Huang Weiqiao, Wei Changgeng, Li Yi, Zhang Yongfan, Lin Wei
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China.
Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen University, Xiamen, Fujian 361005, China.
Phys Chem Chem Phys. 2022 Sep 14;24(35):21461-21469. doi: 10.1039/d2cp02120j.
The Ni-Mo catalyst has attracted significant attention due to its excellent coke-resistance in dry reforming of methane (DRM) reaction, but its detailed mechanism is still vague. Herein, Mo-doped Ni (Ni-Mo) and MoO adsorbed Ni surfaces (MoO@Ni) are employed to explore the DRM reaction mechanism and the effect of coke-resistance. Due to the electron donor effect of Mo, the antibonding states below the Fermi level between Ni and C increase and the adsorption of C decrease, thereby inhibiting the carbonization of Ni. On account of the strong Mo and O interaction, more O atoms gather around Mo, which inhibits the oxidation of Ni and may promote the formation of MoO species on the Ni-Mo catalyst. The presence of Mo-O species promotes the carbon oxidation, forming a unique redox cycle (MoO ↔ MoO) similar to the Mars-van Krevelen (MvK) mechanism, explaining the excellent anti-carbon deposition effect on the Ni-Mo catalyst.
镍钼催化剂因其在甲烷干重整（DRM）反应中出色的抗积碳性能而备受关注，但其详细机理仍不明确。在此，采用钼掺杂的镍（Ni-Mo）和MoO吸附的镍表面（MoO@Ni）来探究DRM反应机理及抗积碳效果。由于钼的电子给体效应，镍与碳之间费米能级以下的反键态增加，碳的吸附减少，从而抑制了镍的碳化。由于钼与氧的强相互作用，更多的氧原子聚集在钼周围，这抑制了镍的氧化，并可能促进镍钼催化剂上MoO物种的形成。Mo-O物种的存在促进了碳的氧化，形成了类似于Mars-van Krevelen（MvK）机理的独特氧化还原循环（MoO ↔ MoO），解释了镍钼催化剂出色的抗积碳效果。
