Photocatalytic water oxidation with cobalt-containing tungstobismutates : Tuning the metal core

Table S1. Crystallographic data and structural refinements for compounds (1), (2) and (3). S2 Table S2. Selected bond distances for Co/Bi-POM (1). S3 Table S3. Selected bond distances for Co/Bi-POM (2). S4 Table S4. Selected bond distances for Mn/Bi-POM (3). S5 Table S5. BVS calculations for Co/Bi-POM (1). S6 Table S6. BVS calculations for Co/Bi-POM (2). S6 Table S7. BVS calculations for Mn/Bi-POM (3). S6 Figure S1. X-ray powder diffraction pattern of bulk Co/Bi-POM (1) vs. calculated pattern. S7 Figure S2. X-ray powder diffraction pattern of bulk Co/Bi-POM (2) vs. calculated pattern. S7 Figure S3. X-ray powder diffraction pattern of bulk Co/Bi-POM (3) vs. calculated pattern. S8 Figure S4. FT-IR spectra of pristine Co/Bi-POM (1), Co/Bi-POM (2) and Mn/Bi-POM (3). S9 Figure S5. TG analysis of pristine Mn/Bi-POM (3). S10 Figure S6. Cyclic voltammogram of Co/Bi-POM (1) in H2SO4 (0.4 M) at pH 3. S11 Figure S7. Cyclic voltammograms of Co/Bi-POM (1) and Co/Bi-POM (2). S11 Figure S8. UV/Vis absorption spectra of Co/Bi-POM (1) and Co/Bi-POM (2). S12 Figure S9. UV/Vis absorption spectrum of Mn/Bi-POM (3). S13 Figure S10. Clark-electrode kinetics for visible-light-driven O2 formation with Co/Bi-POM (1). S14 Figure S11. O2 evolution for Co/Bi-POM (1) and Co/Bi-POM (2). S14 Figure S12. Representative GC kinetics traces of headspace injection of Co/Bi-POM (1). S15 Figure S13. O2 formation kinetics for Co/Bi-POM (1). S15 Table S8. Influence of [Ru(bpy)3]Cl2 and Na2S2O8 on WOC performance of Co/Bi-POM (1). S16 Figure S14. Representative GC traces showing inactivity of Co/Bi-POM (2). S17 Figure S15. FT-IR spectra of pristine POM (1) vs. POM/PS complexes. S18 Figure S16. TG curves of pristine Co/Bi-POM (2) and Co/Bi-POM (2)/PS complex. S18


Experimental procedure for WOC activity tests
Water oxidation performance for all compounds has been monitored simultaneously using Clark electrodes and GC equipment.After the degassing process, first 100 μL of headspace were injected into the GC to monitor the efficiency of the He-purging.The O 2 /N 2 ratio was evaluated and subtracted by the mean of the calibration line.Note that no He-injection in the headspace has been performed in order to rebalance the lower pressure caused by the GC injection.
After evaluation of the purging process, the Clark-electrode was lifted down in the catalytic vial, first in the headspace and once it showed constant voltage, it was moved down into the solution.After 30" of equilibration time at controlled 500 rpm, the irradiation was started and the oxygen evolution kinetics were recorded.
For Co/Bi-POM (1), maximum amounts of O 2 dissolved in solution was obtained after 30 min of Clark electrode monitoring; no GC injection was performed up to this point.GC injection was initiated 1 h after the reaction had started to evaluate the final O 2 yield of the catalytic process (Fig. S10).

Figure S1 .
Figure S1.X-ray powder diffraction pattern of bulk Co/Bi-POM (1) vs. calculated pattern.Intensity differences may be due to preferred orientation of the powder sample.

Figure S2 .
Figure S2.X-ray powder diffraction pattern of bulk Co/Bi-POM (2) vs. calculated pattern.Intensity differences may be due to preferred orientation of the powder sample.

Figure S3 .
Figure S3.X-ray powder diffraction pattern of bulk Co/Bi-POM (3) vs. calculated pattern.Intensity differences may be due to preferred orientation of the powder sample.

Table S3 .
Selected bond distances for Co/Bi-POM (