A Semiconducting Bi2O2(C4O4) Coordination Polymer Showing a Photoelectric Response

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.9b03290.[EN] Inorganic semiconductors are extensively considered to be among the most promising materials to convert solar light into electricity or chemical energy owing to their efficiency in the separation of photoinduced electron/hole. Bismuth oxides, and, in particular, those built up of [Bi2O2](2+) layers, show an efficient charge separation and, thus, high photocatalytic activities. To explore a possible synergetic effect of bismuth metallic nodes combined with the electron-rich linker squarate, Bi2O2(C4O4) or IEF-3 (an IMDEA Energy framework) was hydrothermally prepared and adequately characterized. As determined from the X-ray structure, [Bi2O2](2+) layers are interconnected by squarate ligands, having a pronounced effect of the 6s(2) lone pair on the bismuth local environment. IEF-3 shows high thermal and chemical robustness at industrially relevant model aggressive media. A large panel of physicochemical methods were applied to recognize IEF-3 as an UV-absorbing n-type semiconductor, showing a photocurrent response comparable to that of alpha-Bi2O3, offering further possibilities for tuning its electrochemical properties by modifying the ligand. In this way, the well-known compositional and structural versatility of coordination polymers may be applied in the future to fine-tune metal-organic semiconductor systems.The authors acknowledge Ra-Phuel (Grant ENE2016-79608-C2-1-R), Ramon y Cajal Grant RYC-2014-15039 (Ministerio de Ciencia, Investigacion y Universidades), and Fundacion Ramon Areces (H + MOFs) for financial support. S.N. is thankful for financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovacion y Universidades project (Project RTI2018-099482-A-I00), and Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project. H.G. is thankful for financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa SEV2016 and RTI2018-890237-CO2-1), and Generalitat Valenciana (Prometeo 2017/083) is also gratefully acknowledged.Babaryk, AA.; Contreras Almengor, OR.; Cabrero-Antonino, M.; Navalón Oltra, S.; García Gómez, H.; Horcajada, P. (2020). A Semiconducting Bi2O2(C4O4) Coordination Polymer Showing a Photoelectric Response. Inorganic Chemistry. 59(6):3406-3416. https://doi.org/10.1021/acs.inorgchem.9b03290S34063416596Lund, H. (2007). Renewable energy strategies for sustainable development. 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A Novel Porous Ti-Squarate as Efficient Photocatalyst in the Overall Water Splitting Reaction under Simulated Sunlight Irradiation

[EN] A new porous titanium(IV) squarate metal¿organic framework (MOF), denoted as IEF-11, having a never reported titanium secondary building unit, is successfully synthesized and fully characterized. IEF-11 not only exhibits a permanent porosity but also an outstanding chemical stability. Further, as a consequence of combining the photoactive Ti(IV) and the electroactive squarate, IEF-11 presents relevant optoelectronic properties, applied here to the photocatalytic overall water splitting reaction. Remarkably, IEF-11 as a photocatalyst is able to produce record H2 amounts for MOF-based materials under simulated sunlight (up to 672 µmol gcatalyst in 22 h) without any activity loss during at least 10 d.P.S.-A. and A.A.B. contributed equally to this work. The authors acknowledge the Ramón Areces Foundation project H+MOFs, the M-ERA-NET C-MOF-cell (grant PCI2020-111998 funded by MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/ PRTR) project, and Retos Investigación MOFSEIDON (grant PID2019-104228RB-I00 funded by MCIN/AEI/10.13039/501100011033) project. S.N. thanks financial support by Ministerio de Ciencia, Innovatión y Universidades RTI2018-099482-A-I00 project and Agència Valenciana de la Innovació (AVI, INNEST/2020/111) project. H.G. thanks financial support to the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo2017/083). T.W. acknowledges financial support from the Swedish Research Council (VR, 2019-05465). Parts of this research were carried out at ¿CRISTAL¿ at SOLEIL. P.S. and A.A.B. sincerely thank to the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020 for the support of the synchrotron experiment.Salcedo-Abraira, P.; Babaryk, AA.; Montero-Lanzuela, E.; Contreras Almengor, OR.; Cabrero-Antonino, M.; Svensson, E.; Willhammar, T.... (2021). A Novel Porous Ti-Squarate as Efficient Photocatalyst in the Overall Water Splitting Reaction under Simulated Sunlight Irradiation. Advanced Materials. 33(52):1-9. https://doi.org/10.1002/adma.20210662719335