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- Sun, Qiming, et al.
(författare)
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High performance nanosheet-like silicoaluminophosphate molecular sieves : synthesis, 3D EDT structural analysis and MTO catalytic studies
- 2014
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488. ; 2:42, s. 17828-17839
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Tidskriftsartikel (refereegranskat)abstract
- Nanosheet-like silicoaluminophosphate (SAPO) molecular sieves SAPO-34 (CHA-type) and SAPO-18 (AEI-type) with different silicon contents were synthesized under hydrothermal conditions by using tetraethylammonium hydroxide as the template. Three-dimensional electron diffraction tomography (3D EDT) technique was applied for ab initio structure solutions. Electron microscopy observations confirmed the existence of defects, i.e., intergrowth of CHA- and AEI-type frameworks caused by the different stacking manners of double 6-ring layers, but the layers were highly coherent along c direction. Compositions, acidities, chemical environments, and texture properties of all the samples were characterized by ICP, EDS, NH3-TPD, MAS NMR, and N-2 adsorption-desorption measurements. The catalytic performances of methanol-to-olefin (MTO) reactions over nano SAPO catalysts with different silicon contents were systematically studied. All of these catalysts showed excellent catalytic activity, among which SAPO-34 showed superior catalytic performance compared to SAPO-18. DFT calculations were utilized to study the different catalytic performance of CHA and AEI. Significantly to date, SAPO-34 with the lowest silicon content exhibited the longest catalyst lifetime and the lowest coking rate in the MTO reaction than any of the reported catalysts, tested under similar conditions. The straight 8-ring pore channel along the c direction provided the optimum diffusion pathway as well as the shortest diffusion length for reactant and generated olefins, thus significantly reduced the coking rate. This work demonstrates that a 3D EDT approach combined with TEM and EDS analysis from a single nanocrystal can provide a clear crystal structure, crystal orientation and compositional information of nanocrystals, which are useful for the better understanding of the catalytic performance of nanosized crystalline catalysts.
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- Zhang, Wei, et al.
(författare)
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Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting
- 2022
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Ingår i: Small. - : Wiley. - 1613-6810 .- 1613-6829. ; 18:4
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Tidskriftsartikel (refereegranskat)abstract
- Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2-HS, CoP3-HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx-HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx-HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption–desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm−2) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.
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- Yang, Liting, et al.
(författare)
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Ligand-Directed Conformational Control over Porphyrinic Zirconium Metal-Organic Frameworks for Size-Selective Catalysis
- 2021
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 143:31, s. 12129-12137
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Tidskriftsartikel (refereegranskat)abstract
- Zirconium-based metal-organic frameworks (Zr-MOFs) have aroused enormous interest owing to their superior stability, flexible structures, and intriguing functions. Precise control over their crystalline structures, including topological structures, porosity, composition, and conformation, constitutes an important challenge to realize the tailor-made functionalization. In this work, we developed a new Zr-MOF (PCN-625) with a csq topological net, which is similar to that of the well-known PCN-222 and NU-1000. However, the significant difference lies in the conformation of porphyrin rings, which are vertical to the pore surfaces rather than in parallel. The resulting PCN-625 exhibits two types of one-dimensional channels with concrete diameters of 2.03 and 0.43 nm. Furthermore, the vertical porphyrins together with shrunken pore sizes could limit the accessibility of substrates to active centers in the framework. On the basis of the structural characteristics, PCN-625(Fe) can be utilized as an efficient heterogeneous catalyst for the size-selective [4 + 2] hetero-Diels-Alder cycloaddition reaction. Due to its high chemical stability, this catalyst can be repeatedly used over six times. This work demonstrates that Zr-MOFs can serve as tailor-made scaffolds with enhanced flexibility for target-oriented functions.
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