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Heteroatoms-modified Fe–N–C catalysts have garnered significant attention for enhancing the oxygen reduction reaction (ORR). However, revealing the correlation between the type of heteroatoms used for doping and catalytic performance still faces significant challenges. Herein, based on the density functional theory (DFT), a series of heteroatom-modified Fe–N–C models with the tailored Fe–N 4 -X (X = S, P or B) site are constructed to explore the regulatory mechanism of heteroatoms on the electronic structure and adsorption behavior of Fe centers. Theoretical calculations reveal that the doping of S atoms can optimize the electronic environment of Fe atoms, thus leading the favorable interaction between Fe–N 4 –S site and OH intermediates. As a result, the Fe–N 4 –S site possess a lower energy barrier for the desorption of OH* than that of Fe–N 4 –B and Fe–N 4 –P, indicating higher catalytic activity and kinetics of S-modified Fe–N–C catalysts. [Display omitted] • Heteroatom-modified Fe–N 4 models are analyzed by theoretical calculations. • S doping can optimize the electronic structure around Fe–N 4 sites. • S doping promotes the OH* desorption, thus leading to enhanced kinetics process. • Fe–N 4 –S model exhibits higher activity and stability than Fe–N 4 –B and Fe–N 4 –P. [ABSTRACT FROM AUTHOR]

With the scarcity of fuel energy, non-noble metal compounds assisted water of electrolysis is becoming a potential candidate for cost-effective and high-quality hydrogen production. To date, transition metal phosphide (TMP) has been considered as one of the most promising catalysts for water splitting because of its multitudinous but controlled constituent elements and stoichiometric ratios. In this review, the electronic structure analysis of TMP dialectically reveals the active derivation for catalyzing hydrogen evolution (HER) and oxygen evolution reaction (OER). And then the strategies of rationally designing the structure and composition of electrocatalyst to improve its intrinsic activity are discussed, especially interface engineering. Besides, this review also focuses on the negligible stability issue during the water splitting process. In the end, some key challenges and research orientations of TMPs are pointed out, which is instructive for developing high-efficient and stable electrocatalysts for water splitting. • The activity derivation of transition metal phosphide (TMP) for water splitting. • Optimization strategies for TMPs to modulate their electron structure. • Strategies to improve conductivity and durability for the first time. • Prospects for the development of the design and synthesis of TMP in water splitting. [ABSTRACT FROM AUTHOR]