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. 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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. 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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). 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(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). 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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

Graphene supported NiO/Ni nanoparticles as efficient photocatalyst for gas phase CO2 reduction with hydrogen

[EN] The photocatalytic activity of NiO/Ni nanoparticles (NPs) supported on defective graphene (NiO/Ni-G) has been tested for the photoassisted CO2 reduction with H-2. NiO/Ni-G was prepared by H-2 reduction of NiCl2 adsorbed on few-layers defective G and storage under air. An optimal Ni loading of 23 wt% was found, reaching the maximum specific CH4 formation rate (642 mu mol CH4 g(Ni)(-1) h(-1) at 200 degrees C) and quantum yield of 1.98%. Under the same conditions Ni NPs supported on silica-alumina or NiO NPs exhibit notably lower specific CH4 production rates than NiO/Ni-G. It was found that H2O formed in the reaction has a detrimental influence on the photocatalytic activity and evidence supports that H2O desorption is one of the reasons why the system requires heating. Under continuous flow operation, undesirable water molecules were easier desorbed from the NiO/Ni-G photocatalyst than in the batch mode, reaching a steady specific CH4 production rate of 244.8 mu L h(-1) for 50 mg of NiO/Ni-G catalyst with a residence time of 3.1 s. Quenching experiments with electron donor of different oxidation potential (dimethylaniline, anisole and p-xylene) are compatible with a mechanism involving photoinduced charge separation.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV-2016-0683, Grapas and CTQ2015-69563-CO2-R1) and by the Generalitat Valencia (Prometeo 2013-014) is gratefully acknowledged. J. A. thanks the Universitat Politecnica de Valencia for a postdoctoral scholarship. D. M. also thanks Spanish Ministry of Science for PhD Scholarship.Mateo-Mateo, D.; Albero-Sancho, J.; García Gómez, H. (2018). Graphene supported NiO/Ni nanoparticles as efficient photocatalyst for gas phase CO2 reduction with hydrogen. Applied Catalysis B Environmental. 224:563-571. https://doi.org/10.1016/j.apcatb.2017.10.071S56357122

Photoassisted methanation using Cu2O nanoparticles supported on graphene as a photocatalyst

[EN] Photoassisted CO2 methanation can be carried out efficiently at 250 degrees C using Cu2O nanoparticles supported on few layer graphene (Cu2O/G) as a photocatalyst. The Cu2O/G photocatalyst has been prepared by chemical reduction of a Cu salt (Cu(NO3)(2)) with ethylene glycol in the presence of defective graphene obtained from the pyrolysis of alginic acid at 900 degrees C under Ar flow. Using this photocatalyst a maximum specific CH4 formation rate of 14.93 mmol g(Cu2O)(-1) h(-1) and an apparent quantum yield of 7.84% were achieved, which are among the highest reported values for the gas-phase methanation reaction at temperatures below the Sabatier reaction temperature (4350 degrees C). It was found that the most probable reaction mechanism involves photoinduced electron transfer from the Cu2O/G photocatalyst to CO2, while evidence indicates that light-induced local temperature increase and H-2 activation are negligible. The role of the temperature in the process has been studied, the available data suggesting that heating is needed to desorb the H2O formed as the product during the methanation. The most probable reaction mechanism seems to follow a dissociative pathway involving detachment of oxygen atoms from CO2.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, grapas, and CTQ2015-69563-CO2-R1) and by the Generalitat Valenciana (Prometeo 2013014) is gratefully acknowledged. J. A. thanks the Universitat Politecnica de Valencia for a postdoctoral scholarship. D. M. also thanks the Spanish Ministry of Science for a PhD Scholarship.Mateo-Mateo, D.; Albero-Sancho, J.; García Gómez, H. (2017). Photoassisted methanation using Cu2O nanoparticles supported on graphene as a photocatalyst. Energy & Environmental Science. 10(11):2392-2400. https://doi.org/10.1039/c7ee02287eS239224001011Yuan, L., & Xu, Y.-J. (2015). Photocatalytic conversion of CO2 into value-added and renewable fuels. Applied Surface Science, 342, 154-167. doi:10.1016/j.apsusc.2015.03.050Ganesh, I. (2015). Solar fuels vis-à-vis electricity generation from sunlight: The current state-of-the-art (a review). Renewable and Sustainable Energy Reviews, 44, 904-932. doi:10.1016/j.rser.2015.01.019Tu, W., Zhou, Y., & Zou, Z. (2014). Photocatalytic Conversion of CO2into Renewable Hydrocarbon Fuels: State-of-the-Art Accomplishment, Challenges, and Prospects. Advanced Materials, 26(27), 4607-4626. doi:10.1002/adma.201400087Corma, A., & Garcia, H. (2013). Photocatalytic reduction of CO2 for fuel production: Possibilities and challenges. Journal of Catalysis, 308, 168-175. doi:10.1016/j.jcat.2013.06.008Y. Izumi , in Advances in CO2 Capture, Sequestration, and Conversion, American Chemical Society, 2015, ch. 1, vol. 1194, pp. 1–46INOUE, T., FUJISHIMA, A., KONISHI, S., & HONDA, K. (1979). Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders. Nature, 277(5698), 637-638. doi:10.1038/277637a0J. Albero and H.García, in Heterogeneous Photocatalysis: From Fundamentals to Green Applications, ed. J. C. Colmenares and Y.-J. Xu, Springer-Verlag Berlin Heidelberg, 1 edn, 2016, ch. 1, p. VIII, 41610.1007/978-3-662-48719-8Ozcan, O., Yukruk, F., Akkaya, E. U., & Uner, D. (2007). Dye sensitized CO2 reduction over pure and platinized TiO2. Topics in Catalysis, 44(4), 523-528. doi:10.1007/s11244-006-0100-zGonell, F., Puga, A. V., Julián-López, B., García, H., & Corma, A. (2016). Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide. Applied Catalysis B: Environmental, 180, 263-270. doi:10.1016/j.apcatb.2015.06.019Neaţu, Ş., Maciá-Agulló, J. A., Concepción, P., & Garcia, H. (2014). Gold–Copper Nanoalloys Supported on TiO2 as Photocatalysts for CO2 Reduction by Water. Journal of the American Chemical Society, 136(45), 15969-15976. doi:10.1021/ja506433kXie, X., Kretschmer, K., & Wang, G. (2015). Advances in graphene-based semiconductor photocatalysts for solar energy conversion: fundamentals and materials engineering. Nanoscale, 7(32), 13278-13292. doi:10.1039/c5nr03338aLavorato, C., Primo, A., Molinari, R., & Garcia, H. (2013). N-Doped Graphene Derived from Biomass as a Visible-Light Photocatalyst for Hydrogen Generation from Water/Methanol Mixtures. Chemistry - A European Journal, 20(1), 187-194. doi:10.1002/chem.201303689Kumar, P., Mungse, H. P., Khatri, O. P., & Jain, S. L. (2015). Nitrogen-doped graphene-supported copper complex: a novel photocatalyst for CO2 reduction under visible light irradiation. RSC Advances, 5(68), 54929-54935. doi:10.1039/c5ra05319fLatorre-Sánchez, M., Esteve-Adell, I., Primo, A., & García, H. (2015). 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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

