a†
a†
a
a*
b a Key Lab for Advanced Materials and Institute of Fine Chemicals, East China
University of Science and Technology, 130 Meilong Road, Shanghai, 200237, P. R.
China. b
Department of Applied Chemistry, Graduate School of Engineering, Osaka
Prefecture University, Naka Ku 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan
†
Haibei Liu & Fan Shen contributed equally to this work
To whom correspondence should be addressed.
Jinlong Zhang
E-mail address: jlzhang@ecust.edu.cn
Tel.: +86 21 64252062;
Fax: +86 21 64252062.
Author Email Address:
Jinlong Zhang, jlzhang@ecust.edu.cn
Mingyang Xing, mingyangxing@ecust.edu.cn

Haibei Liu, apfel.law@foxmail.com
Fan Shen, shfaxz126@163.com
Masakazu Anpo, anpo@chem.osakafu-u.ac.jp
1. Experiment
1.1 The vacuum activated treatment: Fig S1 shows the details of the vacuum activation device. In a typical treatment, 0.5g of prepared catalyst precursor was put in the sample tank which was then set into the quartz tube for tube muffle. And then the oil pump was opened to create a vacuum environment low to -0.1Mpa. Afterwards, the precursor was calcined at 300 o C with a stepwidth of 2 o C/min.
After calcination, the prepared catalyst was grinded, marked and sealed for further test.
2. Characterization
XRD analysis of the prepared photo-catalysts was carried out with a Rigaku D/max
2550 VB/PC apparatus using Cu Kα radiation (λ=0.5406 Å) and a graphite monchromator, operated at 40 kV and 100 mA. UV-Vis absorption spectra were obtained using a scan UV-Vis spectrophotometer (Shimadzu UV-2450) equipped with an integrating sphere assembly, while BaSO
4
was used as a reference. Raman measurements were performed using an inVia
+
Reflex Raman spectrometer with the excitation light of 514 nm. X-ray photoelectron spectroscopy (XPS) was recorded with a Perkin-Elmer PHI 5000C ESCA System with Al Kα radiation operated at 250
W. The shift of binding energy due to relative surface charging was corrected using the C 1s level at 284.6 eV as an internal standard. Electron paramagnetic resonance
(EPR) measurements for the catalyst powders were recorded at room temperature on a

Bruker EMX-8/2.7 by accumulating three scans with the microwave frequency of
9.85 GHz and power of 6.35 mW. The photoluminescence (PL) emission spectra for electron-hole separation and recombination rate were measured with a Shimadzu
RF-5301PC at room temperature. The photo-catalytic activity of each photo-catalyst was measured in terms of degradation of Acid Orange 7 (AO7) under visible light illumination. AO7 is an azo-dye, which is frequently-used in textile industry and difficult to decolorize. A 1000 W tungsten halogen lamp equipped with a UV cutoff filters (λ>420 nm) was used as a visible light source (the average light intensity was
60 mW/cm
2
). In a typical photo-catalytic reaction, 0.08 g photo-catalyst was added into a 100 mL quartz tube photo reactor containing 80 mL 20 mg/L AO7 solution. The mixture was stirred for 30 min in the dark to reach the absorption-desorption equilibrium, and then put into the photo-catalytic reactor. At the given time intervals, the analytical samples were taken from the mixture and immediately centrifuged to remove the photo-catalysts. The concentration of the filtrate was analyzed by checking the absorbance at 484 nm with a UV-vis spectrophotometer (Shimadzu
UV-2450).
3. Photo stability experiment: A 1000 W tungsten halogen lamp equipped with a UV cutoff filters (λ>420 nm) was used as a visible light source (the average light intensity was 60 mW/cm
2
). And a 300 W high-pressure Hg lamp for which the strongest emission wavelength is 365 nm was used as a UV light source (the average light intensity was about 1230 µW/cm 2
). 0.5g of 0.0213gV sample was exposed to the irradiation of UV and visible light for 24 hours. Afterward, XRD, DRS, EPR and

photo activity test were done to characterize the properties of the original, the UV irradiated and visible irradiated samples.

Fig S1 The device for vacuum activated treatment with A: muffle controller B: vacuum pump C: thermocouple D: heater strip E: quartz tube F: sample tank G: Teflon sealed rubber stopper
Fig S2 The V 2p XPS results of 0.0106V and 0.0213V
Fig S3 The O 1s XPS spectra of series of samples
Fig S4 The XRD, DRS, EPR and photoactivity results of photo aged samples

Fig.S1 The device for vacuum activated treatment
A: muffle controller B: vacuum pump C: thermocouple D: heater strip E: quartz tube
F: sample tank G: Teflon sealed rubber stopper

Fig.S2 The V 2p XPS results of 0.0106V and 0.0213V

Fig.S3 The O 1s XPS spectra of series of samples

Fig.S4 The XRD, DRS, EPR and photoactivity results of photo aged samples