| 1. |
- He, Yixing, et al.
(författare)
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Chain Length Modulated Dimerization and Cyclization of Terminal Thienyl-Blocked Oligopyrranes
- 2022
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Ingår i: Organic Letters. - : AMER CHEMICAL SOC. - 1523-7060 .- 1523-7052. ; 24:29, s. 5428-5432
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Tidskriftsartikel (refereegranskat)abstract
- Oxidation of thienyl-blocked bilane and pentapyrrane afforded chain length dependent products of the symmetric dimer D1 and the thienyloligopyrrin-appended pentaphyrin analogue P2, respectively, with the latter formed by simultaneous dimerization and cyclization. Coordination of D1 and P2 with Cu(II) afforded di-and monometallic complexes D1-Cu2 and P2 -Cu, respectively. These compounds exhibit distinct NIR absorption, with the absorption tail of D1-Cu2 extended to ca. 1900 nm despite its smaller conjugation framework than that of P2 -Cu.
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| 2. |
- Huang, Yanping, et al.
(författare)
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Syntheses and characterization of dithienyl-blocked hexapyrrin and its mononuclear complexes
- 2023
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Ingår i: Journal of Porphyrins and Phthalocyanines. - : World Scientific. - 1088-4246 .- 1099-1409. ; 27:07N10, s. 1089-1096
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Tidskriftsartikel (refereegranskat)abstract
- With the purpose to develop long chain-conjugated oligopyrrin-like compounds and their metal complexes, and thus achieve tunable near-infrared absorption, a dithienyl-blocked hexapyrrane S-2-P-6 was synthesized by acid-catalyzed [2+4+2] condensation, followed by oxidation with DDQ to afford dithiaoctapyrrin 1, and its mononuclear metal complexes 1-Cu and 1-Zn were synthesized by treating 1 with Cu(II) and Zn(II) acetates. All the compounds were systematically characterized by NMR/EPR, and HRMS. The crystal structures revealed that 1 adopts a double hook-like conformation. Whereas, both complexes 1-Cu and 1-Zn adopt spiral-hook hybrid conformations, showing smaller interplanar angles between the rings within the spiral part, compared with those in the hook-like counterpart of molecule 1, which is favorable for red-shifting the absorption. As expected, the absorption band edges for complexes 1-Cu and 1-Zn are red-shifted to ca. 1560 nm, compared with that of 1260 nm observed for 1.
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| 3. |
- Huang, Yanping, et al.
(författare)
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Syntheses and coordination of linear and macrocyclic pentapyrroles possessing a fused moiety : Confusion modulated structural diversity
- 2024
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Ingår i: Dyes and pigments. - : Elsevier. - 0143-7208 .- 1873-3743. ; 223
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Tidskriftsartikel (refereegranskat)abstract
- Porphyrinoids have attracted wide interest because of their vital roles in biological processes and fascinating structural and functional characters. In this work, a doubly N-confused pentapyrrane precursor N2C–P5 has been synthesized with terminal pyrrole ring A and middle pyrrole C incorporated in the N-confused mode. On this basis, pentapyrrin 1 and sapphyrin 2 have been synthesized by oxidizing N2C–P5 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Both 1 and 2 possess a [5.5.5]-tricyclic fused ring involving pyrrole B and the neighboring confused pyrrole C. Meanwhile, the formation of 2 involves ring closure between the terminal rings A and E. Notably, 2 exists as a diradical showing a half-field signal in the electron paramagnetic resonance (EPR) spectrum and a singlet ground state with a negative singlet-triplet energy gap of −0.50 kcal/mol. Excellent thermal stability has been observed for 2, which may be related to its large π-conjugated framework involving the fused structure. On this basis, 1 and 2 were treated with Cu(acac)2 to afford Cu(II) complexes 3 and 4, respectively. As a result, an acetylacetonyl moiety is attached at the terminal pyrrole ring E to afford an NNNO coordination environment for complex 3, and the sapphyrin macrocycle of 2 has been cleaved between rings A and B to afford a fused pentapyrrin ligand, furnishing an NNNN coordination environment for complex 4, in which a pentafluorophenyl-ketal group generated during the ring cleavage reaction is attached to ring A, and it can be hydrolyzed to the corresponding pentafluorobenzoyl substituent to afford complex 5. Compared with free bases 1 and 2, complexes 3−5 show more intense low-energy near-infrared (NIR) absorption bands at ca. 791, 926 and 907 nm, respectively. This work provides an effective approach for the syntheses of linear and macrocyclic oligopyrroles with intriguing structures and properties by oxidizing oligopyrranes with precisely designed numbers and positions of N-confused pyrroles.
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| 4. |
- Liu, Liang, et al.
(författare)
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The composite electrolyte with an insulation Sm2O3 and semiconductor NiO for advanced fuel cells
- 2018
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Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 43:28, s. 12739-12747
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Tidskriftsartikel (refereegranskat)abstract
- Novel Sm2O3-NiO composite was prepared as the functional electrolyte for the first time. The total electrical conductivity of Sm2O3-NiO is 0.38 S cm(-1) in H-2/air condition at 550 degrees C. High performance, e.g. 718 mW cm(-2), was achieved using Sm2O3-NiO composite as an electrolyte of solid oxide fuel cells operated at 550 degrees C. The electrical properties and electrochemical performance are strongly depended on Sm2O3 and NiO constituent phase of the compositions. Notably, surprisingly high ionic conductivity and fuel cell performance are achieved using the composite system constituting with insulating Sm2O3 and intrinsic p-type conductive NiO with a low conductivity of 4 x 10(-3) S cm(-1). The interfacial ionic conduction between two phases is a dominating factor giving rise to significantly enhanced proton conduction. Fuel cell performance and further ionic conduction mechanisms are under investigation.
