Suchergebnisse

[EN] Seven samples of P25 titania containing Au Pt nanoalloys at constant total metal loading (0.25% wt),very similar particle size (1.5 nm) and different proportions of Pt (0.0, 22.8, 27.8, 35.0, 50.0, 69.0 and 100.0% wt) have been prepared and characterized. Formation of real nanoalloys was supported by the shifts in the binding energy values of Au and Pt 4f7/2 peaks in XPS. Using 532 nm laser excitation it was observed that the six samples exhibit similar photocatalytic activity for hydrogen generation in the presence of methanol as a sacrificial electron donor. In contrast, in pure water remarkable differences in efficiency for hydrogen generation between the sample containing exclusively Au that was the most active and the others containing Pt were observed. In addition, oxygen evolution was also observed in the absence of methanol under visible light irradiation. Our results illustrate the potential that nanoalloys offer to optimize the photocatalytic activity of TiO2. ; Financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2012-31325) is gratefully acknowledged. Partial funding of networking by the European union through project TRAIN2 is also acknowledged. P. Montes-Navajas also thanks the Universidad Politecnica de Valencia for a post-doctoral contract for excellence (CEI-01-11, 20090796). ; Montes Navajas, PM.; Serra, M.; García Gómez, H. (2013). Influence of the irradiation wavelength on the photocatalytic activity of Au-Pt nanoalloys supported on TiO2 for hydrogen generation from water. Catalysis Science and Technology. 3(9):2252-2258. https://doi.org/10.1039/c3cy00102d ; S ; 2252 ; 2258 ; 3 ; 9

2356 2360 3 9 ; S ; [EN] A hybrid benzidinium lead iodide perovskite (formula: PbI(3)benzidinium(0.5)) (3) with a 1D structure has been synthesized and characterized. The hybrid perovskite exhibits visible light (lambda > 450 nm) photocatalytic activity to promote the photoinduced electron transfer cis-to-trans isomerization of stilbene. The solid photocatalyst undergoes changes in the particle morphology, but maintains the crystallinity. Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, and CTQ2015-69563-CO2-R1) and the Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. Yong Peng also thanks the Universitat Politecnica de Valencia for a predoctoral scholarship. Peng, Y.; Albero-Sancho, J.; Alvarez, E.; García Gómez, H. (2019). Hybrid benzidinium lead iodide perovskites with a 1D structure as photoinduced electron transfer photocatalysts. Sustainable Energy & Fuels. 3(9):2356-2360. https://doi.org/10.1039/c9se00182d Kojima, A., Teshima, K., Shirai, Y., & Miyasaka, T. (2009). Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells. Journal of the American Chemical Society, 131(17), 6050-6051. doi:10.1021/ja809598r Ponseca, C. S., Savenije, T. J., Abdellah, M., Zheng, K., Yartsev, A., Pascher, T., … Sundström, V. (2014). Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination. Journal of the American Chemical Society, 136(14), 5189-5192. doi:10.1021/ja412583t Saliba, M., Orlandi, S., Matsui, T., Aghazada, S., Cavazzini, M., Correa-Baena, J.-P., … Nazeeruddin, M. K. (2016). A molecularly engineered hole-transporting material for efficient perovskite solar cells. Nature Energy, 1(2). doi:10.1038/nenergy.2015.17 Zhao, D., Wang, C., Song, Z., Yu, Y., Chen, C., Zhao, X., … Yan, Y. (2018). Four-Terminal All-Perovskite Tandem Solar Cells Achieving Power Conversion Efficiencies Exceeding 23%. ACS Energy Letters, 3(2), ...

This work explores a new methodology to adsorb a subphthalocyanine molecule (SubPc) on a hybrid lead bromide perovskite crystal structure with the aim of extending its photoresponse into the visible region. This process consists in the preparation of multidimensional 2D-3D perovskites. The use of large organic cations allows the possibility to insert guest molecules in the crystal structure of the perovskite. In this work, layered and 3D materials are obtained modifying the ratio of the organic cations (A/R) in the perovskite structure (RNH3)2An-1BnX3n+1. The present results show that incorporation of metal-free subphthalocyanine in the interlayer space provided by the 2D phase is a valid procedure to enhance the photoresponse of the perovskite solar cells. ; We thank the microscopy service at Universitat Politècnica de València (UPV) for the support. S. R.-B. also thanks the Research Executive Agency (REA) and the European Commission for the funding received under the Marie Skłodowska Curie actions (H2020-MSCA-IF-2015/grant agreement number 709023/ZESMO). R. G. A. acknowledges the FPI scholarship from MINECO MAT2015-69669-P. P. A. acknowledges the financial support from the Spanish Government through 'Severo Ochoa" (SEV-2016-0683, MINECO) and PGC2018-099744-B-I00 (MCIU/AEI/FEDER). ; Peer reviewed

