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Activation of C−H Bond of Propane by Strong Basic Sites Generated by Bulk Proton Conduction on V‐Modified Hydroxyapatites for the Formation of Propene.
ChemCatChem ( IF 3.8 ) Pub Date : 2020-03-31 , DOI: 10.1002/cctc.201902181 Sarah Petit 1, 2 , Cyril Thomas 1 , Yannick Millot 1 , Jean‐Marc Krafft 1 , Christel Laberty‐Robert 2 , Guylène Costentin 1
ChemCatChem ( IF 3.8 ) Pub Date : 2020-03-31 , DOI: 10.1002/cctc.201902181 Sarah Petit 1, 2 , Cyril Thomas 1 , Yannick Millot 1 , Jean‐Marc Krafft 1 , Christel Laberty‐Robert 2 , Guylène Costentin 1
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Insights into the catalytic transformation of propane to propene on V‐apatite catalysts are provided based on structure‐reactivity relationships. Substitution of phosphates by vanadates in the hydroxyapatite structure leads to the formation of Ca10(PO4)6‐x(VO4)x(OH)2‐yOy V‐oxy‐hydroxy‐apatite solid solutions (x=0→6). Bulk vanadium incorporation promotes (i) calcium rich terminations (XPS, CO adsorption), (ii) proton deficiency inside the OH− channels (1H NMR) giving rise to O2− native species, (iii) the thermally‐activated formation of additional O2− species along the OH− channels resulting in H‐bonding interaction (in situ DRIFT) and (iv) the proton conduction process that eventually results in the surface exposure of O2− species (in situ impedance spectroscopy). The exposure of Ca2+−O2− surface acid‐base pairs allows the dissociation of hydrogen, emphasizing the strong basicity of the related O2− species. Whereas an increasing vanadium content is beneficial to propene selectivity, it scarcely impacts propane conversion. The reaction proceeds mainly upon oxidative dehydrogenation, even if the minor dehydrogenation route is also observed. Surface O2− generated thanks to proton mobility are involved in the C−H bond activation, as shown by the synergistic effect between the oxidative dehydrogenation of propane reaction and the bulk proton conduction measured under operando conditions. This puts emphasis on the key role of strong basic sites for propane activation.
中文翻译：
V改性羟基磷灰石上质子传导产生的强碱性位激活丙烷的C H键形成丙烯。
基于结构反应性关系，提供了有关在V-磷灰石催化剂上丙烷催化转化为丙烯的见解。羟基磷灰石结构中钒酸盐取代磷酸盐导致形成Ca 10（PO 4）6-x（VO 4）x（OH）2-y O y V-氧-羟基磷灰石固溶体（x = 0→ 6）。大部分钒的掺入促进（ⅰ）富含钙的终端（XPS，CO吸附），（ii）所述OH内部质子缺乏症-通道（1 HNMR）引起至O 2-本地物种，（ⅲ）的热激活形成额外的O2-物种沿OH -导致氢键相互作用（原位DRIFT）和（iv）所述的质子传导工艺通道，在的O-表面曝光最终结果2-物种（原位阻抗谱）。Ca 2+ -O 2-表面酸碱对的暴露可以使氢解离，从而强调了相关O 2-物种的强碱性。钒含量的增加有利于丙烯的选择性，而对丙烷的转化几乎没有影响。该反应主要在氧化脱氢时进行，即使也观察到较小的脱氢途径。表面O 2−质子迁移所产生的质子参与CH键的活化，如丙烷反应的氧化脱氢与在操作条件下测得的大量质子传导之间的协同作用所表明。这着重强调了强大的丙烷活化基础位点的关键作用。
更新日期：2020-03-31
中文翻译：
V改性羟基磷灰石上质子传导产生的强碱性位激活丙烷的C H键形成丙烯。
基于结构反应性关系，提供了有关在V-磷灰石催化剂上丙烷催化转化为丙烯的见解。羟基磷灰石结构中钒酸盐取代磷酸盐导致形成Ca 10（PO 4）6-x（VO 4）x（OH）2-y O y V-氧-羟基磷灰石固溶体（x = 0→ 6）。大部分钒的掺入促进（ⅰ）富含钙的终端（XPS，CO吸附），（ii）所述OH内部质子缺乏症-通道（1 HNMR）引起至O 2-本地物种，（ⅲ）的热激活形成额外的O2-物种沿OH -导致氢键相互作用（原位DRIFT）和（iv）所述的质子传导工艺通道，在的O-表面曝光最终结果2-物种（原位阻抗谱）。Ca 2+ -O 2-表面酸碱对的暴露可以使氢解离，从而强调了相关O 2-物种的强碱性。钒含量的增加有利于丙烯的选择性，而对丙烷的转化几乎没有影响。该反应主要在氧化脱氢时进行，即使也观察到较小的脱氢途径。表面O 2−质子迁移所产生的质子参与CH键的活化，如丙烷反应的氧化脱氢与在操作条件下测得的大量质子传导之间的协同作用所表明。这着重强调了强大的丙烷活化基础位点的关键作用。
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