High electrical conductivity guarantees a rapid electron transfer and thus plays an important role in electrocatalysis. In particular, for the single atom catalysts (SACs), to facilitate interaction between the single atom and supports, precisely engineering the conductivity represents a promising strategy to design SACs with high electrochemical efficiency. Here we show rhodium (Rh) SAC anchored on Co₃O₄ nanosheets arrays on nickel foam (NF), which is modified by a facile phosphorus (P-doped Rh SAC-Co₃O₄/NF), possessing an appropriate electronic structure and high conductivity for electrocatalytic reaction. With the introduction of P atom in the lattice, the electrocatalyst demonstrates outstanding alkaline oxygen evolution reaction (OER) activity with 50 mA·cm⁻² under overpotential of 268 mV, 6 times higher than that of Ir/C/NF. More interestingly, the P-doped Rh SAC-Co₃O₄/NF can get 50 mA·cm⁻² at only 1.77 V for overall water splitting. Both electrical conductivity studies and density functional theory (DFT) calculations reveal that the high conductivity at grain boundary improves the charge transfer efficiency of the Rh catalytic center. Furthermore, other noble-metal (Ir, Pd, and Ru) doped Co₃O₄ nanosheets arrays are prepared to exhibit the general efficacy of the phosphorus doping strategy.

高电导率保证了电子的快速转移，因此在电催化中起着重要作用。特别是对于单原子催化剂（SACs），为了促进单原子和载体之间的相互作用，精确地设计电导率是设计具有高电化学效率的 SACs 的一种有前途的策略。在这里，我们展示了锚定在泡沫镍 (NF)上的 Co ₃ O ₄纳米片阵列上的铑 (Rh) SAC ，它由一种易磷（P 掺杂的 Rh SAC-Co ₃ O ₄/NF)，具有适合电催化反应的电子结构和高电导率。通过在晶格中引入P原子，该电催化剂表现出优异的碱性析氧反应（OER）活性，在268 mV的过电位下为50 mA·cm ^{- 2}，是Ir/C/NF的6倍。更有趣的是，P掺杂的Rh SAC-Co ₃ O ₄ /NF在仅1.77 V的电压下就可以得到50 mA·cm ^{- 2}的整体水分解。电导率研究和密度泛函理论 (DFT) 计算都表明，晶界处的高电导率提高了 Rh 催化中心的电荷转移效率。此外，其他贵金属（Ir、Pd 和 Ru）掺杂 Co_制备3 O ₄纳米片阵列以展示磷掺杂策略的一般功效。