Multilayer N-doped graphene films as photoelectrodes for H2 evolution

[EN] Multilayer N-doped graphene photoelectrodes have been prepared following a straightforward one-step pyrolytic fabrication method. The N-doped graphene photoelectrodes have been demonstrated to work both as semitransparent electrodes and as efficient photoelectrocatalysts for H2 evolution at low bias. N-doped graphene photoelectrodes exhibited a constant H2 generation rate of 3.64 mmolh @1 cm2 at 0.2 V under 3443 Wm@2 irradiation for 17 h, reaching an applied-bias-compensated solar-to-hydrogen efficiency of 1.8%. The N-doped graphene photoelectrodes show light-intensity dependence as well as photocatalytic activity for H2 evolution in the UV/Vis spectral region. Impedance spectroscopy provides experimental evidence indicating that charge separation within N-doped graphene increases upon positive bias polarization of the photoelectrode.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, Grapas and CTQ2015-69153-C02-R1) and Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. J.A. also thanks the Universitat Politecnica de Valencia for a postdoctoral scholarship.García-Gómez, A.; Albero-Sancho, J.; García Gómez, H. (2017). Multilayer N-doped graphene films as photoelectrodes for H2 evolution. ChemPhotoChem. 1(9):388-392. https://doi.org/10.1002/cptc.201700049S3883921

Luminescence control in hybrid perovskites and their applications

[EN] Hybrid metal halide perovskites have emerged as promising semiconductor materials for photovoltaic applications as a consequence of their remarkable intrinsic optoelectronic properties and their compositional flexibility. However, these properties have also been found to be suitable for applications in other different fields. In particular, the photoluminescence properties of hybrid perovskites have demonstrated to give rise to efficient light emitting devices as well as lasing applications. In this manuscript we have reviewed the recent advances of hybrid perovskites in these fields paying attention to the compositional design of perovskites as a tool to modulate the luminescence properties of this class of devices.Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, and CTQ2015-69563-CO2-R1) and from the Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. J. A. also thanks the Universitat Politecnica de Valencia for a postdoctoral scholarship.Albero-Sancho, J.; García Gómez, H. (2017). Luminescence control in hybrid perovskites and their applications. Journal of Materials Chemistry C. 5(17):4098-4110. https://doi.org/10.1039/C7TC00714KS40984110517Kojima, 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/ja809598rZhou, H., Chen, Q., Li, G., Luo, S., Song, T. -b., Duan, H.-S., … Yang, Y. (2014). Interface engineering of highly efficient perovskite solar cells. Science, 345(6196), 542-546. doi:10.1126/science.1254050Jeon, N. J., Noh, J. H., Yang, W. S., Kim, Y. C., Ryu, S., Seo, J., & Seok, S. I. (2015). Compositional engineering of perovskite materials for high-performance solar cells. Nature, 517(7535), 476-480. doi:10.1038/nature14133Muthu, C., Nagamma, S. R., & Nair, V. C. (2014). 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(2015). Review of recent progress in chemical stability of perovskite solar cells. Journa

Formation of C-C and C-Heteroatom Bonds by C-H Activation by Metal Organic Frameworks as Catalysts or Supports

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, 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/acscatal.8b04506"[EN] Cross-coupling reactions catalyzed by transition metals are currently among the most widely used transformations in organic synthesis. In most of these reactions, the coupling involves the reaction of two complementary functional groups, particularly boronates and halides. For the sake of atom economy and simplicity of the starting materials, it is more advantageous when the coupling involves C-H activation of one substrate lacking a reactive functional group. The present review focuses on the use of metal organic frameworks (MOFs) as solid reusable catalysts to promote cross-coupling reactions involving C-H activation. After general considerations, the review is organized according to the bond formed in the coupling, either C-C or C-heteroatom (N, O, B and X). The purpose of this mini review is to show the performance of MOFs as heterogeneous catalysts in these reactions, combining a high activity due to the large percentage of accessible metal sites and high stability allowing the reuse of the material in consecutive cycles. Comparison with homogeneous analogous catalysts indicates that this improved performance derives from the porosity, large surface area and site isolation and immobilization occurring in the MOFs. Considering the growing interests in these reactions the last section forecasts future developments in these areas in near future.A.D. thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. A.D. also thanks the Department of Science and Technology, India, for the financial support through Extra Mural Research Funding (EMR/2016/006500). Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.Dhakshinamoorthy, A.; Asiri, A.; García Gómez, H. (2019). Formation of C-C and C-Heteroatom Bonds by C-H Activation by Metal Organic Frameworks as Catalysts or Supports. ACS Catalysis. 9(2):1081-1102. https://doi.org/10.1021/acscatal.8b04506S108111029

