| 1. |
- Cailotto, Simone, et al.
(författare)
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Design of Carbon Dots for Metal-free Photoredox Catalysis
- 2018
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 10:47, s. 40560-40567
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Tidskriftsartikel (refereegranskat)abstract
- The photoreduction potential of a set of four different carbon dots (CDs) was investigated. The CDs were synthesized by using two different preparation methods—hydrothermal and pyrolytic—and two sets of reagents—neat citric acid and citric acid doped with diethylenetriamine. The hydrothermal syntheses yielded amorphous CDs, which were either nondoped (a-CDs) or nitrogen-doped (a-N-CDs), whereas the pyrolytic treatment afforded graphitic CDs, either non-doped (g-CDs) or nitrogen-doped (g-N-CDs). The morphology, structure, and optical properties of four different types of CDs revealed significant differences depending on the synthetic pathway. The photocatalytic activities of the CDs were investigated as such, that is, in the absence of any other redox mediators, on the model photoreduction reaction of methyl viologen. The observed photocatalytic reaction rates: a-N-CDs ≥ g-CDs > a-CDs ≥ g-N-CDs were correlated with the presence/absence of fluorophores, to the graphitic core, and to quenching interactions between the two. The results indicate that nitrogen doping reverses the photoredox reactivity between amorphous and graphitic CDs and that amorphous N-doped CDs are the most photoredox active, a yet unknown fact that demonstrates the tunable potential of CDs for ad hoc applications.
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| 2. |
- Campalani, Carlotta, et al.
(författare)
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Biobased Carbon Dots: From Fish Scales to Photocatalysis
- 2021
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Ingår i: Nanomaterials. - : MDPI. - 2079-4991. ; 11:2
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis, characterization and photoreduction ability of a new class of carbon dots made from fish scales is here described. Fish scales are a waste material that contains mainly chitin, one of the most abundant natural biopolymers, and collagen. These components make the scales rich, not only in carbon, hydrogen and oxygen, but also in nitrogen. These self-nitrogen-doped carbonaceous nanostructured photocatalyst were synthesized from fish scales by a hydrothermal method in the absence of any other reagents. The morphology, structure and optical properties of these materials were investigated. Their photocatalytic activity was compared with the one of conventional nitrogen-doped carbon dots made from citric acid and diethylenetriamine in the photoreduction reaction of methyl viologen.
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| 3. |
- Enrichi, Francesco, et al.
(författare)
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Ag-Sensitized NIR-Emitting Yb3+-Doped Glass-Ceramics
- 2020
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Ingår i: Applied Sciences. - : MDPI. - 2076-3417. ; 10:6
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Tidskriftsartikel (refereegranskat)abstract
- The optical photoluminescent (PL) emission of Yb3+ ions in the near infrared (NIR) spectral region at about 950–1100 nm has many potential applications, from photovoltaics to lasers and visual devices. However, due to their simple energy-level structure, Yb3+ ions cannot directly absorb UV or visible light, putting serious limits on their use as light emitters. In this paper we describe a broadband and efficient strategy for sensitizing Yb3+ ions by Ag codoping, resulting in a strong 980 nm PL emission under UV and violet-blue light excitation. Yb-doped silica–zirconia–soda glass–ceramic films were synthesized by sol-gel and dip-coating, followed by annealing at 1000 °C. Ag was then introduced by ion-exchange in a molten salt bath for 1 h at 350 °C. Different post-exchange annealing temperatures for 1 h in air at 380 °C and 430 °C were compared to investigate the possibility of migration/aggregation of the metal ions. Studies of composition showed about 1–2 wt% Ag in the exchanged samples, not modified by annealing. Structural analysis reported the stabilization of cubic zirconia by Yb-doping. Optical measurements showed that, in particular for the highest annealing temperature of 430 °C, the potential improvement of the material’s quality, which would increase the PL emission, is less relevant than Ag-aggregation, which decreases the sensitizers number, resulting in a net reduction of the PL intensity. However, all the Ag-exchanged samples showed a broadband Yb3+ sensitization by energy transfer from Ag aggregates, clearly attested by a broad photoluminescence excitation spectra after Ag-exchange, paving the way for applications in various fields, such as solar cells and NIR-emitting devices.
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| 4. |
- Enrichi, Francesco, et al.
