TY - CONF A1 - Woydt, Mathias A1 - Mohrbacher, H. A1 - Vleugels, J. A1 - Huang, S. T1 - Potentials of niobium carbide (NBC) as cutting tools and for wear protection N2 - Niobium is today largely available. NbC displayed lower dry sliding friction over WC grades. The softer Ni- and NiMo-bonded NbC1.0-grades have a higer abrasive wear resistance (ASTM G65), even with lower toughnesses, than the tougher WC-Co grades and harder NbC-Co grades. T2 - 41st International Conference and Exposition on Advanced Ceramics and Composites CY - Daytona Beach, FL, USA DA - 22.01.2017 KW - Niobium Carbide (NbC) KW - Cutting tool KW - Hardness KW - Friction PY - 2017 VL - 38 SP - 1 EP - 13 AN - OPUS4-43430 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - NbC grain growth control and mechanical properties of Ni bonded NbC cermets prepared by vacuum liquid phase sintering N2 - The current study reports on the effect of the sintering temperature and secondary carbide (VC, Mo2C and TiC) and Mo additions on the NbC grain growth, microstructure evolution as well as concomitant Vickers hardness (HV30) and fracture toughness of Ni-bonded NbC cermets. KW - Cermet KW - Niobium carbide KW - Sintering KW - Microstructure KW - Mechanical properties PY - 2018 DO - https://doi.org/10.1016/j.ijrmhm.2017.12.013 SN - 0263-4368 VL - 72 SP - 63 EP - 70 PB - Elsevier Science CY - Amsterdam AN - OPUS4-43582 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Huang, S. A1 - Vleugels, J. A1 - Cannizza, E. A1 - Woydt, Mathias A1 - Liu, Z. A1 - Mohrbacher, H. T1 - Niobium carbide based cermets with secondary carbide and carbonitride addition N2 - In this study, the influence of Ni binder content and carbide/carbonitride additions on the microstructure and mechanical properties of NbC-Ni matrix cermets were investigated. T2 - WORLDPM2018 CY - Beijing, China DA - 16.09.2018 KW - Cermet KW - Niobium carbide KW - Carbonitride KW - Sintering KW - Mechanical properties PY - 2018 SP - Part 5, 801 EP - 809 AN - OPUS4-46201 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Woydt, Mathias A1 - Huang, S. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Cannizza, E. T1 - Tailoring the functional profile of niobium carbide (NbC) as cutting tool materials and for wear protection N2 - In the present work it was shown that the properties of NbCx, like micro-hardness, hot-hardness, sliding wear resistance, elastic modulus and toughness can be tailored by the C/Nb ratio, the addition of secondary carbides and the type of binder. T2 - WORLDPM2018 CY - Beijing, China DA - 16.09.2018 KW - Niobium carbide KW - Properties KW - Wear KW - Machining PY - 2018 SP - Part 5, 785 EP - 795 AN - OPUS4-46204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, S.G. A1 - Vanmeensel, K. A1 - Mohrbacher, H. A1 - Woydt, Mathias A1 - Vleugels, J. T1 - Microstructure and mechanical porperties of NbC-matrix hardmetals with secondary carbide addition and different metal binders N2 - NbC has a relatively high hardness (19.6 GPa) and melting temperature (3600 °C) and is usually applied as a grain growth inhibitor in WC–Co hardmetals. The current study reports on the influence of the sintering technology and overall chemical composition on the microstructure and mechanical properties of NbC-based hardmetals, using Co as a binder. The partial replacement of NbC by 5 wt.