Producción de carbamatos en un recipiente usando catalizadores sólidos

Peer reviewedConsejo Superior de Investigaciones CientíficasT3 Traducción de patente europe

Preparación de carbamatos en “one pot” con catalizadores sólidos.

Titulares: Universidad Politécnica de Valencia. - Consejo Superior de Investigaciones CientíficasPreparación de carbamatos en “one pot” con catalizadores sólidos. Preparación de carbamatos en un solo reactor (“one pot”) con catalizadores sólidos que comprende, la reacción entre al menos: - un compuesto nitro, - un carbonato orgánico de fórmula (OR)(OR’)C=O, - un gas seleccionado entre hidrógeno gas, una mezcla de gases conteniendo hidrógeno y compuestos precursores de hidrógeno, - un catalizador que comprende al menos un óxido metálico y que puede además contener un elemento de los grupos 8, 9, 10 y 11 del sistema periódico. Los carbonatos obtenidos pueden ser transformados en sus correspondientes isocianatos.Peer reviewe

Highly fluorescent C-dots obtained by pyrolysis of quaternary ammonium ions trapped in all-silica ITQ-29 zeolite

[EN] C-dots obtained in the homogeneous phase may exhibit a broad particle size distribution. The formation of C-dots within nanometric reaction cavities could be a methodology to gain control on their size distribution. Among the various possibilities, in the present work, the cavities of small pore size zeolites have been used to confine C-dots generated by the pyrolysis of the organic structure directing agent present in the synthesis of these crystalline aluminosilicates. To explore this methodology, ITQ-29 zeolite having a Linde type A (LTA) structure was prepared as pure silica with 4-methyl-2,3,6,7-tetrahydro-1H, 5H-pyrido[3.2.1-ij] quinolinium as the organic structure directing agent. Pyrolysis under an inert atmosphere at 550 degrees C of a pure-silica ITQ-29 sample (cubic particles of 4 mu m edge) renders a highly fluorescent zeolite containing about 15 wt% of the carbonised residue. While another small pore zeolite, ITQ-12 (ITW), also renders photoluminescent C-dots under similar conditions, medium or large pore zeolites, such as silicalite (MFI) or pure silica Beta (BEA), failed to produce fluorescent powders under analogous thermal treatment and only decomposition and complete removal of the corresponding quaternary ammonium ion templates was observed for these zeolites. The dissolution of the pyrolysed ITQ-29 zeolite framework and the extraction of the carbon residue with ethyl acetate have allowed the characterisation of C-dots with particle sizes between 5 and 12 nm and a photoluminescence quantum yield of 0.4 upon excitation at 350 nm that is among the highest reported for non-surface functionalized C-dots. Photoluminescence varies with the excitation wavelength and is quenched by oxygen. Pyrolysed ITQ-29 powders can act as fluorescent oxygen sensors.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315) and Generalidad Valenciana (Prometeo 2012-014) is gratefully acknowledged.García Baldoví, H.; Valencia Valencia, S.; Alvaro Rodríguez, MM.; Abdullah, AM.; García Gómez, H. (2015). Highly fluorescent C-dots obtained by pyrolysis of quaternary ammonium ions trapped in all-silica ITQ-29 zeolite. Nanoscale. 7(5):1744-1752. https://doi.org/10.1039/C4NR05295AS174417527

