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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical studies on the catalysis of the reverse water-gas shift reaction using first-row transition metal β-diketiminato complexes
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Theoretical studies on the catalysis of the reverse water-gas shift reaction using first-row transition metal β-diketiminato complexes

机译：第一行过渡金属β-二酮亚胺基配合物催化水煤气逆反应的理论研究

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摘要

The reverse water-gas shift reaction CO_2 + H_2 - H_2O + CO has been investigated using a set of homogeneous catalyst models L′M~I (L′ = β-diketiminate, C _3N_2H_5~-; M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamics of prototypical reaction pathways were simulated at two levels of theory: B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ. The modeled catalytic reaction has been considered in the following steps: coordination of CO_2 by the catalyst to generate a carbon dioxide complex, L′M(CO_2); scission of L′M(CO_2) to yield L′M(CO) and L′M(O); L′M(O) hydrogenation to form L′M(H_2O). The final products, H_2O and CO, were obtained from the dissociation of L′M(H_2O) and L′M(CO). All of the reactants, intermediates, and products were modeled, where different possible conformers and multiplicities were identified and considered as potential minima. The reaction enthalpy ΔH, of all steps for each catalyst as a function of transition metal have been determined. The Mn and Fe catalysts show more thermodynamically accessible pathways than the other catalyst models studied. The overall reaction enthalpy has been determined not only by B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ but also via a more rigorous ab initio electron-correlation-based approach, the correlation consistent Composite Approach (ccCA).
机译：已使用一组均相催化剂模型L'M〜I（L'=β-二酮戊二酸酯，C _3N_2H_5〜-; M = Sc，Ti，V，L）进行了反向水煤气变换反应CO_2 + H_2-H_2O + CO Cr，Mn，Fe，Co，Ni，Cu，Zn）。在两个理论水平上模拟了原型反应路径的热力学：B3LYP / 6-311 + G（d）和B3LYP / aug-cc-pVTZ。在以下步骤中已经考虑了模型化的催化反应：催化剂对CO_2的配位以生成二氧化碳配合物L'M（CO_2）;切断L′M（CO_2）以产生L′M（CO）和L′M（O）; L'M（O）加氢形成L'M（H_2O）。最终产物H_2O和CO从L'M（H_2O）和L'M（CO）的解离中获得。对所有反应物，中间体和产物进行建模，在其中识别出不同的可能构象异构体和多重性，并将其视为潜在的最小值。已经确定了每种催化剂作为过渡金属的函数的所有步骤的反应焓ΔH。锰和铁催化剂显示出比其他研究的催化剂模型更多的热力学途径。整个反应焓不仅由B3LYP / 6-311 + G（d）和B3LYP / aug-cc-pVTZ决定，而且还通过更严格的从头算基于电子相关的方法，相关一致的复合方法（ccCA）确定。 ）。

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