Iron catalysis Laboratory

Since 1905, when Coblentz obtained the first IR spectrum, vibrational spectroscopy has become an important analytical research tool. This technique was then applied to the analysis of adsorbates on well-defined surfaces, subsequently moving towards heterogeneous reaction studies. Terenin and Kasparov (1940) made the first attempt to employ IR in adsorption studies using ammonia adsorbed on a silica aerogel containing dispersed iron. This led to a prediction by Eischens et al. from Beacon Laboratories in 1956 that the IR technique would prove to be extremely important in the study of adsorption and catalysis. For an excellent review article in IR spectroscopy, see Ryczkowski and references therein and for a more recent review with applications, see Topsoe. ... 

The association of sulfur and iron into simple to more complex molecular assemblies allows a great flexibility of electron transfer relays and catalysis in metalloproteins. Indeed, the array of different structures, the interactions with amino-acid residues and solvent and their effect on redox potential and spectroscopic signatures is both inspiring for chemists and electrochemists, and of paramount importance for the study of these centers in native conditions. Most of the simpler natural clusters have been synthesized and studied in the laboratory. Particularly, the multiple redox and spin states can be studied on pure synthetic samples with electrochemical and spectroscopic techniques such as EPR or Fe Mossbauer spectroscopy. More complex assembhes still resist structural... 

The first experiments which were carried out in the author s laboratory on organometallic phase-transfer catalysis were concerned with the reduction of nitrobenzenes (4) to anilines (5) by triiron dodecacarbonyl. Such a conversion was reported to occur in benzene containing methanol at reflux for 10-17 h, with the hydridoundecacarbonyltriferrate anion as the likely key intermediate (16). It was our expectation that the trinuclear iron hydride should be generated by phase-transfer catalysis and if so, effect reduction of nitro compounds (4) under exceedingly mild conditions. Indeed this was the case, as illustrated by the results shown in Table I (17). Not only is the reaction complete in 2 h or less using sodium hydroxide as the aqueous phase, benzene as the organic phase, and benzyltrieth-ylammonium chloride as the phase-transfer catalyst, but it occurs at room temperature and requires less metal carbonyl than when the reaction was... 

In the catalysis community, it is generally accepted that there are two types of support materials for heterogeneous oxidation catalysts [84]. One variety is the reducible supports such as iron, titanium, and nickel oxide. These materials have the capacity to adsorb and store large quantities of molecules. The adsorbed molecules diffuse across the surface of the support to the catalyst particle where they are activated to a superoxide or atomically bound state. The catalytic reaction then takes place between the reactant molecules and the activated on the catalyst particle. Irreducible supports, in contrast, have a very low ability to adsorb O. Therefore, can only become available for reaction through direct adsorption onto the catalyst particle. For this reason, catalysts deposited on irreducible supports generally exhibit turnover frequencies that are much lower than those deposited on reducible supports [84]. More recent efforts in our laboratory are focused on characterizing catalyst support materials that are commonly used in industry. These studies are aimed at deciphering how specific catalyst and support material combinations result in superior catalytic activity and selectivity. 

The role of sulfur- and iron-oxidizing bacteria. As already noted, the rates of FeS2 and Fe(II) oxidation in environmental systems often differ substantially from the abiotic rates. Usually natural rates are much faster than laboratory abiotic rates. The reasons include inorganic catalysis and especially enzymatic oxidation by microorganisms. Oxidation of Fe(ll), for example, is catalyzed by some clays and metals, including Al, Fe, Co +, Cu, and Mn, and also HPO (Stumm and Morgan 1981). 

The metal oxides used as supports were AI2O3 (a reference sample from the Catalysis Society of Japan, JRC-ALO-7, specific surface area 180 m /g), TiOz (Degussa., P-25, 60 m /g), and a-FezOz, prepared by calcinations in air at 627 K of the precipitates obtained from an aqueous solution of iron(III) nitrate by neutralizing with sodium carbonate. As an Ir precursor, reagent grade IrC (Kishida Chemicals) and Ir(CH3COCHCOCH3)3 (Tri Chemical Laboratory) were used. (Ir(CH3COCHCOCH3)3 will hereafter be abbreviated Ir(acac)3.)... 

Inspired by the observation of efficient hydrogenation catalysis with iron compounds bearing redox-active tridentate ligands, our laboratory also explored related chemistry with reduced iron compounds with bidentate chelates [92]. Aryl-substituted a-diimines were attractive supporting ligands due to their ease of synthesis, estabUshed one- and two-electron redox-activity [92-95] and precedent in iron-catalyzed C-C bond forming reactions [96-98]. 

The synthesis of ammonia from its elements, N2 + 3H2 2NH3, is one of the largest industrial processes based on heterogeneous catalysis [1-4]. Almost 90% of the present world capacity of about 200 million tons per year is used for the production of fertilizers. Almost all plants employ promoted catalysts based on iron, quite similar to the one developed by A. Mittaschin 1910 attheBadische Anilin and Sodafabrik (BASF) [5]. The above reaction could be successfully realized for the first time in the laboratory in 1909 by Fritz Haber, and was then transferred into a technical... 

In 1920s, the studies on the catalysts for ammonia sjmthesis were performed sporadically in BASF, instead, the company mainly focused on the organic synthesis under high pressm-es and the new fields in heterogeneous catalysis. Dm-ing the development of ammonia synthesis catalysts, researchers provided valuable information about the dm-ability, thermal stability, sensitivity to poisons, and in particular to the concept of promoter. Mittasch smnmarized the roles of various additives as shown in Fig. 1.9. The hypothesis of successful catalyst is multi-component system proposed by Mittasch was confirmed to be very successful. Iron-chromium catalysts for water gas shift reaction, zinc hromium catalystfor methanol synthesis, bismuth iron catalysts for ammonia oxidation and iron/zinc/alkali catalysts for coal hydrogenation were successively developed in BASF laboratories. 

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