Based on the values of pK a , we obtained the dissociation free energy of adsorbed water ∆A diss on BiVO 4 (010) surface according to Eq. 4, giving a value of 0.32 eV. There have always been different views on the dissociation of chemisorbed water at the BiVO 4 interface. Previous theoretical studies had not reported or observed the dissociation of adsorbed water on the BiVO 4 (010) surface, until Wang and Galli found that the dissociation of water does occur on the BiVO 4 (010) surface using ambient pressure resonant photoemission spectroscopy (AP-ResPES) measurements and first-principles simulations . It is worth noting that water dissociation on the pristine rutile TiO 2 (110) surface have been controversial for both the experiment and theory, with the dissociation free energy of adsorbed water 0.45 to 0.6 eV with DFT studies. Nevertheless, with the improvement of experimental techniques and the development of machine learning methods, it is found that the interfacial water can be indeed dissociated on TiO 2 . Compared to TiO 2 , BiVO 4 has a lower ∆A diss (see Table ). Therefore, it is plausible for the spontaneous dissociation of adsorbed water on BiVO 4 surface with a sufficient time-scale, although we did not observe it during the course of our DFTMD simulations at PZC.