Liu Lingtao, Zhang Chenxin, Wang Wenshou, Li Genghong, Zhu Bingtian
SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, China.
Molecules. 2023 Sep 21;28(18):6739. doi: 10.3390/molecules28186739.
Sulfides poisoning of metallic Ni is an important issue in catalyst deactivation. SO, similar to HS and other sulfides, is an impurity presented in reactants or during the regeneration steps. Herein, spin-polarized density functional theory calculations were used to study the adsorption and decomposition of SO on a pristine and metal-doped Ni(111) surface. The adsorption energy, transition state energy, and partial density of state (PDOS) were calculated. On the pristine Ni(111) surface, ten different configurations were considered, and three typical ones were selected for transition state searching. It was found that the reaction barrier of the first S-O bond dissociation was much higher than that of the second one. Doping the top layer with a second metal could strongly change the adsorption and decomposition behavior. Doping with 3/9ML Co slightly increases the adsorption energy of SO for most configurations and decreases the reaction barriers of the SO--2 decomposition, while the others decrease the adsorption ability and increase the barriers. The order of adsorption energy for the most stable configurations is Co > Ni > Cu > Rh > Pd. The order of the first S-O bond dissociation reaction barriers is Pd > Rh > Cu = Ni > Co, and the order of the second bond dissociation barrier is Rh > Pd > Cu > Ni > Co.
金属镍的硫化物中毒是催化剂失活中的一个重要问题。与硫化氢和其他硫化物类似，二氧化硫是反应物中或再生步骤中存在的杂质。在此，利用自旋极化密度泛函理论计算研究了二氧化硫在原始和金属掺杂的Ni(111)表面上的吸附和分解。计算了吸附能、过渡态能量和态密度（PDOS）。在原始的Ni(111)表面上，考虑了十种不同的构型，并选择了三种典型构型进行过渡态搜索。结果发现，第一个S-O键解离的反应势垒远高于第二个。用第二种金属掺杂顶层会强烈改变吸附和分解行为。用3/9ML的钴掺杂，对于大多数构型，会略微增加二氧化硫的吸附能，并降低二氧化硫分解的反应势垒，而其他金属则会降低吸附能力并增加势垒。最稳定构型的吸附能顺序为Co＞Ni＞Cu＞Rh＞Pd。第一个S-O键解离反应势垒的顺序为Pd＞Rh＞Cu = Ni＞Co，第二个键解离势垒的顺序为Rh＞Pd＞Cu＞Ni＞Co。
