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Here, we design amide-linked benzene\u2013triazine covalent organic frameworks (BTA\/TzTA-Hz COFs) and integrate them with carbon nanotubes (CNTs) to form COF\u2013CNT junctions that establish a built-in interfacial electric field. Density functional theory (DFT) and electrostatic potential maps indicate complementary active motifs, with benzene-proximal fragments associated with HER and triazine-proximal motifs associated with OER. CNT integration shifts the contact-potential difference by \u22480.20 V, while operando electrochemical impedance spectroscopy suggests partially separable high-frequency junction-charging and lower-frequency Faradaic\/transport responses. A 300 mT static magnetic field lowers the HER and OER overpotentials by tens of millivolts. Under anodic bias, the effective interfacial charging capacitance increases, and Mott\u2013Schottky analysis shows an apparent \u223c0.15 V flat-band shift with an essentially unchanged slope. Together, these observations are consistent with field-perturbed interfacial charging and altered bias partitioning. Field-dependent impedance and bubble imaging are consistent with magnetohydrodynamic convection that promotes bubble detachment and near-electrode mass transport for both half-reactions, and they reveal an OER-specific high-frequency perturbation under anodic bias. Under field, the heterostructure reaches an OER onset overpotential of \u223c261 mV and requires an overpotential of 366 mV at 10 mA cm\u20132 in alkaline electrolyte. These results illustrate how reticular-framework chemistry, junction engineering, and both built-in and applied fields can program reactivity through interfacial electrostatics and near-electrode transport in organic-framework electrocatalysts.<\/jats:p>","DOI":"10.1021\/jacs.6c03609","type":"journal-article","created":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T13:42:45Z","timestamp":1784814165000},"page":"39483-39500","source":"Crossref","is-referenced-by-count":1,"title":["Field-Coupled\nWater Splitting with Metal-Free Donor\u2013Acceptor\nCovalent Organic-Framework Junctions"],"prefix":"10.1021","volume":"148","author":[{"given":"Lissette","family":"Garcia-Enriquez","sequence":"first","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8439-3141","authenticated-orcid":true,"given":"Daniel","family":"Gomez-Bustos","sequence":"additional","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aruna","family":"Narayanan Nair","sequence":"additional","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kavish","family":"Saini","sequence":"additional","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5798-3584","authenticated-orcid":true,"given":"Dino","family":"Villagran","sequence":"additional","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3728-6578","authenticated-orcid":true,"given":"Srikanth","family":"Pilla","sequence":"additional","affiliation":[{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]},{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]},{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]},{"name":"University of Delaware , , , ,","place":["Newark, Delaware, United States, 19716"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5728-0512","authenticated-orcid":true,"given":"Sreeprasad T.","family":"Sreenivasan","sequence":"additional","affiliation":[{"name":"The University of Texas at El Paso , , , ,","place":["El Paso, Texas, United States, 79968"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,23]]},"reference":[{"issue":"5","key":"2026092311073952700_cit1a","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201703646","article-title":"Covalent Organic\nFramework Electrocatalysts for Clean Energy Conversion","volume":"30","author":"Lin","year":"2018","journal-title":"Adv. Mater."},{"issue":"18","key":"2026092311073952700_cit1b","doi-asserted-by":"publisher","first-page":"6010","DOI":"10.1039\/c2cs35157a","article-title":"Covalent organic frameworks","volume":"41","author":"Feng","year":"2012","journal-title":"Chem. Soc. Rev."},{"issue":"2","key":"2026092311073952700_cit1c","doi-asserted-by":"publisher","first-page":"548","DOI":"10.1039\/C2CS35072F","article-title":"Covalent organic frameworks (COFs):\nfrom design to applications","volume":"42","author":"Ding","year":"2013","journal-title":"Chem. Soc. Rev."},{"issue":"15","key":"2026092311073952700_cit1d","doi-asserted-by":"publisher","first-page":"6152","DOI":"10.1021\/jacs.9b01891","article-title":"Triazine Functionalized Porous Covalent Organic Framework\nfor Photo-organocatalytic E- Z Isomerization of Olefins","volume":"141","author":"Bhadra","year":"2019","journal-title":"J. Am. Chem. 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Mater."},{"issue":"17","key":"2026092311073952700_cit25","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202300283","article-title":"Electrolyte-Wettability\nIssues and Challenges of Electrode Materials in Electrochemical Energy\nStorage, Energy Conversion, and Beyond","volume":"10","author":"Zhao","year":"2023","journal-title":"Adv.\nSci."},{"issue":"1","key":"2026092311073952700_cit26","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-25091-8","article-title":"Real space electron delocalization, resonance, and\naromaticity in chemistry","volume":"12","author":"Reuter","year":"2021","journal-title":"Nat. Commun."},{"issue":"45","key":"2026092311073952700_cit27a","doi-asserted-by":"publisher","first-page":"8598","DOI":"10.1039\/C8SC02990C","article-title":"Unraveling substituent effects on\nfrontier orbitals of conjugated molecules using an absolutely localized\nmolecular orbital based analysis","volume":"9","author":"Mao","year":"2018","journal-title":"Chem. 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