(1.75 V), OsP4 (1.72 V) and IrP4 (0.80 V) indicate that the high enough input energies are required for the effective OER catalytic performance. Additionally, previous study has reported that the robust binding interaction and excess energy go against the elimination of related OER intermediates, impeding the active sites and poisoning the catalysts. Hence, the aforementioned TMP4 catalysts are not regarded as the available catalysts for OER. For TMP4 (TM = Fe, Co, Ni, Cu, Rh, Pd, Ag, Pt and Au) catalysts with the positive ∆𝐺 𝑂𝐻 * , the overpotentials are relatively lower than those of the former TMP4 systems. Specially, for the NiP4, PdP4, AgP4 and AuP4 catalysts, converting from *OH to *O for the second proton-coupled electron transfer step is unlikely due to the larger free energy difference, and which can be considered as the potential-limiting step. In contrast, the potential-limiting step of OER is the third step over FeP4, CuP4 and PtP4 surfaces and the formation of *OOH from *O is rather difficult. According to η OER for FeP4 (0.73 V), NiP4 (0.84 V), CuP4 (2.93 V), PdP4 (0.75 V), AgP4 (1.44 V), PtP4 (0.56 V) and AuP4 (0.67 V), these TMP4 catalysts can also be reported inappropriate for the OER. Remarkably, the CoP4 and RhP4 catalysts exhibit outstanding OER catalytic performance, with the η OER of 0.32 and 0.50 V, respectively, which are better than or comparable to those of Pt1/PMA (0.49 V) , RuO2 (0.42 V) , ZnN4-edge (0.63 V) , and the commonly used IrO2 (0.56 V) catalysts. Thus, the CoP4 and RhP4 can assist as the high active catalysts for the OER. Further studies have been conducted to determine the specific ORR catalytic activities of TMP4 catalysts. It has known that the ORR is a reverse reaction of OER reaction, which also contains four proton-coupled electron transfer steps (see supporting information) on the TM active site. Therefore, Figure and Figure also indicate that the ∆𝐺 𝑂𝐻 * of TMP4 (TM = Ti, V, Cr, Mn, Zr, Nb, Mo, Ru, Hf, Ta, W, Re, Os and Ir) for ORR process are positive and this step can be considered as the potential-limiting step with the much higher overpotentials. Meanwhile, the formation of H2O will be impeded by the robust interaction between OH group and TMP4 catalysts for the final step of ORR. With reference to the η ORR of TiP4 (2.88 V), VP4