In this study, we approach several common problems with the Ni-catalyzed methane steam reformation reaction (MSR) using a two-pronged approach combining density functional theory (DFT) calculations with experimental work. Specifically, we look at the deactivation of a Ni catalyst due to coke formation, its high operating temperature requirements, and the high steam to methane (H₂O/CH₄) ratio needed for proper MSR operation. A DFT-based microkinetic model was developed in the presence and absence of electric fields, and the results were compared with experimental results. The microkinetic model shows that, under various electric fields, the most favorable MSR mechanism changed slightly. It also shows that the presence of a positive electric field decreases the surface coverage of carbon, increases the water coverage, accelerates the rate-limiting step of the C–H bond cleavage in methane, and increases the desorption rates of the syngas product (CO + H₂) during MSR. Consequently, for a given methane conversion, a positive electric field allows for significantly lower H₂O/CH₄ ratio and operating temperatures in comparison to systems without an electric field. These findings correspond well with experimental tests under a variety of operating conditions. In addition, improvement in the catalytic activity due to the presence of a positive electric field remained significant even at industrially relevant applied pressures—improving the hydrogen yield greatly. Overall, we find that an applied electric field can play a significant role in improving the catalytic activity of heterogeneous reactions. This information can guide the design of heterogeneous reactions in the presence of an electric field. By utilizing the electric field generated by various renewable energy sources, electric-field-assisted heterogeneous reactions can open up a paradigm in future energy research.

中文翻译：

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电场重整甲烷蒸汽重整过程中降低反应温度，蒸汽需求和焦炭生成的微观动力学模型和实验研究

在这项研究中，我们通过结合密度泛函理论（DFT）计算和实验工作的两管齐下的方法，解决了镍催化的甲烷蒸汽重整反应（MSR）的几个常见问题。具体来说，我们将研究由于焦炭形成，高运行温度要求以及高蒸汽转化为甲烷（H ₂ O / CH ₄）正确进行MSR操作所需的比率。在存在和不存在电场的情况下建立了基于DFT的微动力学模型，并将结果与​​实验结果进行了比较。微观动力学模型表明，在各种电场下，最有利的MSR机理略有变化。它还表明，存在正电场会降低碳的表面覆盖率，增加水覆盖率，加快甲烷中C–H键裂解的限速步骤并提高合成气产物的脱附率（CO + H ₂）在MSR期间。因此，对于给定的甲烷转化率，正电场可使H ₂ O / CH ₄大大降低与没有电场的系统相比，比率和工作温度。这些发现与各种操作条件下的实验测试非常吻合。此外，即使在工业上相关的施加压力下，由于存在正电场，催化活性的改善仍然显着-大大提高了氢气的产率。总的来说，我们发现施加的电场可以在改善非均相反应的催化活性方面发挥重要作用。该信息可指导电场存在下的异质反应设计。通过利用各种可再生能源产生的电场，电场辅助的异质反应可以为未来的能源研究开辟一个范例。