Carbon monoxide, as a major pollutant of the environment, could be reduced to hydrocarbons by using transition metal catalysts. Different catalysts produce different hydrocarbons, ranging from methane to heavier hydrocarbons. Some catalysts prefer methanation, while some others do Fischer-Tropsch process. Both kinds of catalysts suffer from coke formation on their surfaces. Coke is produced from direct dissociation of CO on the surface of a catalyst. In this paper, direct and indirect dissociation paths of CO on the Ni-doped graphene are studied by periodic and non-periodic DFT calculations. It is shown that direct CO dissociation has very high barrier energy of 5.32 eV which prevents coke formation on the catalyst. Indirect path investigation shows that HCO intermediate is more feasible than COH one. With the addition of one H to CO, barrier energy is reduced from 5.3 eV to 3.09 eV, and introducing one more H to form CH₂O intermediate, the barrier energy is reduced to 1.5 eV. In addition, NBO and QTAIM theories are used to study the donor-acceptor charge transfers and nature of interactions. Data shows that there is a large charge donation and back-donation for CO adsorption on the surface of Ni-doped graphene. Electron density difference graphs and NBO/QTAIM charges show that, in all studied complexes, charge transfer is occurred from Ni to the adsorbed species.

一氧化碳是环境的主要污染物，可以通过使用过渡金属催化剂将其还原为碳氢化合物。不同的催化剂产生不同的烃，从甲烷到重烃。一些催化剂喜欢甲烷化，而另一些则采用费-托法。两种催化剂都在其表面上形成焦炭。焦炭是由催化剂表面上的CO直接分解产生的。本文通过周期性和非周期性的DFT计算研究了CO在Ni掺杂石墨烯上的直接和间接解离路径。已经表明，直接的CO离解具有5.32eV的非常高的势垒能，这阻止了催化剂上焦炭的形成。间接路径研究表明，HCO中间体比COH中间体更可行。在CO中加1 H后，_在2 O中间，势垒能量降低到1.5 eV。此外，NBO和QTAIM理论还用于研究供体-受体电荷转移和相互作用的性质。数据表明，在掺Ni的石墨烯表面上有大量的电荷供体和背电荷供CO吸附。电子密度差图和NBO / QTAIM电荷表明，在所有研究的络合物中，都发生了从Ni到吸附物质的电荷转移。