% WC, Mo2C, VC or TiC allows one to significantly improve the hardness and toughness of the NbC–Co materials. The influence of different binders, i.e., Co, 316L stainless steel and Fe3Al on the microstructure and mechanical properties of NbC-based hardmetals was also investigated. The powder mixtures were sintered in the solid state by PECS and liquid state by conventional vacuum sintering. Detailed microstructural analysis was conducted by EPMA elemental mapping and WDS point analysis. Mechanical properties, including Vickers hardness and indentation toughness were assessed. KW - Niobium carbide KW - Sintering KW - Grain growth KW - Microstructure KW - Mechanical properties PY - 2015 DO - https://doi.org/10.1016/j.ijrmhm.2014.10.014 SN - 0263-4368 SN - 0958-0611 VL - 48 SP - 418 EP - 426 PB - Elsevier AN - OPUS4-31974 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - Microstructure and tribological performance of NbC-Ni cermets modified by VC and Mo2C N2 - The current study reports on the influence of the Addition of 5–15 vol% VC or/and Mo2C carbide on the microstructure and mechanical properties of nickel bonded NbC cermets, which are compared to cobalt bonded NbC cermets. The NbC, Ni and secondary carbides powder mixtures were liquid phase sintered for 1 h at 1420 °C in vacuum. The fully densified cermets are composed of a cubic NbC grains matrix and an evenly distributed fcc Ni binder. NbC grain growth was significantly inhibited and a homogeneous NbC grain size distribution was obtained in the cermets with VC/Mo2C additions. The mechanical properties of the NbC-Ni matrix cermets are strongly dependent on the carbide and Ni binder content and are directly compared to their NbC-Co equivalents. The liquid phase sintered NbC-12 vol% Ni cermet had a modest Vickers hardness (HV30) of 1077 ± 22 kg/mm2 and an indentation toughness of 9.1 ± 0.5 MPa·m1/2. With the addition of 10–15 vol% VC, the hardness increased to 1359 ± 15 kg/mm2, whereas the toughness increased to 11.3 ± 0.1 MPa·m1/2. Addition of 5 and 10 vol% Mo2C into a NbC-12 vol% Ni mixtures generated the same values in HV30 and KIC when compared to VC additions. A maximum flexural strength of 1899 ± 77 MPa was obtained in the cermet with 20 vol% Ni binder and 4 vol% VC+4 vol% Mo2C addition, exhibiting a high fracture toughness of 15.0 ± 0.5 MPa·m1/2, but associated with a loss in hardness due to the high Ni content. The dry sliding wear behaviour was established at room temperature and 400 °C from 0.1 to 10 m/s. KW - Cermet KW - Liquid phase sintering KW - Grain growth KW - Wear KW - Niobium carbide PY - 2017 DO - https://doi.org/10.1016/j.ijrmhm.2017.03.012 SN - 0263-4368 VL - 66 SP - 188 EP - 197 AN - OPUS4-40505 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Woydt, Mathias A1 - Mohrbacher, H. A1 - Vleugels, J. A1 - Huang, S. T1 - Niobium carbide for wear protection - tailoring its properties by processing and stoichiometry N2 - Niobium carbide is a hardly explored carbide but its functional profile shows a high potential for wear protection and tribological applications, which are currently dominated by tungsten carbide. Surprisingly little information is available on niobium carbide (NbC). Niobium carbide can be either synthesized by carbothermal conversion of Nb2O5 or be metallurgically grown and leached out. Furthermore, NbC hardmetal grades can be bonded by all known metallic binders and processed and sintered in exactly the same way as WC-based hardmetals. Niobium is today largely available. NbC can be efficiently produced, provides comparably low friction in many relevant tribo-contacts and displays low wear. NbC and Nb2O5 have so far no REACH classification related to human toxicology and are not listed as substances of very high concern contrary to WO3 and Co3O4. This contribution demonstrates the key characteristics of NbC and discusses its sustainability and reliable value chain. KW - niobium carbide KW - wear KW - machining PY - 2016 DO - https://doi.org/10.1016/j.mprp.2015.12.010 SN - 0026-0657 VL - 71 IS - 4 SP - 265 EP - 272 PB - Elsevier Ltd. AN - OPUS4-37150 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - Influence of VC and Mo2C on the microstructure and mechanical properties of Ni bonded NbC-cermets N2 - The current study reports on the effect of VC and Mo2C carbides on the microstructure and mechanical properties of Ni bonded NbC cermets. T2 - World PM2016 CY - Hamburg, Germany DA - 09.10.2016 KW - Niobium carbide KW - NbC KW - Liquid phase