Photocatalytic CO2 Reduction to C2+Products

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, 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/acscatal.0c00478[EN] There is a considerable interest in the development of photocatalytic CO2 conversion by sunlight, since this process has similarities with natural photosynthesis on which life on Earth is based. At the moment, most of the efforts in this field have been aimed at increasing the productivity, rather than at the control of the product distribution. Particularly, compounds with two or more carbons (C2+) have higher added value than methane, carbon monoxide, or formate, which are typically the major products of CO2 reduction. This review focuses on those reports that have described the formation of compounds of two or more carbon atoms (C2+) in the photocatalytic CO2 reduction either by H2O or as H-2 as a source of electrons and protons. The existing literature has been organized according to the main factor considered to be responsible for the selectivity to C2+ products, including photocatalyst structuration, nature of the co-catalyst, influence of defects, and effects of surface plasmon band. Emphasis has been made on remarking the current empirical knowledge based on experimental results and the lack of predictive capability that could lead to the development of efficient photocatalytic systems for C2+ production.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and No. CTQ2018-89237-CO2R1) and Generalitat Valenciana (Prometeo 2017/83) is gratefully acknowledged.Albero-Sancho, J.; Peng, Y.; García Gómez, H. (2020). Photocatalytic CO2 Reduction to C2+Products. ACS Catalysis. 10(10):5734-5749. https://doi.org/10.1021/acscatal.0c00478573457491010Low, J., Cheng, B., & Yu, J. (2017). Surface modification and enhanced photocatalytic CO2 reduction performance of TiO2: a review. Applied Surface Science, 392, 658-686. doi:10.1016/j.apsusc.2016.09.093Zeng, S., Kar, P., Thakur, U. K., & Shankar, K. (2018). A review on photocatalytic CO2reduction using perovskite oxide nanomaterials. Nanotechnology, 29(5), 052001. doi:10.1088/1361-6528/aa9fb1Ola, O., & Maroto-Valer, M. M. (2015). Review of material design and reactor engineering on TiO2 photocatalysis for CO2 reduction. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 24, 16-42. doi:10.1016/j.jphotochemrev.2015.06.001Tachibana, Y., Vayssieres, L., & Durrant, J. R. (2012). Artificial photosynthesis for solar water-splitting. Nature Photonics, 6(8), 511-518. doi:10.1038/nphoton.2012.175Gust, D., Moore, T. A., & Moore, A. L. (2009). Solar Fuels via Artificial Photosynthesis. 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Synthesis, post-synthetic modification and stability of a 2D styryl ammonium lead iodide hybrid material

