The nitrogen sorption isotherm of CIPN-0.25 (
Fig. 2a) combines the characteristics of the type I and IV isotherms [
35]. A rapid rise at
P/
P0 < 0.05 and the hysteresis loop in the medium-pressure region indicate the coexistence of plentiful micro-, meso- and macropores [
36,
37], and the highest absorptive amount for CIPN-0.25 among the three materials discloses the well-developed porosity in the IPNs-derived carbon material. As observed from pore size distribution curves (
Fig. 2b), CIPN-0.25 shares the similar pore diameters distributed at 0.54 and 1.3 nm in the microporous region and a wide range of 2–30 nm in the mesoporous region with CRF. In contrast, CSA displays a quite different type I isotherm with no distinctive hysteresis loop, suggesting that the SA network rarely participates in the carbon skeleton rearrangement at high temperature [
38,
39]. As the SA proportion in IPN increases from 0.125 to 0.25, the surface area displays a slight downward trend from 1047 m
2/g to 1013 m
2/g owing to the pore diameter enlargement induced by SA decomposition, and the
Vmicro/
Vtotal value consistently decreases (
Figs. 2c and
d, Table S1 in Supporting information). Additionally, excessive SA proportion in IPN could sharply reduce the cross-linking density of the carbon supply, and thus the KOH etching into the flimsy skeleton causes the decayed surface areas and total pore volumes (CIPN-1, 889 m
2/g and 0.65 cm
3/g). The SA decarboxylation results in a preliminary porous frame along with the subsequent chain decomposition (
e.g., glycosidic bond,
β-D-mannuronic) in the initial stage of pyrolyzing, and these resultant nanopores offer intrusive and dispersed etching spaces to accommodate KOH during further programed pyrolyzing for pore structure refinement [
33,
40]. For comparison, the pore structure information of CIPN-0.25
A0 (the carbon prepared without KOH, CIPN-0.25
Ay, where
y refers to the mass ratio of activator to IPN precursors) is displayed to further clarify the effect of SA in IPN as an in-knitted synergistic porogen. CIPN-0.25
A0 owns the surface area of 625 m
2/g and multilevel pore distribution centered at 0.54, 1.3 and 2–11 nm (Figs. S3a, b and Table S1 in Supporting information), demonstrating the preliminary pore-forming effect of relatively thermolabile SA. Among the CIPN-0.25, CIPN-0.25
A0 and CRF, CIPN-0.25 owns the obviously enhanced micropore (centered at 0.54 nm) quantity as well as the enlarged mesopore quantity and diameter compared with the other two carbon samples. Accordingly, owing to the SA/KOH synergistic pore-forming effect, both the specific surface area and total pore volume are increased to 1013 m
2/g and 0.96 cm
3/g for CIPN-0.25, while CIPN-0.25
A0/CRF prepared with the absence of KOH/SA only owns the surface area of 625/620 m
2/g (Figs. S3a and b, Table S1). Furthermore, the KOH dosage also determines the etching degree into the IPNs skeleton and plays an importance influence on the porous structure evolution. As disclosed in Figs. S3c, d and Table S1 (Supporting information), CIPN-0.25
A0.5 prepared under an insufficient activator dosage possesses an unsatisfactory surface area (855 m
2/g) and an undeveloped porosity with tiny mesopores, while the KOH overdose brings about the meso-/macropore collapse or micropore disappearance in CIPN-0.25
A2 and CIPN-0.25
A3. The influence of pyrolysis conditions including the temperature, time and heating rate is also investigated (Figs. S3e and f, Table S1 in Supporting information). An optimal pyrolysis temperature of 600 ℃ can reach the large specific surface area of 1013 m
2/g and balanced micro-/mesopore distribution (
Vmicro/
Vtotal = 31.3%), while inadequate/overmuch pyrolysis at 550/650 ℃ leads to the surface area of 859/914 m
2/g and decayed
Vmicro/
Vtotal values. Meanwhile, the obtained carbon materials prepared at the same temperature of 600 ℃ and the different pyrolysis time of 4 h (CIPN-0.25
PT4) or heating rate of 1.5 ℃/min (CIPN-0.25
HR1.5) share the similar nitrogen sorption isotherms and pore size distributions with CIPN-0.25, demonstrating the suitable setup of the programed pyrolysis. Additionally, Raman spectra (Fig. S4 in Supporting information) reveal the graphitization degree (
ID/
IG) ranging from 0.78 to 0.92, wherein the graphitization degree displays a slight uptrend with the increasing pyrolysis temperature. From the above, the high surface area of CIPN-0.25 is assigned to the optimized cross-linking density of two blended networks in IPN, and the optimization of preparation conditions further gives CIPN-0.25 with the well-developed hierarchical porosity and satisfactory graphitization degree.