TOPO-capped TiO2 have been successfully synthesized via a non-hydrolytic sol-gel process. In this study, TOPO-capped TiO2 catalysts have clearly demonstrated to have excellent photoactivies toward EDCs decompositions. A higher partition efficiency of EDCs on TiO2 surface was due to the TOPO modification. Estrone with the highest log Kow
value exhibited the largest partition amounts on the TOPO-capped TiO2 compared with phenol and BPA. Moreover, there are three steps affect the decomposed reaction: one is partition, another is that adsorbed EDCs diffuse to the TiO2 surface, the other is surface reaction. The partition activity contributes to the acceleration of the EDCs decomposition.
For this reason, surface modification resulted in increasing the surface coverage of pollutants, thus enhanced the photocatalytic rate. According to the EPR results, the Ti4+-O--Ti4+-OH -adducts for TOPO-capped TiO2 is stronger than that of P25. These results reveal TOPO can facilitate the transfer of photogenerated charges from TiO2 to the adsorbed EDCs. The charges at the TiO2 surface can chemiadsorb EDCs significantly upon UV-illumination.
Therefore, the EDCs photodecomposition of TOPO-capped TiO2 mainly occurs by photoinduced charges rather by ·OH radicals which is normally occurred in the P25-based system. After photocatalysis of phenol, BPA and estrone, the phosphorus atoms still chelate on TiO2 surface. In addition, lots of carbon atoms are still remained on the TiO2 surface, revealing the reusable properties of the TOPO-capped TiO2 for next photocatalytic runs.
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Appendix A. Experimental parameters
Appendix A- 1 Operational parameters of XRPD.
Appendix A- 2 Operational parameters of XPS.
Mode
Binding energy
Pass energy Anode Step size Time/steps
Survey 1200-0 eV 23.5 eV Al 1.0 eV 50 ms
Multiplex Depending
on element 23.5 eV Al 0.1 eV 50 ms
Appendix A- 3 Detail operational parameters of XPS in multiplex.
Element
Appendix A- 4 Operational parameters of UV-Visible.
Measurement
Data mode
Starting wavelength
Ending wavelength
Sampling interval
Slit width
Reference
Wavelength
scan %R 800 nm 200 nm 1 nm 1 nm Al2O3
Appendix A- 5 Operational parameters of TGA.
Starting temperature
Maximum temperature
Atmosphere
Heating rate (°C /min)
Air flow rate (ml/min)
20 °C 900 °C Air 10 20
Appendix B. Photocatalysis
200 250 300 350 400 450 500 0.0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Abs
Wavelength (nm)
Phenol
200 250 300 350 400 450 500
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Abs
Wavelength (nm)
BPA
200 250 300 350 400 450 500 0.0
0.1 0.2 0.3 0.4
Abs
Wavelength (nm)
Estrone
Appendix B- 1 UV adsorption spectra of phenol, BPA and estrone.
0 20 40 60 80 100 0.0
0.2 0.4 0.6 0.8 1.0
Degradation time (min) C/C 0
estrone without photocatalyst
Appendix B- 2 Time courses of photodecomposition of estrone without photocatalyst.