[EN] A new hybrid lead iodide material (HP1) having 4-vinylphenylene ammonium as the organic cation has been prepared. The structural formula based on chemical analysis of HP1 corresponds to PbI2.5(4-styrylammonium)(0.5). The crystallinity of HP1 was confirmed by powder X-ray diffraction and high resolution transmission electron microscopy. The presence of the styryl ammonium moiety in HP1 allows post-synthetic modification by radical copolymerization with styrene to obtain the HP2 material with higher hydrophobicity. Stability tests reveal that both HP1 and HP2 show hydrogen evolution in the dark, indicating about 0.6% partial decomposition of the hybrid material. This hydrogen evolution increases by a factor of 3 when HP1 and HP2 are exposed to visible light. X-ray photoelectron spectroscopy analysis shows an increase of NH2 groups and a decrease of NH3+ units suggesting that the origin of hydrogen evolution is the deprotonation of ammonium ions.Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV2016, and RTI2018-890237-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.; García Gómez, H. (2020). Synthesis, post-synthetic modification and stability of a 2D styryl ammonium lead iodide hybrid material. Dalton Transactions. 49(2):395-403. https://doi.org/10.1039/C9DT04285GS395403492Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N., & Snaith, H. J. (2012). Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites. Science, 338(6107), 643-647. doi:10.1126/science.1228604Boix, P. P., Agarwala, S., Koh, T. M., Mathews, N., & Mhaisalkar, S. G. (2015). Perovskite Solar Cells: Beyond Methylammonium Lead Iodide. The Journal of Physical Chemistry Letters, 6(5), 898-907. doi:10.1021/jz502547fEames, C., Frost, J. M., Barnes, P. R. F., O’Regan, B. C., Walsh, A., & Islam, M. S. (2015). Ionic transport in hybrid lead iodide perovskite solar cells. Nature Communications, 6(1). doi:10.1038/ncomms8497Kato, Y., Ono, L. K., Lee, M. V., Wang, S., Raga, S. R., & Qi, Y. (2015). Silver Iodide Formation in Methyl Ammonium Lead Iodide Perovskite Solar Cells with Silver Top Electrodes. Advanced Materials Interfaces, 2(13), 1500195. doi:10.1002/admi.201500195Malinkiewicz, O., Yella, A., Lee, Y. H., Espallargas, G. M., Graetzel, M., Nazeeruddin, M. K., & Bolink, H. J. (2013). Perovskite solar cells employing organic charge-transport layers. Nature Photonics, 8(2), 128-132. doi:10.1038/nphoton.2013.341Christians, J. A., Manser, J. S., & Kamat, P. V. (2015). Multifaceted Excited State of CH3NH3PbI3. Charge Separation, Recombination, and Trapping. The Journal of Physical Chemistry Letters, 6(11), 2086-2095. doi:10.1021/acs.jpclett.5b00594Stranks, S. D., Eperon, G. E., Grancini, G., Menelaou, C., Alcocer, M. J. P., Leijtens, T., … Snaith, H. J. (2013). Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber. Science, 342(6156), 341-344. doi:10.1126/science.1243982Xing, G., Mathews, N., Sun, S., Lim, S. S., Lam, Y. M., Grätzel, M., … Sum, T. C. (2013). Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH 3 NH 3 PbI 3. Science, 342(6156), 344-347. doi:10.1126/science.1243167Albero, J., & García, H. (2017). Luminescence control in hybrid perovskites and their applications. Journal of Materials Chemistry C, 5(17), 4098-4110. doi:10.1039/c7tc00714kCorrea-Baena, J.-P., Abate, A., Saliba, M., Tress, W., Jesper Jacobsson, T., Grätzel, M., & Hagfeldt, A. (2017). The rapid evolution of highly efficient perovskite solar cells. Energy & Environmental Science, 10(3), 710-727. doi:10.1039/c6ee03397kJeon, N. J., Na, H., Jung, E. H., Yang, T.