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| 5. |
- Liu, Yanyan, et al.
(författare)
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Natural CuFe2O4 mineral for solid oxide fuel cells
- 2017
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Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 42:27, s. 17514-17521
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Tidskriftsartikel (refereegranskat)abstract
- Natural mineral, cuprospinel (CuFe2O4) originated from natural chalcopyrite ore (CuFeS2), has been used for the first time in low temperature solid oxide fuel cells. Three different types of devices are fabricated to explore the optimum application of CuFe2O4 in fuel cells. Device with CuFe2O4 as a cathode catalyst exhibits a maximum power density of 180 mW/cm(2) with an open circuit voltage 1.07 V at 550 degrees C. And a power output of 587 mW/cm(2) is achieved from the device using a homogeneous mixture membrane of CuFe2O4, Li2O-ZnO-Sm0.2Ce0.8O2 and LiNi0.8Co0.15Al0.05O2. Electrochemical impedance spectrum analysis reveals different mechanisms for the devices. The results demonstrate that natural mineral, chalcopyrite, can provide a new implementation to utilize the natural resources for next generation fuel cells being cost-effective and make great contributions to the environmentally friendly sustainable energy.
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| 6. |
- Wang, Xunying, et al.
(författare)
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La0.1SrxCa0.9-xMnO3-δ -Sm0.2Ce0.8O1.9 composite material for novel low temperature solid oxide fuel cells
- 2017
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Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 42:27, s. 17552-17558
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Tidskriftsartikel (refereegranskat)abstract
- Lowering the operating temperature of the solid oxide fuel cells (SOFCs) is one of the world R&D tendencies. Exploring novel electrolytes possessing high ionic conductivity at low temperature becomes extremely important with the increasing demands of the energy conversion technologies. In this work, perovskite La0.1SrxCa0.9-xMnO3-δ (LSCM) materials were synthesized and composited with the ionic conductor Sm0.2Ce0.8O1.9 (SDC). The LSCM-SDC composite was sandwiched between two nickel foams coated with semiconductorNi0.8Co0.15Al0.05LiO2- δ (NCAL) to form the fuel cell device. The strontium content in theLSCM and the ratios of LSCM to SDC in the LSCM-SDC composite have significant effects on the electrical properties and fuel cell performances. The best performance has been achieved from LSCM-SDC composite with a weight ratio of 2:3. The fuel cells showed OCV over 1.0 V and excellent maximum output power density of 800 mW/cm2 at 550 ºC. Device processes and ionic transport processes were also discussed.
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| 7. |
- Xia, Chen, et al.
(författare)
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Natural Mineral-Based Solid Oxide Fuel Cell with Heterogeneous Nanocomposite Derived from Hematite and Rare-Earth Minerals
- 2016
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 8:32, s. 20748-20755
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Tidskriftsartikel (refereegranskat)abstract
- Solid oxide fuel cells (SOFCs) have attracted much attention worldwide because of their potential for providing clean and reliable electric power. However, their commercialization is subject to the high operating temperatures and costs. To make SOFCs more competitive, here we report a novel and attractive nanocomposite hematite LaCePrOx (hematite LCP) synthesized from low-cost natural hematite and LaCePr-carbonate mineral as an electrolyte candidate. This heterogeneous composite exhibits a conductivity as high as 0.116 S cm(-1) at 600 degrees C with an activation energy of 0.50 eV at 400-600 degrees C. For the first time, a fuel cell using such a natural mineral-based composite demonstrates a maximum power density of 625 mW cm(-2) at 600 degrees C and notable power output of 386 mW cm(-2) at 450 degrees C. The extraordinary ionic conductivity and device performances are primarily attributed to the heterophasic interfacial conduction effect of the hematite-LCP composite. These superior properties, along with the merits of ultralow cost, abundant storage, and eco-friendliness, make the new composite a highly promising material for commercial SOFCs.
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| 8. |
- Xu, Rong, et al.
(författare)
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Enhanced ionic conductivity of yttria-stabilized ZrO2 with natural CuFe-oxide mineral heterogeneous composite for low temperature solid oxide fuel cells
- 2017
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Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 42:27, s. 17495-17503
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Tidskriftsartikel (refereegranskat)abstract
- We report for the first time that the commercial yttrium stabilized zirconia (YSZ) nano composite with a natural CuFe-oxide mineral (CF) exhibits a greatly enhanced ionic conductivity in the low temperature range (500-600 degrees C), e.g. 0.48 S/cm at 550 degrees C. The CF YSZ composite was prepared via a nanocomposite approach. Fuel cells were fabricated by using a CF YSZ electrolyte layer between the symmetric electrodes of the Ni0.8Co0.2Al0.5Li (NCAL) coated Ni foam. The maximum power output of 562 mW/cm(2) has been achieved at 550 degrees C. Even the CF alone to replace the electrolyte the device reached the maximum power of 281 mW/cm(2) at the same temperature. Different ion-conduction mechanisms for YSZ and CF YSZ are proposed. This work provides a new approach to develop natural mineral composites for advanced low temperature solid oxide fuel cells with a great marketability.
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