Metal-free nitrogen-doped carbons were prepared by D-glucose – citric acid polymerization followed by mild air carbonization.

Structure and surface chemistry were examined by XRD and Raman for local graphitic order, XPS for nitrogen 

speciation, SEM-EDX for morphology and elemental distribution, and N2 isothermal adsorption-desorption for textural 

properties. Catalytic tests for sodium borohydride methanolysis were carried out in anhydrous methanol at 30 °C and 

2.5 wt% NaBH4, with hydrogen volume logged in real time and initial rates used for Arrhenius analysis. The optimized 

catalyst, NC-CA2.0 reached an HGR of 5200 mL.gcat−1.min⁻¹ at 30 °C and showed an apparent activation energy of 

25.4±1.8 kJ.mol⁻¹. Capacity was preserved over five cycles, whereas the peak rate declined to about 45% of the initial 

value. Together with strong inhibition by added base, the kinetic behavior is consistent with an interfacial Eley–Rideal 

pathway in which edge nitrogen assists adsorption or polarization of methanol and borohydride derived intermediates and 

N environments in more graphitized domains facilitate charge transport within the sp² framework. The data indicate that 

methanolysis performance is governed by the combination of local graphitic order and accessible edge nitrogen rather than 

by total nitrogen content, providing guidance for the design of robust metal-free carbons for on-demand hydrogen release.