Semiconductor d‐Band Engineering for Enhanced Photocatalytic Nitrogen Fixation: Progress and Perspectives

ABSTRACT

Regulating the d‐band center of semiconductors through elemental doping presents a promising strategy for enhancing the efficiency of photocatalytic nitrogen conversion. This review systematically summarizes recent advances in d‐band center engineering for photocatalytic nitrogen fixation. It begins with a concise introduction to the fundamental principles and mechanisms of photocatalytic nitrogen fixation. The core d‐band center theory is subsequently elaborated, detailing how the position of the d‐band center governs catalytic activity. In discussing its applications, the review examines the influence of metal surface configurations and electric field modulation on the electronic structure, emphasizing how precise heteroatom doping can effectively tune the d‐band center. To further improve photocatalytic nitrogen fixation performance, targeted strategies for d‐band center regulation are proposed. These include: (i) modulating adsorption energies via elemental doping, and precisely controlling the number of d‐electrons through valence state adjustment, redox tuning, or charge transfer induction and (ii) adjusting the d‐band width, thereby influencing the d‐band center position and adsorption energy, through the introduction of tensile/compressive strain or by altering the coordination number and strength. Finally, this review concludes with a perspective on the implications of d‐band center engineering for photocatalytic nitrogen fixation, aiming to provide a comprehensive understanding of both the theoretical framework and its practical applications in this field.