Photocatalytic C–H Bond Activation of Toluene on Rutile TiO2(110)
Source abstract
Abstract
The activation of sp 3 C–H bond over photoactive TiO 2 catalysts has emerged as a promising means to realize the functionalization of hydrocarbons under mild conditions. However, a fundamental understanding of the microscopic mechanism is still unclear. In this work, we have systematically investigated the photochemistry of toluene on rutile (R)-TiO 2 (110) with temperature-programmed desorption (TPD) and density functional theory (DFT). The TPD results demonstrate that UV light (355 nm) efficiently facilitates the methyl C–H bond activation of toluene at 100 K, forming the stable C 6 H 5 CH 2 group intermediate adsorbed on five-coordinated Ti 4+ sites (Ti 5c ) until around room temperature (∼300 K). Further DFT calculations suggest that the photocatalytic C–H bond cleavage follow a homolytic manner via the formation of active benzyl radical (C 6 H 5 CH 2 • ). Our findings provide an insightful understanding of photocatalytic hydrocarbon functionalization on TiO 2 catalysts.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Advanced Photocatalysis Techniques · Catalytic Processes in Materials Science · Covalent Organic Framework Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Shenzhen Key Laboratory of Energy Chemistry and Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, People’s Republic of China
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People’s Republic of China
College of Environmental Sciences and Engineering, Dalian Maritime University, Dalian, Liaoning 116026, People’s Republic of China
Funding
Ministry of Science and Technology of the People's Republic of China · National Natural Science Foundation of China · Chinese Academy of Sciences · Shenzhen Science and Technology Innovation Committee · Guangdong Innovative & Entrepreneurial Research Team Program
References (52)
Show source-provided references
1. 10.1038/nature0736910.1038/nature07369 ↗
2. Rousseaux S. · 2012 · 1
3. 10.1021/acs.chemrev.7b0030710.1021/acs.chemrev.7b00307 ↗
4. 10.1038/nchem.160710.1038/nchem.1607 ↗
5. 10.1021/i260013a02210.1021/i260013a022 ↗
6. 10.1021/ie00097a00810.1021/ie00097a008 ↗
7. 10.1039/D1NJ04239D10.1039/D1NJ04239D ↗
8. 10.1039/C9CY01581G10.1039/C9CY01581G ↗
9. 10.1021/om060848h10.1021/om060848h ↗
10. 10.1021/om700751h10.1021/om700751h ↗
11. 10.1002/jccs.20120063510.1002/jccs.201200635 ↗
12. 10.1039/D1CC06507F10.1039/D1CC06507F ↗
13. 10.1039/D0EE01860K10.1039/D0EE01860K ↗
14. 10.1021/jp077314u10.1021/jp077314u ↗
15. 10.1038/s41929-018-0170-x10.1038/s41929-018-0170-x ↗
16. 10.1021/acscatal.8b0244110.1021/acscatal.8b02441 ↗
17. 10.1023/A:101892090772510.1023/A:1018920907725 ↗
18. 10.1016/S1010-6030(98)00366-910.1016/S1010-6030(98)00366-9 ↗
19. 10.1016/j.apcatb.2013.04.07110.1016/j.apcatb.2013.04.071 ↗
20. 10.1016/j.cattod.2007.01.01610.1016/j.cattod.2007.01.016 ↗
21. 10.1016/j.cattod.2008.05.01710.1016/j.cattod.2008.05.017 ↗
22. 10.1016/S1010-6030(03)00228-410.1016/S1010-6030(03)00228-4 ↗
23. 10.1016/j.cej.2019.12222810.1016/j.cej.2019.122228 ↗
24. 10.1016/j.apcatb.2009.01.01510.1016/j.apcatb.2009.01.015 ↗
25. 10.1016/j.jallcom.2012.11.06110.1016/j.jallcom.2012.11.061 ↗
26. 10.1016/S0926-3373(00)00211-310.1016/S0926-3373(00)00211-3 ↗
27. 10.1016/j.apcatb.2008.08.00310.1016/j.apcatb.2008.08.003 ↗
28. 10.1088/1674-0068/25/05/507-51210.1088/1674-0068/25/05/507-512 ↗
29. 10.1016/0927-0256(96)00008-010.1016/0927-0256(96)00008-0 ↗
30. 10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
31. 10.1103/PhysRevB.50.1795310.1103/PhysRevB.50.17953 ↗
32. 10.1103/PhysRevLett.77.386510.1103/PhysRevLett.77.3865 ↗
33. 10.1002/jcc.2175910.1002/jcc.21759 ↗
34. 10.1063/1.132322410.1063/1.1323224 ↗
35. 10.1103/PhysRevB.80.08520210.1103/PhysRevB.80.085202 ↗
36. 10.1103/PhysRevB.57.150510.1103/PhysRevB.57.1505 ↗
37. 10.1103/PhysRevLett.96.06610710.1103/PhysRevLett.96.066107 ↗
38. 10.1016/j.susc.2007.08.02510.1016/j.susc.2007.08.025 ↗
39. 10.1039/C4CP04159C10.1039/C4CP04159C ↗
40. 10.1103/PhysRevB.13.518810.1103/PhysRevB.13.5188 ↗
41. 10.1021/jp409605y10.1021/jp409605y ↗
42. 10.1021/acscatal.6b0334810.1021/acscatal.6b03348 ↗
43. 10.1021/jp300753f10.1021/jp300753f ↗
44. 10.1021/acs.jpcc.9b0335510.1021/acs.jpcc.9b03355 ↗
45. 10.1016/j.susc.2008.02.03110.1016/j.susc.2008.02.031 ↗
46. 10.1021/acs.jpclett.0c0272910.1021/acs.jpclett.0c02729 ↗
47. 10.1016/j.susc.2008.02.03110.1016/j.susc.2008.02.031 ↗
48. 10.1021/ja304049x10.1021/ja304049x ↗
49. 10.1021/acsami.0c0812010.1021/acsami.0c08120 ↗
50. 10.1021/jacsau.1c0046610.1021/jacsau.1c00466 ↗
51. 10.1021/acs.chemrev.6b0071510.1021/acs.chemrev.6b00715 ↗
52. 10.1126/science.aam914710.1126/science.aam9147 ↗