tert-Butanol Chemistry on Rutile TiO2(110): The Effect of Surface Oxidation

Liu, Peng1,2; Xue, Guigu1,2; Lai, Yuemiao1,2; Li, Yinuo1,2; Chen, Xiao1,2; Guo, Qing1,2

2022-02-24

10.1021/acs.jpcc.2c00844

Journal of Physical Chemistry C   影响因子和分区

1932-7447

1932-7455

We have studied the surface chemistry of tert-butanol ((CH3)(3)COH) on reduced and oxidized rutile (R-) TiO2(110) surfaces using the temperature-programmed desorption (TPD) method. On the reduced R-TiO2(110) surface, (CH3)(3)COH molecules mainly decompose into isobutene (iso-C4H8) and water (H2O) at the oxygen vacancy (O-v) sites at about 440 K, with a small amount of iso-C4H8 formed on the five-coordinated Ti4+ sites (Ti-5c). On the oxidized R-TiO2(110) surfaces, O-v's can be occupied by O-2, thus inhibiting the iso-C4H8 formation channel at the O-v sites. However, a new reaction pathway for iso-C4H8 production occurs on the Ti-5c sites and gradually becomes dominant with increasing O-2 exposure. At 0.5 L O-2 exposure, the yield of iso-C4H8 production is nearly 5 times bigger than that on the reduced surface, illustrating that surface oxidation can enhance iso-C4H8 formation on R-TiO2(110) significantly. In addition, a small amount of (CH3)(3)COH can be detected at about 500 K, which is attributed to recombinative desorption of tert-butyl ((CH3)(3)CO) and OH groups. More interestingly, a low-temperature pathway possibly producing an alkene product on the oxidized surface was observed. Our results demonstrate that surface oxidation can not only enhance iso-C4H8 production via the dehydration of (CH3)(3)COH but also alter reaction channels, which provides a deeper insight into oxide-based catalysis.

SCI ; EI

英语

第一 ; 通讯

National Key R&D Program of China[2018YFE0203002] ; National Natural Science Foundation of China[22173041,22103031] ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDB17000000] ; Shenzhen Science and Technology Innovation Committee["J C Y J 2 0 1 9 0 8 0 9 1 4 0 2 1 6 6 0","ZDSYS20200421111001787"] ; Guangdong Innovative & Entrepreneurial Research Team Program["2019ZT08L455","2019JC01X091"] ; International Partnership Program of the Chinese Academy of Sciences[121421KYSB20170012]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:000766230000016

AMER CHEMICAL SOC

20220911704865

Oxide minerals ; Surface chemistry ; Temperature programmed desorption ; Titanium dioxide

Minerals:482.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Inorganic Compounds:804.2

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Key Lab Energy Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China

Liu, Peng,Xue, Guigu,Lai, Yuemiao,et al. tert-Butanol Chemistry on Rutile TiO2(110): The Effect of Surface Oxidation[J]. Journal of Physical Chemistry C,2022,126(7):3457-3465.

Liu, Peng,Xue, Guigu,Lai, Yuemiao,Li, Yinuo,Chen, Xiao,&Guo, Qing.(2022).tert-Butanol Chemistry on Rutile TiO2(110): The Effect of Surface Oxidation.Journal of Physical Chemistry C,126(7),3457-3465.

Liu, Peng,et al."tert-Butanol Chemistry on Rutile TiO2(110): The Effect of Surface Oxidation".Journal of Physical Chemistry C 126.7(2022):3457-3465.