杂原子磷调控氧还原反应单原子电催化剂的研究进展

Research Progress on Heteroatom Phosphorus Regulated Single-atom Electrocatalysts for Oxygen Reduction Reaction

摘要

氧还原反应（ORR）是燃料电池和金属-空气电池等能源储存和转换装置的重要电化学过程. ORR涉及复杂的多电子/质子转移， 反应动力学缓慢， 制约了其在能源储存和转换装置中的能量转换效率. 单原子电催化剂因其较大的原子利用率和独特的电子结构， 成为异相催化领域的热点. 杂原子掺杂是调控ORR性能的有效策略， 其中， 杂原子磷（P）的3p轨道上的孤对电子能够调节中心金属原子的配位微环境和电荷分布， 进而调控含氧中间体的吸/脱附行为， 从而影响ORR性能. 本文综合评述了杂原子P对单原子电催化剂ORR性能的调控机制： （1） 在第一配位层中， P直接取代与中心金属原子配位的N原子； （2) P位于第二或第三配位层或者更为外层的区域； （3） 含P化合物调控. 本文阐明了杂原子P对ORR性能的影响机制， 明确了通过杂原子掺杂设计合成高活性、 高耐久性ORR单原子电催化剂的指导原则.

Abstract

Oxygen reduction reaction（ORR） is a key electrochemical process in energy storage and conversion devices such as fuel cells and metal-air batteries. ORR involves complex multi-electron and proton transfer processes， and its sluggish kinetics severely limits the energy conversion efficiency of these devices. Single-atom electrocatalysts（SACs） have emerged as a prominent focus in heterogeneous catalysis due to their high atomic utilization and unique electronic structures. Heteroatom doping serves as an effective strategy for modulating ORR performance. Among various heteroatoms， phosphorus（P） possesses lone pair electrons in its 3p orbitals， which can regulate the coordination microenvironment and charge distribution around the central metal atom， thereby tuning the adsorption/desorption strength of oxygen-containing intermediates and influencing ORR catalytic activity. This review systematically summarizes the regulatory mechanisms of P heteroatoms on the ORR performance of SACs， specifically in three aspects： （1） in the first coordination sphere， where P directly substitutes for N atoms coordinated to the central metal atom； （2） in the second or third coordination sphere， or in more peripheral regions； （3） through regulation by phosphorus compounds. This review elucidates the mechanisms by which heteroatom P influences ORR performance and establishes guiding principles for the design and synthesis of high-activity and high-durability single-atom ORR electrocatalysts viaheteroatom doping.

关键词

磷掺杂 / 氧还原反应 / 单原子电催化剂

Key words

Phosphorus doping / Oxygen reduction reaction / Single-atom electrocatalyst

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基金资助

国家自然科学基金(52172208)

泰山学者青年专家计划(tsqn202306216)