Arkan, Mesude Z.Mesude Z.ArkanBartolomé, LuisLuisBartoloméEglītis, RaivisRaivisEglītisBrinker, ManuelManuelBrinkerAmayuelas López, EderEderAmayuelas LópezHuber, PatrickPatrickHuberChorążewski, MirosławMirosławChorążewskiMeloni, SimoneSimoneMeloniŠutka, AndrisAndrisŠutkaGrosu, YaroslavYaroslavGrosu2026-09-252026-09-252026-07-28Journal of Physical Chemistry C 130 (36): 12748-12756 (2026)https://hdl.handle.net/11420/65050Solid–liquid contact electrification is widely studied using diverse experimental geometries that are often implicitly assumed to probe equivalent interfacial processes. Here, we directly test this assumption by comparing immersion–emersion, droplet-based contact, and pressure-driven intrusion–extrusion electrification using the same hydrophobic nanoporous silicon monolith and isotopically substituted liquids (H2O and D2O). Despite identical surface chemistry, isotopic substitution produces qualitatively different electrical responses depending on the wetting regime. Immersion–emersion experiments show polarity inversion between H2O and D2O, while droplet measurements reveal distinct charge evolution and periodic opposite-polarity events. In contrast, forced nanopore intrusion preserves polarity but strongly enhances electrical output for D2O. These results demonstrate that wetting of surface nanoroughness during droplet, vs immersion–emersion, vs complete nanopores wetting upon intrusion–extrusion correspond to fundamentally different electrification states. By using isotope substitution as a controlled probe, this work establishes a general framework for disentangling protocol-dependent effects in solid–liquid contact electrification and triboelectric energy conversion.de1932-74552026361274812756American Chemical Society (ACS)https://creativecommons.org/licenses/by/4.0/Natural Sciences and Mathematics::541: Physical; Theoretical::541.3: Physical Chemistry::541.37: ElectrochemistryTechnology::620: Engineering::620.1: Engineering Mechanics and Materials Science::620.11: Engineering MaterialsJournal Article10.1021/acs.jpcc.6c0413410.15480/882.18617