Visible-light-induced tandem reaction of o-aminothiophenols and alcohols to benzothiazoles over Fe-based MOFs: Influence of the structure elucidated by transient absorption spectroscopy

[EN] MIL-100(Fe) and MIL-68(Fe), two Fe-based MOFs, were found to be active for oxidative condensation between alcohols and o-aminothiophenols to form 2-substituted benzothiazoles under visible light irradiation using oxygen (02) as oxidant. This reaction can be applied to a wide range of substrates with medium to high yield. Controlled experiments and ESR results revealed a superoxide radical (O-2(center dot-))-mediated pathway, which is derived from the reduction of O-2 by photogenerated Fe2+ on Fe-O clusters. The whole multistep reaction is limited by the step of the photo-oxidation of alcohols to aldehydes. MIL-100(Fe) showed catalytic performance superior to that of MIL-68(Fe) because its higher concentration of long-lived (mu s time scale) positive holes can be photogenerated over MIL-100(Fe), in contrast to MIL-68(Fe). This study not only provides an economical, sustainable, and thus green process for the production of 2-substituted benzothiazoles, but also illustrates the potential of using transient absorption spectroscopy as an important tool for understanding the photophysics of MOFs, which are believed to show great potential as multifunctional catalysts for light-induced organic transformations. (C) 2017 Elsevier Inc. All rights reserved.This work was supported by the 973 Program (2014CB239303), the NSFC (21273035), the National Key Technologies R&D Program of China (2014BAC13B03), and an Independent Research Project of the State Key Laboratory of Photocatalysis on Energy and Environment (2014A03). Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153-CO2-1-R) is also gratefully acknowledged. Z. Li thanks the Award Program for Minjiang Scholar Professorship for financial support.Wang, D.; Albero-Sancho, J.; García Gómez, H.; Li, Z. (2017). Visible-light-induced tandem reaction of o-aminothiophenols and alcohols to benzothiazoles over Fe-based MOFs: Influence of the structure elucidated by transient absorption spectroscopy. Journal of Catalysis. 349:156-162. https://doi.org/10.1016/j.jcat.2017.01.014S15616234

Sobre la presencia de Powellita, Mo O4 Ca, en Gualba de Dalt (Barcelona)

Se cita por primera vez la powellita, Mo O, Ca, en Catalunya (Gualba de Dalt, Barcelona). Los ejemplares recolectados se estudiaron mediante las técnicas siguientes: analisis quimico, picnometria, difractometria y espectrografia por fluorescencia de rayos X. Se consideran las posibles relaciones entre la powellita y la molibdenita, S, Mo, presente en el mismo yacimiento

Hybrid benzidinium lead iodide perovskites with a 1D structure as photoinduced electron transfer photocatalysts

[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/c9se00182dS235623603