-Y., Lee, Y. G., Kim, G., … Seo, J. (2018). A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nature Energy, 3(8), 682-689. doi:10.1038/s41560-018-0200-6Sahli, F., Werner, J., Kamino, B. A., Bräuninger, M., Monnard, R., Paviet-Salomon, B., … Ballif, C. (2018). Fully textured monolithic perovskite/silicon tandem solar cells with 25.2% power conversion efficiency. Nature Materials, 17(9), 820-826. doi:10.1038/s41563-018-0115-4Dhakshinamoorthy, A., Navalon, S., Corma, A., & Garcia, H. (2012). Photocatalytic CO2 reduction by TiO2 and related titanium containing solids. Energy & Environmental Science, 5(11), 9217. doi:10.1039/c2ee21948dAlbero, J., Asiri, A. M., & García, H. (2016). Influence of the composition of hybrid perovskites on their performance in solar cells. Journal of Materials Chemistry A, 4(12), 4353-4364. doi:10.1039/c6ta00334fPark, S., Chang, W. J., Lee, C. W., Park, S., Ahn, H.-Y., & Nam, K. T. (2016). Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution. Nature Energy, 2(1). doi:10.1038/nenergy.2016.185Niu, G., Guo, X., & Wang, L. (2015). Review of recent progress in chemical stability of perovskite solar cells. Journal of Materials Chemistry A, 3(17), 8970-8980. doi:10.1039/c4ta04994bSharma, S. K., Phadnis, C., Das, T. K., Kumar, A., Kavaipatti, B., Chowdhury, A., & Yella, A. (2019). Reversible Dimensionality Tuning of Hybrid Perovskites with Humidity: Visualization and Application to Stable Solar Cells. Chemistry of Materials, 31(9), 3111-3117. doi:10.1021/acs.chemmater.8b04115Berhe, T. A., Su, W.-N., Chen, C.-H., Pan, C.-J., Cheng, J.-H., Chen, H.-M., … Hwang, B.-J. (2016). Organometal halide perovskite solar cells: degradation and stability. Energy & Environmental Science, 9(2), 323-356. doi:10.1039/c5ee02733kWang, R., Mujahid, M., Duan, Y., Wang, Z., Xue, J., & Yang, Y. (2019). A Review of Perovskites Solar Cell Stability. Advanced Functional Materials, 29(47), 1808843. doi:10.1002/adfm.201808843Ma, J., Fang, C., Chen, C., Jin, L., Wang, J., Wang, S., … Li, D. (2019). Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence. ACS Nano, 13(3), 3659-3665. doi:10.1021/acsnano.9b00302Tremblay, M.-H., Thouin, F., Leisen, J., Bacsa, J., Srimath Kandada, A. R., Hoffman, J. M., … Marder, S. R. (2019). (4NPEA)2PbI4 (4NPEA = 4-Nitrophenylethylammonium): Structural, NMR, and Optical Properties of a 3 × 3 Corrugated 2D Hybrid Perovskite. Journal of the American Chemical Society, 141(11), 4521-4525. doi:10.1021/jacs.8b13207Spanopoulos, I., Hadar, I., Ke, W., Tu, Q., Chen, M., Tsai, H., … Kanatzidis, M. G. (2019). Uniaxial Expansion of the 2D Ruddlesden–Popper Perovskite Family for Improved Environmental Stability. Journal of the American Chemical Society, 141(13), 5518-5534. doi:10.1021/jacs.9b01327Febriansyah, B., Koh, T. M., John, R. A., Ganguly, R., Li, Y., Bruno, A., … England, J. (2018). Inducing Panchromatic Absorption and Photoconductivity in Polycrystalline Molecular 1D Lead-Iodide Perovskites through π-Stacked Viologens. Chemistry of Materials, 30(17), 5827-5830. doi:10.1021/acs.chemmater.8b02038Zhao, Y.-Q., Ma, Q.-R., Liu, B., Yu, Z.-L., Yang, J., & Cai, M.-Q. (2018). Layer-dependent transport and optoelectronic property in two-dimensional perovskite: (PEA)2PbI4. Nanoscale, 10(18), 8677-8688. doi:10.1039/c8nr00997jByun, J., Cho, H., Wolf, C., Jang, M., Sadhanala, A., Friend, R. H., … Lee, T.-W. (2016). Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes. Advanced Materials, 28(34), 7515-7520. doi:10.1002/adma.201601369Li, N., Zhu, Z., Chueh, C.-C., Liu, H., Peng, B., Petrone, A., … Jen, A. K.