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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >FTIR and Reaction Kinetics Studies of the Hydrodehalogenation of CF_2Br_2, CH_2Br_2, and CD_2Br_2 over a Pd/γ-Al_2O_3 Catalyst
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FTIR and Reaction Kinetics Studies of the Hydrodehalogenation of CF_2Br_2, CH_2Br_2, and CD_2Br_2 over a Pd/γ-Al_2O_3 Catalyst

机译：Pd /γ-Al_2O_3催化剂上CF​​_2Br_2，CH_2Br_2和CD_2Br_2加氢脱卤的FTIR和反应动力学

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摘要

A combination of FTIR and chemical reaction kinetics studies was employed to investigate the hydrodehalogenation of CF_2Br_2, CH_2Br_2, and CD_2Br_2 catalyzed by Pd/-Al_2O_3. The products of the CF_2Br_2+H_2 reaction (CF_2H_2, CF_3H, C_1-C_3 hydrocarbons) are typical for a reaction mechanism with the participation of :CF_2 and :CH_2 carbenes as the reaction intermediates. It was not possible to detect :CF2 carbenes by FTIR during the adsorption studies. It is proposed that the carbenes are unstable on the Pd surface in the absence of H_2 and readily decompose to form carbonaceous deposits and adsorbed halogen atoms. Thus, room-temperature hydrogenation of the surface species formed during adsorption of CF_2Br_2 on Pd/γ-Al_2O_3 at room temperature yields only CH_4, HBr, and HF. The :CD_2 and :CH_2 carbenes formed from dissociation of CD_2Br_2 and CH_2Br_2 adsorbed on the Pd surface are stable at room temperature, as indicated by the formation of CD2H2 upon hydrogenation of adsorbed species by H_2 and D_2, respectively.
机译：结合红外光谱和化学反应动力学研究了Pd / -Al_2O_3对CF_2Br_2，CH_2Br_2和CD_2Br_2的加氢脱卤作用。 CF_2Br_2 + H_2反应的产物（CF_2H_2，CF_3H，C_1-C_3碳氢化合物）是典型的反应机理，其中以：CF_2和：CH_2碳烯为反应中间体。在吸附研究中不可能通过FTIR检测到：CF2卡宾。有人提出，在没有H_2的情况下，碳烯在Pd表面不稳定，容易分解形成碳质沉积物和吸附的卤素原子。因此，在室温下CF_2Br_2在Pd /γ-Al_2O_3上吸附过程中形成的表面物质的室温氢化仅产生CH_4，HBr和HF。由吸附在Pd表面上的CD_2Br_2和CH_2Br_2分解形成的：CD_2和：CH_2碳烯在室温下是稳定的，这是由吸附的物质分别被H_2和D_2氢化形成CD2H2所表明的。

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