Multimetal oxyhydroxides have recently been reported that outperform noble metal catalysts for oxygen evolution reaction (OER). In such 3d-metal-based catalysts, the oxidation cycle of 3d metals has been posited to act as the OER thermodynamic-limiting process; however, further tuning of its energetics is challenging due to similarities among the electronic structures of neighbouring 3d metal modulators. Here we report a strategy to reprogram the Fe, Co and Ni oxidation cycles by incorporating high-valence transition-metal modulators X (X = W, Mo, Nb, Ta, Re and MoW). We use in situ and ex situ soft and hard X-ray absorption spectroscopies to characterize the oxidation transition in modulated NiFeX and FeCoX oxyhydroxide catalysts, and conclude that the lower OER overpotential is facilitated by the readier oxidation transition of 3d metals enabled by high-valence modulators. We report an ~17-fold mass activity enhancement compared with that for the OER catalysts widely employed in industrial water-splitting electrolysers.

最近有报道称，多金属羟基氧化物的性能优于用于氧气析出反应（OER）的贵金属催化剂。在这样的3 d -金属基催化剂，3种的氧化循环d金属已被假定充当OER热力学限制工艺; 然而，由于相邻3 d的电子结构之间的相似性，对其能量学的进一步调整具有挑战性金属调制器。在这里，我们报告了通过结合高价过渡金属调制剂X（X = W，Mo，Nb，Ta，Re和MoW）对Fe，Co和Ni氧化循环进行重新编程的策略。我们使用原位和异位软，硬X射线吸收光谱来表征调制NiFeX和FeCoX羟基氧化物催化剂中的氧化转变，并得出结论，较低的OER超电势是由3d金属的较高的氧化转变所促进的。价调节剂。与广泛用于工业水分解电解槽的OER催化剂相比，我们报道了约17倍的质量活度提高。