4827 4833 1 12 ; S ; [EN] By applying the well-known templating mechanism employed for the synthesis of mesoporous silicas to the structuration of sodium alginate, a novel defective 3D tubular graphene material (graphenolite) with hierarchical macro/meso/micro-porous structure, very high powder specific surface area (1820 m2 g¿1) and regular micropore size (0.6 nm) has been obtained. The key feature of the process is the filmogenic property of alginate that is able to replicate the liquid crystal rods formed by the CTAC template in the aqueous phase. The 3D graphene exhibits 2.5 times higher capacitance using Li+ electrolyte compared to K+, indicating that Li+ can ingress to the ultramicropores which, in contrast, are not accessible to K+. Electrochemical impedance measurements also indicate much lower resistance for Li+ in comparison to K+ electrolyte, confirming the benefits of controlled microporosity of 3D graphene granting selective access to Li+, but not to K+. The present report opens the door for the synthesis of a wide range of 3D graphene materials that could be prepared following similar strategies to those employed for the preparation of zeolites and periodic mesoporous aluminosilicates Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-98237-CO2-R1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. A.P. thanks the Spanish Ministry of Science and Education for a Ramon y Cajal research associate contract. We are indebted to Dr Miguel Palomino for CO 2 adsorption measurements and Dr Pedro Atienzar for measurement of the electrical conductivity. Peng, L.; Domenech-Carbo, A.; Primo Arnau, AM.; García Gómez, H. (2019). 3D defective graphenes with subnanometric porosity obtained by soft-templating following zeolite procedures. Nanoscale Advances. 1(12):4827-4833. https://doi.org/10.1039/C9NA00554D Wu, Z.-S., Yang, S., Sun, Y., Parvez, K., Feng, X., & Müllen, K. (2012). 3D Nitrogen-Doped Graphene Aerogel-Supported Fe3O4 ...

Copper-doped titanium dioxide materials with anatase phase (Cu-TiO2, atomic Cu contents ranging from 0 to 3% relative to the sum of Cu and Ti), and particle sizes of 12–15 nm, were synthesised by a solvo-thermal method using ethanol as the solvent and small amounts of water to promote the hydrolysis-condensation processes. Diffuse reflectance UV-vis spectroscopy show that the edges of absorption of the titania materials are somewhat shifted to higher wavelengths due to the presence of Cu. X-Ray Photoelectron Spectroscopy (XPS) indicate that Cu(II) is predominant. Photocatalytic CO2 reduction experiments were performed in aqueous Cu-TiO2 suspensions under UV-rich light and in the presence of different solutes. Sulfide was found to promote the efficient production of H2 from water and formic acid from CO2. The effect of the Cu content on the photoactivity of Cu-TiO2 was also studied, showing that copper plays a role on the photocatalytic reduction of CO2. ; 1) Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315). F.G. 2) Financial support from Spanish Government (AP2010-2748 PhD grant and MAT2011- 27008 project) 3) Jaume I University (P1 1B2014-21 project). 4) Consejo Superior de Investigaciones Cientifiıcas (CSIC) and the European Social Fund (ESF) for a JAE-Doc postdoctoral grant.

