000164132 001__ 164132
000164132 005__ 20251121161352.0
000164132 0247_ $$2doi$$a10.1021/acsanm.5c03130
000164132 0248_ $$2sideral$$a146294
000164132 037__ $$aART-2025-146294
000164132 041__ $$aeng
000164132 100__ $$0(orcid)0000-0001-8572-1760$$aPérez-Miana, Marta$$uUniversidad de Zaragoza
000164132 245__ $$aHigh Pressure-Based Synthesis of Nanoporous Metal–Organic Framework ZIF-93 Giving Rise to a Phase for Proton Conduction
000164132 260__ $$c2025
000164132 5060_ $$aAccess copy available to the general public$$fUnrestricted
000164132 5203_ $$aThis study aims to develop a green, solvent-free synthesis of ZIF-93 (ZIF stands for zeolitic imidazolate framework) and to explore the formation of different phases. We report the solvent-free synthesis of a previously unreported nanoporous ZIF phase, ZIF-93_HP (HP referring to “high-pressure”), from zinc oxide using a dual high-pressure (150 MPa) and thermal (110 °C) method. The influence of key synthesis parameters, such as the amount of NH4NO3 promotor and reaction steps, was systematically investigated to maximize the conversion of ZnO into the intermediate ZIF-93_HP, while, in parallel, preventing its further conversion into nanoporous ZIF-93 phase. The material was extensively characterized by X-ray diffraction, thermogravimetry, electron microscopy and N2 and CO2 adsorption, which revealed insights into the structure, morphology and nanoporosity of ZIF-93_HP. ZIF-93_HP, with empirical formula of Zn(C5N2OH5)2·1.2(NH4NO3)·(H2O), is related to the previously reported ZIF-93 (Zn(C5N2OH5)2). Water washing of this phase led to the transformation into ZIF-93 and a significant increase in the BET specific surface area (from 4 to 181 m2/g). In addition, the presence of NH4+ and NO3– ions into its structure makes ZIF-93_HP proton conductor at room temperature and moisture conditions (3.76 × 10–3 S/cm), a property that decreases with increasing temperature due to dehydration. The discovery of ZIF-93_HP highlights the potential of the high-pressure, solvent-free synthesis as a powerful tool for the exploration of different ZIFs and reticular materials that are inaccessible through traditional solvothermal methods. As crystallization under solvent-free conditions is often influenced by nonthermodynamic equilibrium, this approach holds a great potential for expanding the material landscape by enabling the discovery of different phases and structures with unique properties, such as the promising proton conductivity demonstrated here.
000164132 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E13-23R$$9info:eu-repo/grantAgreement/ES/DGA/T68-23R$$9info:eu-repo/grantAgreement/ES/MCIU/CNS2023-144346$$9info:eu-repo/grantAgreement/ES/MCIU/RYC-2018-024561-I$$9info:eu-repo/grantAgreement/ES/MICIU/CEX2023-001286-S$$9info:eu-repo/grantAgreement/ES/MICIU/PID2021-122940OB-C31$$9info:eu-repo/grantAgreement/ES/MICIU/PID2022-138582OB-I00
000164132 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000164132 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000164132 700__ $$aFernández de Luis, Roberto
000164132 700__ $$aFidalgo-Marijuan, Arkaitz
000164132 700__ $$aLi, Junyan
000164132 700__ $$0(orcid)0000-0002-5229-2717$$aMayoral, Álvaro
000164132 700__ $$0(orcid)0000-0003-1512-4500$$aCoronas, Joaquín$$uUniversidad de Zaragoza
000164132 7102_ $$15005$$2555$$aUniversidad de Zaragoza$$bDpto. Ing.Quím.Tecnol.Med.Amb.$$cÁrea Ingeniería Química
000164132 773__ $$g8, 43 (2025), 20713-20725$$pACS appl. nano mater.$$tACS APPLIED NANO MATERIALS$$x2574-0970
000164132 8564_ $$s12174628$$uhttps://zaguan.unizar.es/record/164132/files/texto_completo.pdf$$yVersión publicada
000164132 8564_ $$s3395282$$uhttps://zaguan.unizar.es/record/164132/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000164132 909CO $$ooai:zaguan.unizar.es:164132$$particulos$$pdriver
000164132 951__ $$a2025-11-21-14:27:09
000164132 980__ $$aARTICLE