van der Waals (vdW) corrected periodic density functional theory (DFT) calculations and microkinetic modeling were employed to elucidate the mechanism and energetics of dehydrogenation of tetrahydropyrrole, a model organic hydrogen carrier, on Pt(111). The overall dehydrogenation is endothermic while individual dehydrogenation steps can be endothermic or exothermic. The calculations indicate that the first dehydrogenation step proceeds via the C–H scission of an α-carbon (with respect to nitrogen). Subsequently, the remaining α- and two β-C–H bonds can be dissociated via multiple energetically similar pathways, wherein the second dehydrogenation step is rate controlling. The inclusion of vdW forces shifts the potential energy surface (PES) downward by an average 0.6 eV indicating that while the activation barriers remain unaffected, there can be significant influence on the overall rate due to increased coverage of intermediates. N-methylation of tetrahydropyrrole weakens adsorption of initial intermediates, indicating that the PES may generally be shifted up thereby affecting the overall kinetics. Finally, there exists a generally linear relationship between the transition state and final state energies of the dehydrogenation reaction.

使用范德华（vdW）校正的周期密度泛函理论（DFT）计算和微动力学模型来阐明模型有机氢载体四氢吡咯在Pt（111）上的脱氢机理和能量。总体脱氢是吸热的，而各个脱氢步骤可以是吸热或放热的。计算表明，第一个脱氢步骤是通过α-碳（相对于氮）的C–H断裂来进行的。随后，剩余的α-和两个β-C-H键可通过多个能量相似的途径解离，其中第二个脱氢步骤是速率控制。包含vdW力会使势能表面（PES）平均向下移动0.6 eV，这表明尽管激活势垒不受影响，四氢吡咯的N-甲基化减弱了初始中间体的吸附，表明PES通常可以上移，从而影响整体动力学。最后，脱氢反应的过渡态能量与最终态能量之间通常存在线性关系。