(författare)
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Ag-sensitized Tb3+/Yb3+ codoped silica-zirconia glasses and glass-ceramics : systematic and detailed investigation of the broadband energy-transfer and downconversion processes
- 2021
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Ingår i: Ceramics International. - : Elsevier. - 0272-8842 .- 1873-3956. ; 47:13, s. 17939-17949
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Tidskriftsartikel (refereegranskat)abstract
- Various studies report that Tb3+/Yb3+ co-doped materials can split one UV or 488 nm (visible) photon in two near infrared (NIR) photons at 980 nm by an energy-transfer process involving one Tb3+ and two Yb3+ ions. Additionally, it was demonstrated that Ag multimers can provide an efficient optical sensitizing effect for rare earth ions (RE3+ ions), resulting in a broadband enhanced excitation, which could have a significant technological impact, overcoming their limited spectral absorptions and small excitation cross sections. However, a systematic and detailed investigation of the down-conversion process enhanced by Ag nanoaggregates is still lacking, which is the focus of this paper. Specifically, a step by step analysis of the energy-transfer quantum-cutting chain in Ag-exchanged Tb3+/Yb3+ co-doped glasses and glass-ceramics is presented. Moreover, the direct Ag-Yb3+ energy-transfer is also considered. Results of structural, compositional, and optical characterizations are given, providing quantitative data for the efficient broadband Ag-sensitization of Tb3+/Yb3+ quantum cutting. A deeper understanding of the physical processes beneath the optical properties of the developed materials will allow a wiser realization of more efficient energy-related devices, such as spectral converters for silicon solar cells and light-emitting devices (LEDs) in the visible and NIR spectral regions.
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| 5. |
- Enrichi, Francesco, et al.
(författare)
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Ag-Sensitized Yb3+ Emission in Glass-Ceramics
- 2018
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Ingår i: Micromachines. - : MDPI. - 2072-666X. ; 9:8
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Tidskriftsartikel (refereegranskat)abstract
- Rare earth doped materials play a very important role in the development of many photonic devices, such as optical amplifiers and lasers, frequency converters, solar concentrators, up to quantum information storage devices. Among the rare earth ions, ytterbium is certainly one of the most frequently investigated and employed. The absorption and emission properties of Yb3+ ions are related to transitions between the two energy levels 2F7/2 (ground state) and 2F5/2 (excited state), involving photon energies around 1.26 eV (980 nm). Therefore, Yb3+ cannot directly absorb UV or visible light, and it is often used in combination with other rare earth ions like Pr3+, Tm3+, and Tb3+, which act as energy transfer centres. Nevertheless, even in those co-doped materials, the absorption bandwidth can be limited, and the cross section is small. In this paper, we report a broadband and efficient energy transfer process between Ag dimers/multimers and Yb3+ ions, which results in a strong PL emission around 980 nm under UV light excitation. Silica-zirconia (70% SiO2-30% ZrO2) glass-ceramic films doped by 4 mol.% Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000 °C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 430 °C to induce the migration and aggregation of the metal. The structural, compositional, and optical properties were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag dimers/multimers, which could have important applications in different fields, such as PV solar cells and light-emitting near-infrared (NIR) devices.
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| 6. |
- Enrichi, Francesco, et al.
(författare)
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Effect of the crystal structure on the optical properties and Ag sensitization of Tb3+/Yb3+ ions in silica-zirconia glasses and glass-ceramics
- 2022
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Ingår i: Ceramics International. - : Elsevier. - 0272-8842 .- 1873-3956. ; 49:24 Part B
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Tidskriftsartikel (refereegranskat)abstract
- The role of the material structure in the energy transfer between Ag and Tb3+/Yb3+ ions is studied in silica-soda-zirconia sol-gel glasses and glass-ceramics. The preparation of Tb3+ and Yb3+ doped silica-soda-zirconia layers was carried out by sol-gel and dip-coating, followed by thermal annealing. The precipitation of zirconia nanocrystals was obtained by controlling the annealing temperature: from a full amorphous glass at 700 °C into a glass-ceramic at 1000 °C. A different crystalline structure of zirconia nanocrystals, tetragonal or cubic, was controlled by the rare-earth doping and investigated in relation to the Tb3+/Yb3+ optical properties. Moreover, Ag codoping was introduced by ion-exchange, obtaining a significant photoluminescence enhancement, both in the intensity and in the broadness of the excitation band, covering the whole UV region and part of the violet-blue region. Ag-sensitized Tb3+/Yb3+ doped silica-soda-zirconia glass-ceramics were attested to be potential candidates for energy-related applications, such as spectral conversion layers for solar cells, lasers and light-emitting devices (LEDs) in the visible and NIR spectral regions.
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| 7. |
- Enrichi, Francesco, et al.
(författare)
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Structural and optical properties of Eu3+-doped sol–gel silica–soda glasses
- 2024
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Ingår i: The European Physical Journal Plus. - : Springer Nature. - 2190-5444. ; 139:4
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Tidskriftsartikel (refereegranskat)abstract
- Rare earths (REs) incorporated in glasses, mostly in the form of RE3+ ions, have several applications such as lasers and optical amplifiers, spectral conversion layers for solar cells, light emitters and sensors. In this context, both the composition and the structural properties of the glass, as well as the dopant concentration play an important role in determining the optical properties and the efficiency of the system. Usually, the concentration of REs is small, below 1 at%, to avoid clustering and optical quenching. In this paper, we report the case of sol–gel Eu-doped silica–soda glass films. The addition of soda to silica can reduce RE clustering and precipitation, according to molecular dynamic simulations, but brings structural instabilities to the network. Here, sodium was varied from 10 to 30 at% and Eu from 0 to 8 at%. It was shown that Eu plays a significant role in the stabilization of the matrix, improving the transparency, the refractive index and the thickness of the films. The increase of Eu concentration provides a decrease of site symmetry and an increase of quantum efficiency (QY), reaching 71% for the highest 8 at% Eu doping, with remarkable absence of concentration quenching.