sintering (LPS) KW - Hard materials PY - 2016 SN - ISBN 978-1-899072-47-7 SP - 1 EP - 7 AN - OPUS4-37891 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - Densification and tribological profile of niobium oxide N2 - The origin of the intrinsic wear resistance of NbC-based materials is investigated through an assessment of the tribological performance of fully dense, crack-free spark plasma sintered Nb2O5 (here as a reduced polymorph: monoclinic Nb12O29 or NbO2.416). The most likely wear mechanism on NbC is the tribo-oxidation to Nb2O5. The unlubricated (dry) friction and wear behavior of alumina (99.7%) mated against rotating disks of crack-free niobium(V)oxide (Nb2O5) under unidirectional sliding (0.03–10m/s; 22°C and 400°C) and oscillation (f=20 Hz, dx=200 mm, 2/50/98% rel. humidity, n=105/106 cycles) will be presented. The microstructure and mechanical properties of the crack-free Nb2O5 are assessed. The tribological data obtained are benchmarked with different NbC grades, ceramics, cermets and thermally sprayed coatings. KW - Friction KW - Wear KW - Nb2O5 KW - Nb12O29 KW - Niobium oxide KW - Strength KW - Modulus KW - High temperatures PY - 2016 DO - https://doi.org/10.1016/j.wear.2016.02.003 SN - 0043-1648 VL - 352-353 SP - 65 EP - 71 PB - Elsevier B.V. AN - OPUS4-35805 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - NbC grain growth control and mechanical properties of Ni bonded NbC cermets prepared by vacuum liquid phase sintering N2 - The current study reports on the effect of the sintering temperature and secondary carbide (VC, Mo2C and TiC) additions on the microstructure and concommitant Vickers hardness (HV30) and fracture toughness of Ni-bonded NbC cermets. All cermets were prepared by pressureless sintering in vacuum. Detailed microstructural investigation was performed by electron probe microanalysis (EPMA) and X-ray diffraction (XRD) analysis. Sintering results indicated that both the sintering temperature and secondary carbide additions had a significant effect on the properties of NbC-Ni cermets. Nickel pools and residual pores were observed in the cermets sintered at temperatures ≤ 1340 °C. Increasing of the sintering temperature up to 1420 or 1480 °C resulted in fully densified NbC-Ni based cermets composed of homogeneous contrast cubic NbC grains for the single carbide (VC or Mo2C) modyfied system, whereas core-rim structured NbC grains were observed with the additon of TiC + VC or TiC+Mo2C. The secondary carbide doped cermets with 5–10 vol.% VC/Mo2C and 10 vol.% TiC showed a significantly improved hardness and fracture toughness, as compared to the plain NbC-Ni cermets. T2 - 19. Plansee Seminar CY - Reutte, Austria DA - 29.05.2017 KW - Cermet KW - Hard materials KW - Sintering KW - Microstructure KW - Core-rim KW - Mechanical properties PY - 2017 SP - HM 13/1 EP - HM 13/11 AN - OPUS4-40592 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Woydt, Mathias A1 - Mohrbacher, H. A1 - Vleugels, J. A1 - Huang, S. T1 - Potentials of niobium carbide (NbC) as cutting tools and for wear protection N2 - The tool lifes of uncoated NiMo and NiMo2C-bonded stoichiometric NbC1.0 grades under dry turning 42CrMo4 and C45E were between +30 % to + 100 % higher and up compared to WC-6Co (fine grain). Niobium is today largely available. NbC grades displayed lower dry sliding friction over WC grades. T2 - 19. Plansee Seminar CY - Reutte, Austria DA - 29.05.2017 KW - Niobium carbide KW - Friction KW - Wear KW - NbC KW - Hard metal KW - Machining KW - Nickel PY - 2017 SP - HM 102/1 EP - HM 102/16 AN - OPUS4-40593 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Huang, S. G. A1 - Vleugels, J. A1 - Mohrbacher, H. A1 - Woydt, Mathias T1 - Effect of carbon content on the microstructure and mechanical properties of NbC-Ni based cermets N2 - The aim of this work was to correlate the carbon content in NbC-Ni starting powders with the resulting