Heteroatom occupancy plays a key role in the precise modulation of specific material regions by introducing foreign elements into the main material matrix, yet it urgently requires further understanding from a spatial perspective. Herein, we propose a pioneering “satellite atom-spinel crystal” concept by synthesizing model catalysts with Fe atoms strategically positioned at two different spatial positions of spinel Co3O4 (satellite-Fe at Co3O4 (Fe(Sat)-Co3O4) and Fe-doped Co3O4 (Co3Fe(in)O4)), through which a new catalytic phenomenon is found. Multidimensional in situ spectroscopies revealed that Fe(Sat)-Co3O4 overcomes the crystal field potential energy (FeSat-O > FeSat-O-CoOh) and exhibits 1%(Fe atom) lower impedance than that of Co3Fe(in)O4 due to the resistance-free electron delocalization layer formed in Fe(Sat)-Co3O4, which results in tens of times increase of the turnover frequency and mass activity and then a great reduction in the overpotential by 120 mV when used to catalyze the electrochemical oxygen evolution reaction compared to that of Co3Fe(in)O4. Density functional theory calculations further dynamically reveal the mechanisms governing electron itinerancy modulation. This study not only provides valuable insights into the impact of heteroatomic spatial positioning on material properties but also significantly expands our understanding of atomic manipulation.