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| 8. |
- Moretti, Elisa, et al.
(författare)
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Photocatalytic performance of Cu-doped titania thin films under UV light irradiation
- 2021
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Ingår i: Applied Surface Science. - : Elsevier. - 0169-4332 .- 1873-5584. ; 553
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Tidskriftsartikel (refereegranskat)abstract
- We investigated the effect of copper doping on the photocatalytic properties of TiO2 thin films. Titania thin films doped with three different copper concentrations were synthesized via radiofrequency-assisted (RF) magnetron sputtering, then annealed at 600 °C in controlled atmosphere (Ar, O2, H2 flow). The impact of the annealing in inert, oxidizing or reducing atmosphere on the crystalline and surface structure, and photocatalytic performance in the methylene blue degradation under UV light irradiation was investigated by X-ray diffraction, UV-Vis Spectroscopy, Rutherford Backscattering Spectrometry, electron scanning microscopy. Annealing induced very different crystallization in different atmospheres, with strong copper out-diffusion in samples annealed in reducing atmosphere and formation of large embedded nanoparticles. The Cu-doped titania films exhibited higher photocatalytic activity than pure titania film and the best performing catalyst, treated in H2 atmosphere, suggests that the presence of embedded copper nanoparticles (both metallic and oxidized) is able to strongly enhance the photocatalytic properties of the host titania matrix. Incorporated Cu particles can act as trapped sites for generated electrons, and this leads to the reduction of carrier recombination which, ultimately, plays a significant role in the increase of photoactivity. The recyclability of the best system was ascertained by a suitable 3-cycle stability test.
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| 9. |
- Shifa, Tofik Ahmed, et al.
(författare)
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In Situ-Generated Oxide in Sn-Doped Nickel Phosphide Enables Ultrafast Oxygen Evolution
- 2021
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 11:8, s. 4520-4529
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Tidskriftsartikel (refereegranskat)abstract
- Water splitting is considered one of the most promising approaches to power the globe without the risk of environmental pollution. The oxygen evolution reaction (OER) is even more challenging because the generation of only one oxygen molecule involves the transfer of four e– and removal of four H+ ions from water. Thus, developing highly efficient catalysts to meet industrial requirements remains a focus of attention. Herein, the prominent role of Sn in accelerating the electron transfer kinetics of Ni5P4 nanosheets in OER is reported. The post catalytic survey elucidates that the electrochemically induced Ni–Sn oxides at the vicinity of phosphides are responsible for the observed catalytic activity, delivering current densities of 10, 30, and 100 mA cm–2 at overpotentials of only 173 ± 5.2, 200 ±7.4, and 310 ± 5.5 mV, respectively. The density functional theory calculation also supports the experimental findings from the basis of the difference observed in density of states at the Fermi level in the presence/absence of Sn. This work underscores the role of Sn in OER and opens a promising avenue toward practical implementation of hydrogen production through water splitting and other catalytic reactions.
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| 10. |
- Solomon, Getachew, et al.
(författare)
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NiMoO4@Co3O4 Core–Shell Nanorods : In Situ Catalyst Reconstruction toward High Efficiency Oxygen Evolution Reaction
- 2021
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Ingår i: Advanced Energy Materials. - : Wiley-VCH Verlagsgesellschaft. - 1614-6832 .- 1614-6840. ; 11:32
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Tidskriftsartikel (refereegranskat)abstract
- The sluggish kinetics of the oxygen evolution reaction (OER) is the bottleneck for the practical exploitation of water splitting. Here, the potential of a core–shell structure of hydrous NiMoO4 microrods conformally covered by Co3O4 nanoparticles via atomic layer depositions is demonstrated. In situ Raman and synchrotron-based photoemission spectroscopy analysis confirms the leaching out of Mo facilitates the catalyst reconstruction, and it is one of the centers of active sites responsible for higher catalytic activity. Post OER characterization indicates that the leaching of Mo from the crystal structure, induces the surface of the catalyst to become porous and rougher, hence facilitating the penetration of the electrolyte. The presence of Co3O4 improves the onset potential of the hydrated catalyst due to its higher conductivity, confirmed by the shift in the Fermi level of the heterostructure. In particular NiMoO4@Co3O4 shows a record low overpotential of 120 mV at a current density of 10 mA cm−2, sustaining a remarkable performance operating at a constant current density of 10, 50, and 100 mA cm−2 with negligible decay. Presented outcomes can significantly contribute to the practical use of the water-splitting process, by offering a clear and in-depth understanding of the preparation of a robust and efficient catalyst for water-splitting.
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