The current work focused on the sunlight-driven thermo-photocatalytic reduction of carbon dioxide (CO), the primary greenhouse gas, by ethane (C H), the second most abundant element in shale gas, aiming at the generation of ethanol (EtOH), a renewable fuel. To promote this process, a hybrid catalyst was prepared and properly characterized, comprising of strontium titanate (SrTiO) co-doped with ruthenium oxide (RuO) and nickel oxide (NiO). The photocatalytic activity towards EtOH production was assessed in batch-mode and at gas-phase, under the influence of different conditions: (i) dopant loading; (ii) temperature; (iii) optical radiation wavelength; (vi) consecutive uses; and (v) electron scavenger addition. From the results here obtained, it was found that: (i) the functionalization of the SrTiO with RuO and NiO allows the visible light harvest and narrows the band gap energy (ca. 14–20%); (ii) the selectivity towards EtOH depends on the presence of Ni and irradiation; (iii) the catalyst photoresponse is mainly due to the visible photons; (iv) the photocatalyst loses > 50% efficiency right after the 2nd use; (v) the reaction mechanism is based on the photogenerated electron-hole pair charge separation; and (vi) a maximum yield of 64 µmol EtOH g was obtained after 45-min (85 µmol EtOH g h) of simulated solar irradiation (1000 W m) at 200 C, using 0.4 g L of SrTiO:RuO:NiO (0.8 wt.% Ru) with [CO ]:[C H ] and [Ru]:[Ni] molar ratios of 1:3 and 1:1, respectively. Notwithstanding, despite its exploratory nature, this study offers an alternative route to solar fuels' synthesis from the underutilized C H and CO. ; This work was financially supported by the Base Funding—UIDB/50020/2020 of the Associate Laboratory LSRE-LCM—funded by national funds through FCT/MCTES (PIDDAC). Larissa O. Paulista also wants to acknowledge for her doctoral fellowship (reference SFRH/BD/137639/2018), supported by FCT. Tânia F. C. V. Silva and Vítor J. P. Vilar acknowledge the FCT Individual Call to Scientific Employment Stimulus 2017 (CEECIND/01386/2017 and CEECIND/01317/2017, respectively). Josep Albero and Hermenegildo García are also grateful to the Spanish Ministry of Science and Innovation (RTI2018-098237-CO2-R1 and Severo Ochoa), Generalitat Valencia (Prometeo 2017/083) and European Union's Horizon 2020 research and innovation programme under grant agreement No 862453, project FlowPhotochem, by financial contribution.

Copper-doped titanium dioxide materials with anatase phase (Cu-TiO2, atomic Cu contents ranging from 0 to 3% relative to the sum of Cu and Ti), and particle sizes of 12-15 nm, were synthesised by a solvo-thermal method using ethanol as the solvent and small amounts of water to promote the hydrolysiscondensation processes. Diffuse reflectance UV-vis spectroscopy show that the edges of absorption of the titania materials are somewhat shifted to higher wavelengths due to the presence of Cu. X-ray photoelectron spectroscopy (XPS) indicate that Cu(II) is predominant. Photocatalytic CO2 reduction experiments were performed in aqueous Cu-TiO2 suspensions under UV-rich light and in the presence of different solutes. Sulfide was found to promote the efficient production of H-2 from water and formic acid from CO2. The effect of the Cu content on the photoactivity of Cu-TiO2 was also studied, showing that copper plays a role on the photocatalytic reduction of CO2. ; Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315) is gratefully acknowledged. F.G. and B.J.-L. are thankful for financial support from Spanish Government (AP2010-2748 PhD grant and MAT2011-27008 project) and Jaume I University (P1 1B2014-21 project). SCIC from Jaume I University and Servicio de Microscopia Electronica at Universitat Politecnica de Valencia are also acknowledged for instrumental facilities. A.V.P. is grateful to both the Consejo Superior de Investigaciones Cientifficas (CSIC) and the European Social Fund (ESF) for a JAE-Doc postdoctoral grant. Lichen Liu is gratefully acknowledged for assistance in recording HRTEM images. ; Gonell-Gómez, F.; Puga Vaca, A.; Julián López, B.; García Gómez, H.; Corma Canós, A. (2016). Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H-2 from aqueous sulfide. Applied Catalysis B: Environmental. 180:263-270. https://doi.org/10.1016/j.apcatb.2015.06.019 ; S ; 263 ; 270 ; 180

[EN] Thermal annealing at 400 degrees C of perylenetetracarboxylic anhydride in low molecular mass PEG gives rise to the formation of well defined nanoobjects of 2.5 nm height and size distribution from 10 to 65 nm (average 40 nm) after purification of the raw mixture with silicagel chromatography. TEM reveals that the flat nanoobjects are constituted of concentric graphenic rings (0.34 nm interlayer distance). The morphology of the nanoparticles resembles onion rings of nanometric dimensions (nanoonion rings C-NOR). C-NOR particles have an excitation dependent emission with lambda(em) from 430 to 570 nm and a maximum emission quantum yield of 0.49. C-NOR particles can be internalized into Hep3B human hepatoma cells as determined by confocal fluorescence microscopy and are remarkably biocompatible affecting slightly cell viability according to the MTT test. ; Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315) and Generalidad Valenciana (Promoteo 2012-013) is gratefully acknowledged. JRH and VMV are recipients of contracts from Valencian Regional Government, the Ministry of Health (CP13/00252) and Carlos III Health Institute (PI13/1025), respectively. HGB and JRH thank the Generidad Valenciana and FIS for a postgraduate scholarship and a research contract, respectively. ; García Baldoví, H.; Herance Camacho, JR.; Víctor, VM.; Alvaro Rodríguez, MM.; García Gómez, H. (2015). Perylenetetracarboxylic anhydride as a precursor of fluorescent carbon nanoonion rings. Nanoscale. 7(29):12484-12491. https://doi.org/10.1039/C5NR02903A ; S ; 12484 ; 12491 ; 7 ; 29

