Cooperative Effect between Cation and Anion of Copper Phosphate on the

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1 Ref: jp--7u Supporting Information Cooperative Effect between Cation and Anion of Copper Phosphate on the Photocatalytic Activity of TiO for Phenol Degradation in Aqueous Suspension Haihang Chen, and Yiming Xu* Department of Chemistry, Zhejiang University, Hangzhou 7, China Table S Content of CuO in CuO/TiO samples with different units Samples CuO(wt %) Cu/Ti atomic ratio Cu/Ti atomic per (at%) CuTi.CuTi CuTi CuTi CuTi CuTi CuTi CuTi CuTi CuTi Table S Content of Ca (PO ) in Cu (PO ) /TiO samples with different units Samples Ca (PO ) (wt %) P/Ti atomic ratio P/Ti.CaPTi.999.E-.7.CaPTi CaPTi CaPTi CaPTi CaPTi CaPTi CaPTi atomic per (at %) Table S Content of Cu (PO ) in Cu (PO ) /TiO samples with different units

2 Samples Cu (PO ) (wt %) Cu/Ti Atomic ratio P/Ti atomic ratio Cu/Ti atomic per (at %) CuPTi P/Ti atomic per (at %). CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi CuPTi # # 9.CuO/TiO * 9.CaP/TiO.8CuO/TiO.8CaP/TiO Intensity(cps).9CuO/TiO.CuO/TiO.CuO/TiO.CuO/TiO Intensity(cps).9CaP/TiO.CaP/TiO.CaP/TiO.CaP/TiO TiO TiO CuO Ca (PO ) Theta Theta Figure S. XRD patterns of CuO/TiO, and CaP/TiO. The symbols # and * represent the crystalline phases of CuO (PDF #6-9), and Ca (PO ) (PDF #8-), respectively.

3 a b nm c nm d nm nm f e nm nm Figure S. SEM images of TiO, CuP, (c).cup/tio, (d) CuP/TiO, (e).8cup/tio, and (f) 9. CuP/TiO.

4 Figure S. The distribution of Ti, O, Cu, and P elements in the samples of (top) CuP/TiO, and (bottom) 9. CuP/TiO.The element mapping was recorded by EDS.

5 Intensity Intensity Bidentate O P O - Cu +- O P O O O Ti Ti Ti O O Ti Monodentate O O - P Cu + O O - Ti Binding energy (ev) 7 6 Binding energy (ev) Figure S. XPS spectrum of P p recorded CuP/TiO. Original, and Fitted spectra. CuO Cu x(po ) y 6 Magnetic Field (G) Figure S6. EPR spectra of bare CuO and Cu (PO ), recorded at room temperature. M-K unit FR.... F R (d) 6 λ (nm) K-M unit F R 9 6 CaP TiO.CaP/TiO 9.CaP/TiO.. 6 Wavelength λ (nm) (c) x Wavelength (nm) Figure S6. Diffuse reflectance spectra of CuO/TiO at the CuO loading (wt.%) of,, (c) 9., and (d), and CaP/TiO with different CaP loading as indicated in the legend. The y-axis is expressed by Kubelka Munk unit, F R = ( R) /R, where R is the reflectance.

6 .. C (mm). (c).. Irradiation time (min) Figure S7. Time profiles of hydroquinone (solid bars) and benzoquinone (open bars), produced from phenol degradation over TiO,.CuP/TiO, and (c) CuO/TiO... k obs (min - ) Ca (PO ) loading (wt.%) Figure S8. Effect of CaP loading on the photocatalytic activity of CaP/TiO for phenol degradation in the aerated aqueous suspension under UV light. kobs ( - min - ) Surface area normalized rate constant ( -, g m - min - ) Atomic ratio of Cu to Ti 6 8 Modifier loading (wt.%) Figure S9. Apparent rate constants of phenol degradation as a function of Cu/Ti atomic ratio. Surface area-normalized rate constants of phenol degradation. Data come from Figures and for the catalysts of CuP/TiO and CuO/TiO. 6

7 Intensity 7 7 Magnetic Field (G) Figure S. EPR spectra of.cup/tio obtained under N and in air. Dark and red lines represent the signals recorded in the dark, and after UV irradiation for min, respectively. PL Intensity Wavelength (nm) Figure S. PL spectra of TiO (black line) and.cup/tio (red line) samples. q ( - mol/g) (c) (d) 7 Ceq ( - M) Figure S. Adsorption isotherm of,-dichlorphenol in aqueous suspension on the catalysts (. g/l) of. CuP/TiO, CuO/TiO, (c). CaP/TiO, and (d) bare TiO.