This study reports the design of N- and S-doped ordered mesoporous carbon hollow spheres (OMCHS) as metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. Three electrocatalysts were synthesized using molecular precursors: (i) 2-thiophenemethanol (S-OMCHS), (ii) 2-pyridinecarboxaldehyde/2-thiophenemethanol (N1-S-OMCHS), and (iii) pyrrole/2-thiophenemethanol (N2-S-OMCHS). Among them, S-OMCHS exhibited the best activity (E_onset = 0.88 V, E_½ = 0.81 V, n ≈ 3.95), surpassing both co-doped analogs. After conducting an accelerated degradation test (ADT), S-OMCHS and N1-S-OMCHS showed improved catalytic behavior and outstanding long-term stability. Surface analysis confirmed that performance evolution correlates with heteroatom reorganization: S-OMCHS retained and regenerated thiophene-S and C=O/quinone species, while N1-S-OMCHS converted N-quaternary into N-pyridinic/pyrrolic, both enhancing O₂ adsorption and *OOH reduction through synergistic spin–charge coupling. Conversely, oxidation of N and loss of thiophene-S in N2-S-OMCHS led to partial deactivation. These results establish a direct link between surface chemistry evolution and electrocatalytic durability, demonstrating that controlled heteroatom doping stabilizes active sites and sustains the four-electron ORR pathway. The approach provides a rational design framework for next-generation, metal-free carbon electrocatalysts in alkaline fuel cells and energy conversion technologies.

Two-dimensional (2D) materials, particularly MXenes and transition metal dichalcogenides (TMDs), have attracted intense interest as supercapacitor electrodes due to their high surface area and tunable electronic structure. However, large discrepancies persist between the quantum capacitance values predicted by density functional theory (DFT) calculations and experimentally measured gravimetric capacitances. In this review, we critically analyze DFT methodologies, surface models, normalization strategies, and electrochemical characterization protocols, and compile an extensive dataset of reported MXene and TMD systems to quantify the degree of experimental–theoretical agreement. We show that MXenes typically achieve less than 20% of their predicted capacitance because of restacking, surface terminations, and limited ion accessibility, whereas TMDs exhibit substantially better correspondence, often approaching or exceeding 70% of theoretical values. These results indicate that the theoretical capacitance predicted by DFT is primarily determined by the electronic structure of the material, which defines the upper limit of charge storage, whereas the experimentally achieved capacitance is largely controlled by morphological factors, surface chemistry, and electrode architecture that limit ion accessibility.