Reactions of Fe with H₂O and FeO with H₂. A Combined Matrix Isolation FTIR and Theoretical Study

Abstract

The study of the reactions of transition metal atoms with water is continued in this work. Here we report the study of the reactions of Fe with H2O and FeO with H2. In agreement with previous thermal atom experiments, laser-ablated Fe atoms reacted with H2O to form the FeOH2 and HFeOH molecules as characterized by matrix isolation FTIR spectroscopy. On photolysis, the Fe atoms could further insert into the OH bonds in H2O molecules with a stepwise pattern to form multi metal−oxo core species including HFeOFeH, HFeOFeOH, and possibly HFeOFeOFeH, which were identified by isotopic substitutions and density functional calculations. Reactions of FeO with H2 also lead to HFeOH as the primary product. In addition, a potential energy surface for the Fe + H2O ⇔ FeO + H2 reaction was constructed to elucidate the reaction mechanisms.

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

“…Chromium dioxide also reacts with H 2 ; as in case of D 2 and VO 2 , the hydride HCrO(OH) is formed by irradiation only . The same holds for the reaction of manganese oxide MnO with H 2 to form HMnOH, whereas FeO reacts spontaneously to form HFeOH …”

“…The investigation of the reaction of matrix-isolated transition metal clusters is essentially restricted to the metal oxides, MO, and metal dioxides, MO 2 .R eactions with small inorganic molecules like H 2 O, [116][117][118] N 2 , [119][120][121] CO, [122] CO 2 , [123][124][125] and H 2 [126][127][128][129][130] as well as organic molecules like CH 4 , [131][132][133] CH 3 Cl, [134][135][136][137] CH 3 OH, [138] C 2 H 2 , [139][140][141][142] and C 2 H 4 [143] have been investigated. Reactions of monoxides MO with CH 4 have been reviewed by Wang and Zhou.…”

“…[128] The same holds for the reactiono fm anganese oxide MnO with H 2 to form HMnOH, [129] whereas FeO reacts spontaneously to form HFeOH. [130] CH 4 ,C H 3 Cl, CH 3 OH:T he reactions of CH 4 with TiO, [131] NbO, [132] Ta O, [132] NbO 2 , [132] Ta O 2 , [132] MnO, [133] and FeO [133] have been investigated. Without activation by irradiation, only the adduct formation is observed.…”

Understanding the formation of ultrafine spinel CoFe2O4 nanoplatelets and their magnetic properties

“…35 The absorption band around 600 cm À1 is slightly larger than the typical value of metal oxide ($560 cm À1 ) but smaller than that of metal hydroxide ($660 cm À1 ). 36 Thus, it might be considered to be arisen from vibrations of mixture of O-Co-O, O-Fe-O and Co-OH, Fe-OH. This means, after hydrothermal treatment at room temperature, some cobalt and iron oxides were formed.…”

How a Quantum Chemical Topology Analysis Enables Prediction of Electron Density Transfers in Chemical Reactions. The Degenerated Cope Rearrangement of Semibullvalene

“…20 While chemical reactions of the bare transition metal oxide cations with H 2 have received a significant interest, [24][25][26][27][28][29][30][31][32][33][34][35][36][37] neutral metal oxides have gained much less attention. [38][39][40][41][42][43][44][45][46][47][48][49][50] Recently Zhou et al 51 have reported a combined experimental and theoretical study on the hydrogenation reactions by group V metal dioxides using matrix isolation spectroscopy. These results show a thermodynamically favorable reaction for the dihydrogen cleavage process with small barrier for VO 2 In this work, we present a theoretical study on the reaction mechanism for the dihydrogen activation by neutral group IV metal dioxides (MO 2 , M = Ti, Zr, and Hf) according to the following reaction:…”