microstructure, hardness and fracture toughness of Ni-bonded NbC cermets. T2 - 19. Plansee Seminar CY - Reutte, Austria DA - 29.05.2017 KW - Cermet KW - Liquid phase sintering KW - Microstructure KW - Hardness KW - Carbon PY - 2017 SP - HM 109/1 EP - HM 109/11 AN - OPUS4-40595 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Woydt, Mathias A1 - Mohrbacher, H. A1 - Vleugels, J. A1 - Huang, S. T1 - Status of nickel bonded niobium carbide (NbC) as a substitute for cobalt-bonded tungsten carbide (WC) as cutting tools and for wear protection N2 - Niobium is today largely available. The initial NbC grade was substoichiometric, SPS sintered and cobalt bonded (NbC0.88-12Co SPS). The NiMo-bonded stoichiometric NbC1.0 grades enable the subtituion of cobalt by nickel, SPS by conventional sintering and NbC0.88 by NbC1.0 in view of functional properties. Nickel bonded NbC grades have improved toughnesses versus cobalt bonded NbC grades, but lose hardness. NiMo and NiMo2C bonded NbC1.0 grades compensated the loss in hardness while keeping the toughness. T2 - POWDERMET 2017 CY - Las Vegas, USA DA - 13.06.2017 KW - Niobium carbide (NbC) KW - Cutting tools KW - Wear PY - 2017 SP - 721 EP - 734 PB - Metal Powder Industries Federation AN - OPUS4-40671 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pu, Y. A1 - Lawrence, M. J. A1 - Celorrio, V. A1 - Wang, Q. A1 - Gu, M. A1 - Sun, Z. A1 - Agudo Jácome, Leonardo A1 - Russell, A. E. A1 - Huang, L. A1 - Rodriguez, P. T1 - Nickel confined in 2D earth-abundant oxide layers for highly efficient and durable oxygen evolution catalysts N2 - Low cost, high-efficiency catalysts towards water splitting are urgently required to fulfil the increasing demand for energy. In this work, low-loading (<20 wt%) Ni-confined in layered metal oxide anode catalysts (birnessite and lepidocrocite titanate) have been synthesized by facile ion exchange methodology and subjected to systematic electrochemical studies. It was found that Ni-intercalated on K-rich birnessite (Ni-KMO) presents an onset overpotential (ηonset) as low as 100 mV and overpotential at 10 mA cm−2 (η10) of 206 mV in pH = 14 electrolyte. By combining electrochemical methods and X-ray absorption and emission spectroscopies (XAS and XES), we demonstrate Ni sites are the active sites for OER catalysis and that the Mn3+ sites facilitate Ni intercalation during the ion-exchange process, but display no observable contribution towards OER activity. The effect of the pH and the nature of the supporting electrolyte on the electrochemical performance was also evaluated. KW - Confined catalyst KW - Low-loading KW - Layered manganese oxide KW - Oxygen evolution reaction KW - Transmission electron microscopy (TEM) PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515027 DO - https://doi.org/10.1039/D0TA04031B SN - 2050-7496 SN - 2050-7488 VL - 8 IS - 26 SP - 13340 EP - 13350 PB - Royal Society of Chemistry CY - London AN - OPUS4-51502 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Sekine, R. A1 - Huang, J. A1 - Steckenmesser, D. A1 - Steffens, D. A1 - Huthwelker, T. A1 - Borca, C. A1 - Pradas del Real, A. A1 - Castillo-Michel, H. A1 - Adam, Christian T1 - Effects of a nitrification inhibitor on nitrogen species in the soil and the yield and phosphorus uptake of maize N2 - Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P fertilizers from recycled materials, which often have low plant availability. Specific co-fertilization with ammoniumcan enhance P plant availability in soils amended with these P fertilizers, and thus the yield of plants. To investigate this effect, we performed a pot experiment with maize in slightly acidic soil (pH 6.9) with one water-soluble (triple superphosphate [TSP]) and two water-insoluble (sewage sludge-based and hyperphosphate [Hyp]) P fertilizers and anammoniumsulfate nitrate with or without a nitrification inhibitor (NI). The dry matter yield of maize was significantly