In the present work, two carbon quantum dots with onion ring morphology, C-NOR and C-NOR(Eu) with an average size of 40 nm differing in the absence or presence of Eu3+ as Lewis acids during their preparation were synthesized and fully characterized by several techniques. These nanoparticles can be internalized into human HeLa and Hep3B carcinoma cells where they exhibit interesting photoluminescent properties, in the same manner as in solution, confirming their utility as bioimaging agents. To address this possibility, a complete in vitro toxicological study has been performed here. Viability, proliferation, apoptosis and oxidative stress assessments upon limited or continuous exposure were done. It was observed that both nanoparticles did not show toxicity in both situations at low concentration, although some toxicity has been determined at higher concentrations under continuous exposure. These results support the possible use of C-NOR and C-NOR(Eu) nanoparticles as bioimaging agents. ; The present work was supported by grants CP13/00252, PI13/1025 from Carlos III Health Institute, and by the European Regional Development Fund (ERDF). In addition, this study was financed by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ-2012-32315), Generalitat Valenciana (Prometeo 2013/19), and FISABIO (UGP-14-95). This work was supported by the Ministerio de Economia y Competitividad (JCI-2012-15124 grant to A. B.-G.), and the Conselleria d'Educacio, Formacio i Ocupacio, Generalitat Valenciana (ACIF/2013/136 grant to M. P). V. M. V. is recipient of a contract from the Ministry of Health of the Valencian Regional Government and Carlos III Health Institute (CES10/030). ; Blas García, A.; Baldovi, HG.; Polo, M.; Victor, VM.; García Gómez, H.; Herance Camacho, JR. (2016). Toxicological properties of two fluorescent carbon quantum dots with onion ring morphology and their usefulness as bioimaging agents. RSC Advances. 6(36):30611-30622. https://doi.org/10.1039/c5ra27662d ; S ; 30611 ; 30622 ; 6 ; 36

This is the peer reviewed version of the following article:Mateo-Mateo, Diego, De Masi, Deborah , Albero-Sancho, Josep, Lacroix, Lisa-Marie , Fazzini, Pier-Francesco , Chaudret, Bruno , García Gómez, Hermenegildo. (2018). Synergism of Au and Ru Nanoparticles in Low-Temperature Photoassisted CO2 Methanation.Chemistry - A European Journal, 24, 69, 18436-18443. DOI:10.1002/chem.201803022, which has been published in final form at http://doi.org/10.1002/chem.201803022. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions ; [EN] Au and Ru nanoparticles have been deposited on Siralox® substrate by impregnation and chemical reduction, respectively (Au-Ru-S). The as-prepared material has demonstrated to be very active for the selective CO2 metanation to CH4 at temperatures below 250 oC. In addition, Au-Ru-S exhibits CH4 production enhancement upon UV-Vis light irradiation starting at temepratures higher than 200 oC, although the contribution of the photoassisted pathway of CH4 production decreases as temperature increases. Thus, a maximum CH4 production of 204 mmol/gRu at 250 oC upon 100 mW/cm2 irradiation was achieved. Control experiments using Ru-S and Au-S materials revealed that Ru nanoparticles are the CO2 methanation active sites, while Au NPs contribute harvesting light, mainly visible as consequence of the strong Au plasmon band centrered at 529 nm. The visible light absorbed by Au NPs plasmon could act as local heaters of neighbouring Ru NPs, increasing their temperature and enhancing CH4 production. ; D. M., J.A., and H.G. thank the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV2016-0683 and CTQ2015-69563-CO2-1), Generalitat Valenciana (Prometeo 2017-083) for financial support. J.A. and D.M. also thank UPV for a postdoctoral scholarship and the Spanish Ministry of Science for a PhD Scholarship, respectively. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation ...

[EN] The hydrogenation of CO2 into hydrocarbons promoted by the action of sunlight has been studied on Co nanoparticles covered by thin carbon layers. In particular, nearly 100% selectivity to hydrocarbons is obtained with increased selectivities towards C2 + hydrocarbons and alcohols (mainly ethanol) when using nanostructured materials comprising metallic cobalt nanoparticles, carbon layers, and sodium as promoter (NaCo@C). In the contrary, larger amount of CH4 and lower selectivity to C2 + hydrocarbons and alcohols were obtained in the conventional thermal catalytic process. When using Co@C nanoparticles in the absence of Na or bare Co3O4 as catalyst, methane is essentially the main product (selectivity > 96%). Control experiments in the presence of methanol as a hole scavenger suggest the role of light in generating charges by photon absorption as promoting factor. The reaction mechanism for photoassisted CO2 hydrogenation on the Co-based catalysts was investigated by near ambient-pressure X-ray photoelectron (AP-XPS) and in situ Raman spectroscopies, which provided information on the role of light and Na promoter in the modulation of product distribution for CO2 hydrogenation. Spectroscopic studies suggested that surface CO2 dissociation to CO, the stabilization of CO adsorbed on the surface of Na-Co@C catalyst and the easy desorption of reaction products is a key step for photothermal CO2 hydrogenation to ethanol and C2 + hydrocarbons. ; L.L. thanks ITQ for providing a contract. A.V.P. thanks the Spanish Government (Agencia Estatal de Investigacion) and the European Union (European Regional Development Fund) for a grant for young researchers (CTQ2015-74138-JIN, AEI/FEDER/UE). J.C. thanks the Spanish Government-MINECO for a "Severo Ochoa" grant (BES-2015-075748). The AP-XPS experiments were performed at NAPP endstation of CIRCE beamline at ALBA Synchrotron with the collaboration of ALBA staff. The authors also thank the Microscopy Service of UPV for kind help on FESEM, TEM and STEM measurements. Financial ...

Most developments in the chemistry and applications of metal-organic frameworks (MOFs) have been made possible thanks to the value of reticular chemistry in guiding the unlimited combination of organic connectors and secondary building units (SBUs) into targeted architectures. However, the development of new titanium-frameworks still remains limited by the difficulties in controlling the formation of persistent Ti-SBUs with predetermined directionality amenable to the isoreticular approach. Here we report the synthesis of a mesoporous Ti-MOF displaying a MIL-100 topology. MIL-100(Ti) combines excellent chemical stability and mesoporosity, intrinsic to this archetypical family of porous materials, with photoactive Ti(μ-O) metal-oxo clusters. By using high-throughput synthetic methodologies, we have confirmed that the formation of this SBU is thermodynamically favored as it is not strictly dependent on the metal precursor of choice and can be regarded as an adequate building block to control the design of new Ti-MOF architectures. We are confident that the addition of a mesoporous solid to the small number of crystalline, porous titanium-frameworks available will be a valuable asset to accelerate the development of new porous photocatalysts without the pore size limitations currently imposed by the microporous materials available. ; This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish MINECO (MDM-2015-0538 & CTQ2017- 83486-P). C. M.-G. and J. C.-G. thank the Spanish MINECO for a Ramón y Cajal Fellowship (RYC-2012-10894) and FPI Scholarship (CTQ2014-59209-P). N. M. P. thanks the European Union for a Marie Skłodowska-Curie Global Fellowship (H2020-MSCAIF-2016-GF-749359-EnanSET). We thank the ISIS Facility for the access to synchrotron radiation, BSC-RES and Prof. Enrique Ort´ı for computational resources and Bel´en Lerma-Berlanga for technical help.

Ceria nanoparticles are cell compatible antioxidants whose activity can be enhanced by gold deposition and by surface functionalization with positive triphenylphosphonium units to selectively target the mitochondria. The antioxidant properties of these nanoparticles can serve as the basis of a new strategy for the treatment of several disorders exhibiting oxidative stress, such as cancer, diabetes or Alzheimer's disease. However, all of these pathologies require a specific antioxidant according with their mechanism to remove oxidant species excess in cells and diminish their effect on mitochondrial function. The mechanism through which ceria nanoparticles neutralize oxidative stress and their effect on mitochondrial function have not been characterized yet. In the present study, the mitochondria antioxidant effect of ceria and ceria‐supported gold nanoparticles, with or without triphenylphosphonium functionalization, was assessed in HeLa cells. The effect caused by ceria nanoparticles on mitochondria function in terms of mitochondrial membrane potential (∆Ψm), adenosine triphosphate (ATP) production, nuclear respiratory factor 1 (NRF1) and nuclear factor erythroid–2–like 1 (NFE2L1) was reversed by the presence of gold. Furthermore, this effect was enhanced when nanoparticles were functionalized with triphenylphosphonium. Our study illustrates how the mitochondrial antioxidant effect induced by ceria nanoparticles can be modulated by the presence of gold. ; This research was funded by Carlos III Health Institute and the European Regional Development Fund, grant number CP13/00252 and PI16/1083; the Catalonian Agency for Management of University and Research Grants, grant number 2017SGR1303; the Ministry of Education of the Valencian Regional Government, grant number PROMETEO/2019/027, The Foundation for the Promotion of Health and Biomedical Research of Valencia Region, grant number Nanobetes2.

[EN] Ceria nanoparticles are cell compatible antioxidants whose activity can be enhanced by gold deposition and by surface functionalization with positive triphenylphosphonium units to selectively target the mitochondria. The antioxidant properties of these nanoparticles can serve as the basis of a new strategy for the treatment of several disorders exhibiting oxidative stress, such as cancer, diabetes or Alzheimer's disease. However, all of these pathologies require a specific antioxidant according with their mechanism to remove oxidant species excess in cells and diminish their effect on mitochondrial function. The mechanism through which ceria nanoparticles neutralize oxidative stress and their effect on mitochondrial function have not been characterized yet. In the present study, the mitochondria antioxidant effect of ceria and ceria-supported gold nanoparticles, with or without triphenylphosphonium functionalization, was assessed in HeLa cells. The effect caused by ceria nanoparticles on mitochondria function in terms of mitochondrial membrane potential (Delta Psi m), adenosine triphosphate (ATP) production, nuclear respiratory factor 1 (NRF1) and nuclear factor erythroid-2 like 1 (NFE2L1) was reversed by the presence of gold. Furthermore, this effect was enhanced when nanoparticles were functionalized with triphenylphosphonium. Our study illustrates how the mitochondrial antioxidant effect induced by ceria nanoparticles can be modulated by the presence of gold. ; This research was funded by Carlos III Health Institute and the European Regional Development Fund, grant number CP13/00252 and PI16/1083; the Catalonian Agency for Management of University and Research Grants, grant number 2017SGR1303; the Ministry of Education of the Valencian Regional Government, grant number PROMETEO/2019/027, The Foundation for the Promotion of Health and Biomedical Research of Valencia Region, grant number Nanobetes2. ; Gutiérrez-Carcedo, P.; Navalón Oltra, S.; Simó, R.; Setoain, X.; Aparicio-Gómez, C.; Abasolo, I.; Victor, ...

[EN] Most developments in the chemistry and applications of metal-organic frameworks (MOFs) have been made possible thanks to the value of reticular chemistry in guiding the unlimited combination of organic connectors and secondary building units (SBUs) into targeted architectures. However, the development of new titanium-frameworks still remains limited by the difficulties in controlling the formation of persistent Ti-SBUs with predetermined directionality amenable to the isoreticular approach. Here we report the synthesis of a mesoporous Ti-MOF displaying a MIL-100 topology. MIL-100(Ti) combines excellent chemical stability and mesoporosity, intrinsic to this archetypical family of porous materials, with photoactive Ti-3((3)-O) metal-oxo clusters. By using high-throughput synthetic methodologies, we have confirmed that the formation of this SBU is thermodynamically favored as it is not strictly dependent on the metal precursor of choice and can be regarded as an adequate building block to control the design of new Ti-MOF architectures. We are confident that the addition of a mesoporous solid to the small number of crystalline, porous titanium-frameworks available will be a valuable asset to accelerate the development of new porous photocatalysts without the pore size limitations currently imposed by the microporous materials available. ; This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish MINECO (MDM-2015-0538 & CTQ2017-83486-P). C. M.-G. and J. C.-G. thank the Spanish MINECO for a Ramon y Cajal Fellowship (RYC-2012-10894) and FPI Scholarship (CTQ2014-59209-P). N. M. P. thanks the European Union for a Marie Skodowska-Curie Global Fellowship (H2020-MSCA-IF-2016-GF-749359-EnanSET). We thank the ISIS Facility for the access to synchrotron radiation, BSC-RES and Prof. Enrique Orti for computational resources and Belen Lerma-Berlanga for technical help. ; Castells-Gil, J.; Padial, NM.; Almora-Barrios, N.; Da Silva, I.; Mateo-Mateo, D.; Albero-Sancho, J.; García Gómez, H. (2019). De novo ...