-Y. (2016). Mixed Cation FAxPEA1-xPbI3with Enhanced Phase and Ambient Stability toward High-Performance Perovskite Solar Cells. Advanced Energy Materials, 7(1), 1601307. doi:10.1002/aenm.201601307Arabpour Roghabadi, F., Alidaei, M., Mousavi, S. M., Ashjari, T., Tehrani, A. S., Ahmadi, V., & Sadrameli, S. M. (2019). Stability progress of perovskite solar cells dependent on the crystalline structure: From 3D ABX3 to 2D Ruddlesden–Popper perovskite absorbers. Journal of Materials Chemistry A, 7(11), 5898-5933. doi:10.1039/c8ta10444aKhuong, K. S., Jones, W. H., Pryor, W. A., & Houk, K. N. (2005). The Mechanism of the Self-Initiated Thermal Polymerization of Styrene. Theoretical Solution of a Classic Problem. Journal of the American Chemical Society, 127(4), 1265-1277. doi:10.1021/ja0448667Yao, K., Wang, X., Li, F., & Zhou, L. (2015). Mixed perovskite based on methyl-ammonium and polymeric-ammonium for stable and reproducible solar cells. Chemical Communications, 51(84), 15430-15433. doi:10.1039/c5cc05879aBubnova, O. (2016). 2D materials: Hybrid interfaces. Nature Nanotechnology. doi:10.1038/nnano.2016.13Saidaminov, M. I., Abdelhady, A. L., Murali, B., Alarousu, E., Burlakov, V. M., Peng, W., … Bakr, O. M. (2015). High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nature Communications, 6(1). doi:10.1038/ncomms8586Baikie, T., Fang, Y., Kadro, J. M., Schreyer, M., Wei, F., Mhaisalkar, S. G., … White, T. J. (2013). Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications. Journal of Materials Chemistry A, 1(18), 5628. doi:10.1039/c3ta10518kDou, L., Wong, A. B., Yu, Y., Lai, M., Kornienko, N., Eaton, S. W., … Yang, P. (2015). Atomically thin two-dimensional organic-inorganic hybrid perovskites. Science, 349(6255), 1518-1521. doi:10.1126/science.aac7660Milot, R. L., Sutton, R. J., Eperon, G. E., Haghighirad, A. A., Martinez Hardigree, J., Miranda, L., … Herz, L. M. (2016). Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites. Nano Letters, 16(11), 7001-7007. doi:10.1021/acs.nanolett.6b03114Véron, A. C., Linden, A., Leclaire, N. A., Roedern, E., Hu, S., Ren, W., … Nüesch, F. A. (2018). One-Dimensional Organic–Inorganic Hybrid Perovskite Incorporating Near-Infrared-Absorbing Cyanine Cations. The Journal of Physical Chemistry Letters, 9(9), 2438-2442. doi:10.1021/acs.jpclett.8b00458Peng, Y., Albero, J., Álvarez, E., & García, H. (2019). Hybrid benzidinium lead iodide perovskites with a 1D structure as photoinduced electron transfer photocatalysts. Sustainable Energy & Fuels, 3(9), 2356-2360. doi:10.1039/c9se00182dWang, S., Ono, L. K., Leyden, M. R., Kato, Y., Raga, S. R., Lee, M. V., & Qi, Y. (2015). Smooth perovskite thin films and efficient perovskite solar cells prepared by the hybrid deposition method. Journal of Materials Chemistry A, 3(28), 14631-14641. doi:10.1039/c5ta03593gZhang, F., & Srinivasan, M. P. (2007). Multilayered Gold-Nanoparticle/Polyimide Composite Thin Film through Layer-by-Layer Assembly. Langmuir, 23(20), 10102-10108. doi:10.1021/la0635045Singh, T., Öz, S., Sasinska, A., Frohnhoven, R., Mathur, S., & Miyasaka, T. (2018). Sulfate‐Assisted Interfacial Engineering for High Yield and Efficiency of Triple Cation Perovskite Solar Cells with Alkali‐Doped TiO 2 Electron‐Transporting Layers. Advanced Functional Materials, 28(14), 1706287. doi:10.1002/adfm.201706287Yang, J., & Kelly, T. L. (2016). Decomposition and Cell Failure Mechanisms in Lead Halide Perovskite Solar Cells. Inorganic Chemistry, 56(1), 92-101. doi:10.1021/acs.inorgchem.6b01307Huang, W., Manser, J. S., Kamat, P. V., & Ptasinska, S. (2015). Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH3NH3PbI3 Perovskite under Ambient Conditions. Chemistry of Materials, 28(1), 303-311. doi:10.1021/acs.chemmater.5b0412

Surface Silylation of Hybrid Benzidinium Lead Perovskite and its Influence on the Photocatalytic Activity

This is the peer reviewed version of the following article: Y. Peng, J. Albero, H. García, ChemCatChem 2019, 11, 6384, which has been published in final form at https://doi.org/10.1002/cctc.201901681. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Surface coating of benzidinium lead iodide perovskite has been successfully accomplished by silanization with three different silylating agents, obtaining samples with average thickness from 2 to 6 nm as revealed by transmission electron microscopy. The obtained (organo)silica-coated hybrid perovskites exhibit enhanced hydrophobic character and, therefore, increased stability against moisture. However, its photocatalytic activity towards the cis-to-trans isomerization of stilbene diminishes as a function of the coating thickness, although a notable activity for this photocatalytic reaction is still observed.Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, and RTI2018-890237-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.; García Gómez, H. (2019). Surface Silylation of Hybrid Benzidinium Lead Perovskite and its Influence on the Photocatalytic Activity. ChemCatChem. 11(24):6384-6390. https://doi.org/10.1002/cctc.201901681S638463901124Q. Jiang Y. Zhao X. Zhang X. Yang Y. Chen Z. Chu Q. Ye X. Li Z. Yin J. You Nat. Photonics2019.Kakiage, K., Aoyama, Y., Yano, T., Oya, K., Fujisawa, J., & Hanaya, M. (2015). Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes. Chemical Communications, 51(88), 15894-15897. doi:10.1039/c5cc06759fSaravanan, R., Gracia, F., & Stephen, A. (2017). Basic Principles, Mechanism, and Challenges of Photocatalysis. Springer Series on Polymer and Composite Materials, 19-40. doi:10.1007/978-3-319-62446-4_2Bisquert, J., Cahen, D., Hodes, G., Rühle, S., & Zaban, A. (2004). Physical Chemical Principles of Photovoltaic Conversion with Nanoparticulate, Mesoporous Dye-Sensitized Solar Cells. The Journal of Physical Chemistry B, 108(24), 8106-8118. doi:10.1021/jp0359283Kamat, P. V. (2017). Semiconductor Surface Chemistry as Holy Grail in Photocatalysis and Photovoltaics. Accounts of Chemical Research, 50(3), 527-531. doi:10.1021/acs.accounts.6b00528Boyd, C. C., Cheacharoen, R., Leijtens, T., & McGehee, M. D. (2018). Understanding Degradation Mechanisms and Improving Stability of Perovskite Photovoltaics. Chemical Reviews, 119(5), 3418-3451. doi:10.1021/acs.chemrev.8b00336Aristidou, N., Eames, C., Sanchez-Molina, I., Bu, X., Kosco, J., Islam, M. S., & Haque, S. A. (2017). Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells. Nature Communications, 8(1). doi:10.1038/ncomms15218Y. Peng J. Albero E. Álvarez H. García Sustainable Energy Fuels2019.Cortecchia, D., Neutzner, S., Srimath Kandada, A. R., Mosconi, E., Meggiolaro, D., De Angelis, F., … Petrozza, A. (2016). Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation. Journal of the American Chemical Society, 139(1), 39-42. doi:10.1021/jacs.6b10390Kawano, N., Koshimizu, M., Sun, Y., Yahaba, N., Fujimoto, Y., Yanagida, T., & Asai, K. (2014). Effects of Organic Moieties on Luminescence Properties of Organic–Inorganic Layered Perovskite-Type Compounds. The Journal of Physical Chemistry C, 118(17), 9101-9106. doi:10.1021/jp4114305Albero, J., & García, H. (2017). Luminescence control in hybrid perovskites and their applications. Journal of Materials Chemistry C, 5(17), 4098-4110. doi:10.1039/c7tc00714kRonlan, A., Coleman, J., Hammerich, O., & Parker, V. D. (1974). Anodic oxidation of methoxybiphenyls. Effect of the biphenyl linkage on aromatic cation Radical and Dication Stability. Journal of the American Chemical Society, 96(3), 845-849. doi:10.1021/ja00810a033Talipov, M. R., Boddeda, A., Timerghazin, Q. K., & Rathore, R. (2014). Key Role of End-Capping Groups in Optoelectronic Properties of Poly-p-phenylene Cation Radicals. The Journal of Physical Chemistry C, 118(37), 21400-21408. doi:10.1021/jp5082752Zapata, P. A., Huang, Y., Gonzalez-Borja, M. A., & Resasco, D. E. (2013). Silylated hydrophobic zeolites with enhanced tolerance to hot liquid water. Journal of Catalysis, 308, 82-97. doi:10.1016/j.jcat.2013.05.024Bu, J., & Rhee, H. (2000). Catalysis Letters, 65(1/3), 141-145. doi:10.1023/a:1019096617082Kuwahara, Y., Maki, K., Matsumura, Y., Kamegawa, T., Mori, K., & Yamashita, H. (2009). Hydrophobic Modification of a Mesoporous Silica Surface Using a Fluorine-Containing Silylation Agent and Its Application as an Advantageous Host Material for the TiO2 Photocatalyst. The Journal of Physical Chemistry C, 113(4), 1552-1559. doi:10.1021/jp809191vYoshida, W., Castro, R. P., Jou, J.-D., & Cohen, Y. (2001). Multilayer Alkoxysilane Silylation of Oxide Surfaces. Langmuir, 17(19), 5882-5888. doi:10.1021/la001780sBerhe, T. A., Su, W.-N., Chen, C.-H., Pan, C.-J., Cheng, J.-H., Chen, H.-M., … Hwang, B.-J. (2016). Organometal halide perovskite solar cells: degradation and stability. Energy & Environmental Science, 9(2), 323-356. doi:10.1039/c5ee02733kVelichenko, A. ., Amadelli, R., Baranova, E. ., Girenko, D. ., & Danilov, F. . (2002). Electrodeposition of Co-doped lead dioxide and its physicochemical properties. 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Metal Organic Frameworks as Versatile Hosts of Au Nanoparticles in Heterogeneous Catalysis

[EN] The present review describes the state of the art of the use of metal organic framework (MOF)-encapsulated Au nanoparticles (NPs) as heterogeneous catalysts. The purpose is to show that catalysts with very good performance, frequently among the most active Au catalysts reported so far, can be obtained by incorporation of Au NPs inside MOFs. The available data indicate that the high catalytic activity of MOF-encapsulated Au NPs derives from (i) small particle size, (ii) high dispersion and homogeneous distribution inside MOFs crystals, (iii) stabilization of particle size by confinement of Au NPs inside MOFs cages, and (iv) the synergy that can arise by the combination of the activity of Au NPs and MOFs. After some introductory sections presenting general issues commenting about the relevance of Au catalysis, how to determine the internal versus external location of Au NPs, and evidence in support for catalyst stability, this mini review covers reactions using Au@MOFs as catalysts for oxidations, reductions, tandem processes, and photocatalysis with the emphasis in providing a comparison with the performance of other alternative Au-containing catalysts. In the final section, we summarize in our view the current achievements and which are the next targets in this area.A.D.M. thanks University Grants Commission, New Delhi for the award of Assistant Professorship under its Faculty Recharge Programme. A.D.M. also thanks Department of Science and Technology, India, for the financial support through Fast Track project (SB/FT/CS-166/2013) and the Generalidad Valenciana for financial aid supporting his stay at Valencia through the Prometeo programme. Financial support by the Spanish Ministry of Economy and Competitiveness (CTQ-2015-69153-CO2-R1 and Severo Ochoa) and Generalidad Valenciana (Prometeo 2013-014) is gratefully acknowledged.Dhakshinamoorthy, A.; Asiri, AM.; García Gómez, H. (2017). Metal Organic Frameworks as Versatile Hosts of Au Nanoparticles in Heterogeneous Catalysis. ACS Catalysis. 7(4):2896-2919. https://doi.org/10.1021/acscatal.6b03386S289629197