increased by the NI with the Hyp (from 14.7 to 21.5 g/pot) and TSP (from 40.0 to 45.4 g/pot) treatments. Furthermore, P uptake was slightly increased in all three P treatments with the NI, but not significantly. Olsen-P extraction and P K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy showed that apatite-P of the water insoluble P fertilizers mobilized during the plant growth period. In addition, novel nitrogen (N) K-edge micro-XANES spectroscopy and the Mogilevkina method showed that the application of an NI increased the fixation of ammonium in detectable hot spots in the soil. Thus, the delay in the nitrification process by the NI and the possible slow-release of temporarily fixed ammoniumin the soil resulted in a high amount of plant available Ammonium in the soil solution. This development probably decreases the rhizosphere pH due to release of H+ by plants during ammoniumuptake, whichmobilizes phosphorus in the amended soil and increases the dry matter yield of maize. This is especially important for water-insoluble apatite-based P fertilizers (conventional and recycled), which tend to have poor plant availability. KW - Fertilzer KW - Phosphorus recovery KW - Ammonium KW - Nitrification inhibitor KW - XANES spectroscopy KW - Diffusive gradients in thin films (DGT) PY - 2020 DO - https://doi.org/10.1016/j.scitotenv.2020.136895 SN - 1879-1026 VL - 715 SP - 1 EP - 8 PB - Elsevier CY - Amsterdam AN - OPUS4-50477 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Woydt, Mathias A1 - Huang, S. A1 - Cannizza, E. A1 - Vleugels, J. A1 - Mohrbacher, H. T1 - Niobium carbide for machining and wear protection - Evolution of properties N2 - The sales of niobium carbide (NbC) have grown in the last years, but NbC is still a hidden carbide and mainly used as grain growth inhibitor in hard metals. In the present work it was shown that the progress in the key properties, like HV30, KIC and strength, followed by machining and tribological results of the respective NbC grades. KW - Niobium carbide KW - Hard metals KW - Tribology PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-485507 DO - https://doi.org/10.1016/j.mprp.2019.02.002 SN - 0026-0657 VL - 74 IS - 2 SP - 82 EP - 89 PB - Elsevier Ltd. AN - OPUS4-48550 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pu, Y. A1 - Celorrio, V. A1 - Stockmann, Jörg Manfred A1 - Sobol, Oded A1 - Sun, Z. A1 - Wang, W. A1 - Lawrence, M. J. A1 - Radnik, Jörg A1 - Russel, A. E. A1 - Hodoroaba, Vasile-Dan A1 - Huang, L. A1 - Rodriguez, P. T1 - Surface galvanic formation of Co-OH on Birnessite and its catalytic activity for the oxygen evolution reaction N2 - Low-cost, high-efficient catalysts for water splitting can be potentially fulfilled by developing earthabundant metal oxides. In this work, surface galvanic formation of Co-OH on K0.45MnO2 (KMO) was achieved via the redox reaction of hydrated Co2+ with crystalline Mn4+. The synthesis method takes place at ambient temperature without using any surfactant agent or organic solvent, providing a clean, green route for the design of highly efficient catalysts. The redox reaction resulted in the formation of ultrathin Co-OH nanoflakes with high electrochemical surface area. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the changes in the oxidation state of the bulk and surface species on the Co-OH nanoflakes supported on the KMO. The effect of the anions, such as chloride, nitrate and sulfate, on the preparation of the catalyst was evaluated by electrochemical and spectrochemical means. XPS and Time of flight secondary ion mass spectrometry (ToF-SIMS) analysis demonstrated that the layer of CoOxHy deposited on the KMO and its electronic structure strongly depend on the anion of the precursor used during the synthesis of the catalyst. In particular, it was found that Cl- favors the formation of Co-OH, changing the rate-determining step of the reaction, which enhances