Disproportionation

About: Disproportionation is a research topic. Over the lifetime, 6423 publications have been published within this topic receiving 125210 citations. The topic is also known as: dismutation & redox disproportionation.

Reduction behavior of iron oxides in hydrogen and carbon monoxide atmospheres

Abstract: The reduction of various iron oxides in hydrogen and carbon monoxide atmospheres has been investigated by temperature programmed reduction (TPR H2 and TPR CO ), thermo-gravimetric and differential temperature analysis (TG-DTA-MS), and conventional and “ in situ ” XRD methods Five different compounds of iron oxides were characterized: hematite α-Fe 2 O 3 , goethite α-FeOOH, ferrihydrite Fe 5 HO 8 ·4H 2 O, magnetite Fe 3 O 4 and wustite FeO In the case of iron oxide-hydroxides, goethite and ferrihydrite, the reduction process takes place after accompanying dehydration below 300 °C Instead of the commonly accepted two-stage reduction of hematite, 3 α-Fe 2 O 3 → 2 Fe 3 O 4 → 6 Fe, three-stage mechanism 3Fe 2 O 3 → 2Fe 3 O 4 → 6FeO → 6Fe is postulated especially when temperature of reduction overlaps 570 °C Up to this temperature the postulated mechanism may also involve disproportionation reaction, 3Fe 2+ ⇌ 2Fe 3+ + Fe, occurring at both the atomic scale on two-dimensional interface border Fe 3 O 4 /Fe or stoichiometrically equivalent and thermally induced, above 250 °C, phase transformation—wustite disproportionation to magnetite and metallic iron, 4FeO ⇌ Fe 3 O 4 + Fe Above 570 °C, the appearance of wustite phase, as an intermediate of hematite reduction in hydrogen, was experimentally confirmed by “ in situ ” XRD method In the case of FeO–H 2 system, instead of one-step simple reduction FeO → Fe, a much more complex two-step pathway FeO → Fe 3 O 4 → Fe up to 570 °C or even the entire sequence of three-step process FeO → Fe 3 O 4 → FeO → Fe up to 880 °C should be reconsidered as a result of the accompanying FeO disproportionation wustite ⇌ magnetite + iron manifesting its role above 150 °C and occurring independently on the kind of atmosphere—inert argon or reductive hydrogen or carbon monoxide The disproportionation reaction of FeO does not consume hydrogen and occurs above 200 °C much easier than FeO reduction in hydrogen above 350 °C The main reason seems to result from different mechanistic pathways of disproportionation and reduction reactions The disproportionation reaction wustite ⇌ magnetite + iron makes simple wustite reduction FeO → Fe a much more complicated process In the case of thermodynamically forced FeO disproportionation, the oxygen sub-lattice, a closely packed cubic network, does not change during wustite → magnetite transformation, but the formation of metallic iron phase requires temperature activated diffusion of iron atoms into the region of inter-phase FeO/Fe 3 O 4 Depending on TPR H2 conditions (heating rate, velocity and hydrogen concentration), the complete reduction of hematite into metallic iron phase can be accomplished at a relatively low temperature, below 380 °C Although the reduction behavior is analogical for all examined iron oxides, it is strongly influenced by their size, crystallinity and the conditions of reduction

FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces

Abstract: The adsorption of formaldehyde on different oxides (silica, pure and fluorided alumina, magnesia, titania, thoria, zirconia, and iron oxide) has been studied by FT-IR spectroscopy in the temperature range 170-570 K. The following adsorbed species have been identified and characterized spectroscopically: (i) physisorbed HCHO, (ii) coordinated HCHO, (iii) dioxymethylene, (iv) polyoxymethylene, (v) formate ions, and (vi) methoxy groups. On silica at 170 K formaldehyde physisorbs on surface OH groups and, by warming, polymerizes producing linear polyoxymethylene. On ionic oxides at about 250 K dioxymethylene is always observed, generally together with variable amounts of the linear polymer that has been isolated on magnesia at 170 K. Heating up to or above room temperature results in the disproportionation of dioxymethylene into formate and methoxide groups, probably via a Cannizzaro-type mechanism. Such a route probably parallels an oxidative route, involving direct oxidation of dioxymethylene into formates, as observed on iron oxide.

Large Sulfur Isotope Fractionation Does Not Require Disproportionation

Abstract: The composition of sulfur isotopes in sedimentary sulfides and sulfates traces the sulfur cycle throughout Earth’s history. In particular, depletions of sulfur-34 (34S) in sulfide relative to sulfate exceeding 47 per mil (‰) often serve as a proxy for the disproportionation of intermediate sulfur species in addition to sulfate reduction. Here, we demonstrate that a pure, actively growing culture of a marine sulfate-reducing bacterium can deplete 34S by up to 66‰ during sulfate reduction alone and in the absence of an extracellular oxidative sulfur cycle. Therefore, similar magnitudes of sulfur isotope fractionation in sedimentary rocks do not unambiguously record the presence of other sulfur-based metabolisms or the stepwise oxygenation of Earth’s surface environment during the Proterozoic.

Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts.

Abstract: Manganese oxides function as efficient electrocatalysts for water oxidation to molecular oxygen in strongly alkaline conditions, but are inefficient at neutral pH. To provide new insight into the mechanism underlying the pH-dependent activity of the electrooxidation reaction, we performed UV-vis spectroelectrochemical detection of the intermediate species for water oxidation by a manganese oxide electrode. Layered manganese oxide nanoparticles, δ-MnO(2) (K(0.17)[Mn(4+)(0.90)Mn(3+)(0.07)□(0.03)]O(2)·0.53H(2)O) deposited on fluorine-doped tin oxide electrodes were shown to catalyze water oxidation at pH from 4 to 13. At this pH range, a sharp rise in absorption at 510 nm was observed with a concomitant increase of anodic current for O(2) evolution. Using pyrophosphate as a probe molecule, the 510 nm absorption was attributable to Mn(3+) on the surface of δ-MnO(2). The onset potential of the water oxidation current was constant at approximately 1.5 V vs SHE from pH 4 to pH 8, but sharply shifted to negative at pH > 8. Strikingly, this behavior was well reproduced by the pH dependence of the onset of 510 nm absorption, indicating that Mn(3+) acts as the precursor of water oxidation. Mn(3+) is unstable at pH < 9 due to the disproportionation reaction resulting in the formation of Mn(2+) and Mn(4+), whereas it is effectively stabilized by the comproportionation of Mn(2+) and Mn(4+) in alkaline conditions. Thus, the low activity of manganese oxides for water oxidation under neutral conditions is most likely due to the inherent instability of Mn(3+), whose accumulation at the surface of catalysts requires the electrochemical oxidation of Mn(2+) at a potential of approximately 1.4 V. This new model suggests that the control of the disproportionation and comproportionation efficiencies of Mn(3+) is essential for the development of Mn catalysts that afford water oxidation with a small overpotential at neutral pH.