt ion in high spin states are more reactive than that in low spin states. High spin states of metal ions are achieved by modification of ligands. Shirai et al. have applied these materials as fiber deodorizers for such odors as ammonia, trimethylamine, hydrogen sulfide, and methanethiol, in which the phthalocyanine compounds are supported on fibers of cotton, wool, rayon, and artificial fibers. 

Orient Chemicals market iron phthalocyanine derivatives and cobalt phthalocyanine derivatives as deodorizers under the trade name of DEORASE. These materials were developed in collaboration with Shirai et al. Figure 17-8 shows the deodorizing effects of the products supported on textiles on ammonia and hydrogen sulfide. 

The complexes frans-[Ru(NH3)4 P(OR)3 2] and trans-[Ru(NH3)4 P(OEt)3 P(OR)3 ], with R = methyl, isopropyl, or butyl, aquate to give a monophosphite product with rate constants which vary little with the nature of the complex or solvent composition (up to 80% ethanol). The results support the dissociative mechanism previously proposed for the triethyl phosphite complex. Trans effects are here dominated by 7T acceptor properties of these phosphite ligands. Trans effects in substitution in bis-ligand ruthenium (and iron) phthalocyanine complexes follow the order... 

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