the catalytic activity towards the OER, producing the most active OER catalyst in alkaline media. KW - Nanoparticles KW - Oxygen evolution reaction (OER) KW - Catalysis KW - ToF-SIMS KW - XPS KW - K-rich Birnessite (K0.45MnO2) PY - 2021 DO - https://doi.org/10.1016/j.jcat.2021.02.025 VL - 396 SP - 304 EP - 314 PB - Elsevier Inc. AN - OPUS4-52328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, Junhao A1 - Klahn, Marcus A1 - Tian, Xinxin A1 - Bartling, Stephan A1 - Zimina, Anna A1 - Radtke, Martin A1 - Rockstroh, Nils A1 - Naliwajko, Pawel A1 - Steinfeldt, Norbert A1 - Peppel, Tim A1 - Grunwaldt, Jan‐Dierk A1 - Logsdail, Andrew J. A1 - Jiao, Haijun A1 - Strunk, Jennifer T1 - Fundamental Structural and Electronic Understanding of Palladium Catalysts on Nitride and Oxide Supports N2 - The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single‐atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non‐metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non‐metal and metal oxide). Through thorough oxidation state investigations by X‐ray absorption spectroscopy (XAS), X‐ray photoelectron spectroscopy (XPS), CO‐DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd−N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity. KW - BAmline KW - XANES KW - Catalyst PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608341 DO - https://doi.org/10.1002/anie.202400174 SN - 1433-7851 VL - 63 IS - 20 SP - 1 EP - 9 PB - Wiley AN - OPUS4-60834 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ermilov, Eugeny A. A1 - Liu, J.-Y. A1 - Menting, R. A1 - Huang, Y.-S. A1 - Röder, B. A1 - Ng, D. K. P. T1 - An artificial photosynthetic model based on a molecular triad of boron dipyrromethene and phthalocyanine N2 - A boron dipyrromethene (BDP) unit and its monostyryl derivative (MSBDP) were introduced at the axial positions of a silicon(IV) phthalocyanine (SiPc) core. The absorption spectrum of this compound virtually covered the entire visible region (300-700 nm) and could be interpreted as a superposition of the spectra of individual components. The intramolecular photoinduced energy and charge transfer processes of this triad were studied using steady-state and time-resolved spectroscopic methods in polar and nonpolar solvents. Upon BDP-part excitation, a fast and highly efficient excitation energy transfer (EET) occurred resulting in strong quenching of its fluorescence and the formation of the first excited singlet state of SiPc or MSBDP. It was found that both EET and charge transfer (CT) processes competed with each other in the depopulation of the first excited singlet state of the MSBDP moiety. The former strongly superseded CT in nonpolar toluene, whereas the latter was dominant in a polar environment. Direct or indirect (via EET) excitation of the SiPc-part of the triad was followed by CT yielding the charge-separated (CS) species BDP-SiPc center dot--MSBDP center dot+. The energy gap between the CS state and the S-1-state of the SiPc moiety was found to be only 0.06 eV in toluene, which facilitated the back CT process and resulted in the appearance of thermally activated delayed fluorescence. With increasing solvent polarity, the energy of the CS state reduced resulting in the disappearance of the delayed fluorescence in CHCl3, tetrahydrofuran or N,N-dimethylformamide. The charge recombination rate, k(CR), was very fast in polar DMF (3.3 x 10(10) s(-1)), whereas this process was two-orders of magnitude slower in nonpolar toluene (k(CR) = 4.0 x 10(8) s(-1)). KW - Photoinduced electron-transfers KW - Zinc phthalocyanine KW - Solar-energy KW - Charge separation KW - Solvent polarity KW - Porphyrin KW - Excitation KW - Fullerene KW - Recombination KW - Carotenoids PY - 2016 DO - https://doi.org/10.1039/c6cp00920d VL - 18 IS - 16 SP - 10964 EP - 10975 PB - Royal Soc Chemistry CY - Cambridge, UK AN - OPUS4-36271 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -