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oai:figshare.com:article/34037329 2026-10-01T00:13:26Z category_1 category_4 category_8 category_272 category_873 category_39 category_734 category_64 portal_63 item_type_6 month_year_10_2026

Anion-Activated Supramolecular Proton Relays Enable Neutral-pH and Seawater Oxidation Faezeh Sarafraz (25147132) Afshin Pashabadi (17635601) Avat Arman Taherpour (2505475) Mojtaba Shamsipur (1395787) Biophysics Biochemistry Microbiology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Ecology Biological Sciences not elsewhere classified Cancer varying nitrogen content unconventional one aza seawater oxidation neutral neutral phosphate buffer management layers rather graphite sheet delivers direct seawater oxidation dft analyses reveal coupled electron transfer conventional redox catalysts confined azacrown macrocycles computational studies show competitive chloride corrosion combined gerischer impedance 4 ° c maximal proton affinity dominated proton shuttling substituting cu foam oer activity follows interfacial activity free oer supramolecular proton sluggish proton proton storage type hopping superior catalysis overstabilizes protons enables rapid employ surface critically hindered ambient temperature Neutral-pH and direct seawater oxidation are critically hindered by sluggish proton-coupled electron transfer (PCET) and competitive chloride corrosion. Here, we employ surface-confined azacrown macrocycles of varying nitrogen content as supramolecular proton-management layers rather than conventional redox catalysts. In neutral phosphate buffer, OER activity follows an unconventional one aza > two aza ≫ six aza macrocycle trend, with Cu/Hexaaza exhibiting purely capacitive behavior that switches to superior catalysis at 4 °C. Combined Gerischer impedance and DFT analyses reveal an anion-assisted PCET mechanism wherein phosphate binding narrows the HOMO–LUMO gap, transforming electronically inert hosts into a highly polarizable proton–anion assembly. The computational studies show that the interfacial activity is governed not by maximal proton affinity, but by an optimal enthalpy–entropy balance between proton storage and Grotthuss-type hopping. While hexaaza (HAZ) overstabilizes protons at ambient temperature, monoaza (MAZ) enables rapid, exchange-dominated proton shuttling. Substituting Cu foam with a graphite sheet delivers a metal-free OER in intact seawater without pH adjustment or desalination. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/acs.jpcc.6c03999.s001 https://figshare.com/articles/journal_contribution/Anion-Activated_Supramolecular_Proton_Relays_Enable_Neutral-pH_and_Seawater_Oxidation/34037329 CC BY-NC 4.0