| 1. |
- Gao, Aiping, et al.
(författare)
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Asymmetric oxidation of sulfides catalyzed by vanadium(IV) complexes of dibromo- and diiodo-functionalized chiral Schiff bases
- 2006
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 27:8, s. 743-748
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Tidskriftsartikel (refereegranskat)abstract
- The catalyst system of VO(acac)(2) and Schiff base ligands derived from 3,5-dibromo- or 3,5-diiodosalicylaldehyde and inexpensive chiral amino alcohols was prepared. This catalyst displayed good yields and moderate to high enantioselectivity for the asymmetric oxidation of aryl methyl sulfides at room temperature when 1% catalyst (VO(acac)(2)/ligand molar ratio of 1: 2) and H2O2 Oxidant were used. The ligands derived from ( S)valinol exhibited considerably higher enantioselectivity than those ligands derived from ( S)-phenylalaninol and (R)-leucinol. The enantiomeric excess values were improved up to 88% for methyl phenyl sulfoxide and 92% for methyl p-bromophenyl sulfoxide by slow dropwise addition of H2O2 with the ligand prepared from 3 15-diiodosalicylaldehyde and (s)-valinol. The present study showed that the catalytic efficiency of VO(acac)(2) /Schiff base systems could not be improved by the addition of carboxylic acids or carboxylate salts.
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| 2. |
- Han, Xin-Bao, et al.
(författare)
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Fe-substituted cobalt-phosphate polyoxometalates as enhanced oxygen evolution catalysts in acidic media
- 2020
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Ingår i: Cuihuà xuébào. - : Science Press. - 0253-9837 .- 1872-2067. ; 41:5, s. 853-857
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Tidskriftsartikel (refereegranskat)abstract
- All-inorganic and earth-abundant bi-/trimetallic hydr(oxy)oxides are widely used as oxygen evolution electrocatalysts owing to their remarkable performance. However, their atomically precise structures remain undefined, complicating their optimization and limiting the understanding of their enhanced performance. Here, the underlying structure-property correlation is explored by using a well-defined cobalt-phosphate polyoxometalate cluster [{Co-4(OH)(3)(PO4)}(4)(SiW9O34)(4)](32-) (1), which may serve as a molecular model of multimetal hydr(oxy)oxides. The catalytic activity is enhanced upon replacing Co by Fe in 1, resulting in a reduced overpotential (385 mV) for oxygen evolution (by 66 mV) compared to that of the parent 1 at 10 mA cm(-2) in an acidic medium; this overpotential is comparable to that for the IrO2 catalyst. These abundant-metal-based polyoxometalates exhibit high stability, with no evidence of degradation even after 24 h of operation.
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| 3. |
- Jia, Xiaomin, et al.
(författare)
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Single crystal metal-organic framework constructed by vertically self-pillared nanosheets and its derivative for oriented lithium plating
- 2021
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Ingår i: Cuihuà xuébào. - : Elsevier BV. - 0253-9837 .- 1872-2067. ; 42:9, s. 1553-1560
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Tidskriftsartikel (refereegranskat)abstract
- This vertically self-pillared (VSP) structure extends the application range of traditional porous materials with facile mass/ion transport and enhanced reaction kinetics. Here, we prepare a single crystal metal-organic framework (MOF), employing the ZIF-67 structure as a proof of concept, which is constructed by vertically self-pillared nanosheets (VSP-MOF). We further converted VSP-MOF into VSP-cobalt sulfide (VSP-CoS2) through a sulfidation process. Catalysis plays an important role in almost all battery technologies; for metallic batteries, lithium anodes exhibit a high theoretical specific capacity, low density, and low redox potential. However, during the half-cell reaction (Li++e=Li), uncontrolled dendritic Li penetrates the separator and solid electrolyte interphase layer. When employed as a composite scaffold for lithium metal deposition, there are many advantage to using this framework: 1) the VSP-CoS2 substrate provides a high specific surface area to dissipate the ion flux and mass transfer and acts as a pre-catalyst, 2) the catalytic Co center favors the charge transfer process and preferentially binds the Li+ with the enhanced electrical fields, and 3) the VSP structure guides the metallic propagation along the nanosheet 2D orientation without the protrusive dendrites. All these features enable the VSP structure in metallic batteries with encouraging performances.
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| 4. |
- Jiang, Yi, et al.
(författare)
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Chemical and photocatalytic water oxidation by mononuclear Ru catalysts
- 2013
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 34:8, s. 1489-1495
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Tidskriftsartikel (refereegranskat)abstract
- Four mononuclear Ru complexes with different substituents on the para position of the pyridine ligand of Ru(bda)(pic)(2) (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = picoline) were synthesized and characterized by H-1 nuclear magnetic resonance or X-ray crystallography. The electrochemical properties of this series of compounds in acidic and neutral conditions were studied by cyclic voltammetry. Their catalytic activity towards water oxidation was investigated using a chemical oxidant ([Ce(NH4)(2)(NO3)(6)] (Ce-IV) in acidic solution, or driven by visible light in a three-component system containing a photosensitizer ([Ru(bpy)(3)](2+)) and an electron acceptor (S2O82-). For the chemical water oxidation, complex 1 was found to be the most effective, exhibiting a turnover number (TON) of up to 4000. The pyridine substituent at the 4-position in 1 may be protonated giving an intensive electron-withdrawing effect. Complex 2 bears the most electron-withdrawing trifluoromethyl group under neutral conditions and showed the highest photocatalytic activity with a TON of 270 over 2 h. It was concluded that the more electron-withdrawing substituents led to higher activity towards oxygen evolution for this type of Ru catalysts in the oxidation of water.
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| 5. |
- Li, F., et al.
(författare)
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Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor
- 2017
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Ingår i: Cuihuà xuébào. - : Science Press. - 0253-9837 .- 1872-2067. ; 38:11, s. 1812-1817
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Tidskriftsartikel (refereegranskat)abstract
- In this study, we fabricated a NiOx film by electrodeposition of an ethanediamine nickel complex precursor (pH = 11) on a fluorine-doped tin oxide substrate. The resulting film is robust and exhibits high catalytic activity for electrochemical water oxidation. Water oxidation is initiated with an overpotential of 375 mV (1 mA/cm2) and a steady current density of 8.5 mA/cm2 is maintained for at least 10 h at 1.3 V versus the normal hydrogen electrode. Kinetic analysis reveals that there is a 2e−/3H+ pre-equilibrium process before the chemical rate-determining step. The low-cost preparation, robustness, and longevity make this catalyst competitive for applications in solar energy conversion and storage.
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| 6. |
- Li, F., et al.
(författare)
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Visible light-driven oxygen evolution using a binuclear Ru-bda catalyst
- 2018
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Ingår i: Cuihuà xuébào. - : Science Press. - 0253-9837 .- 1872-2067. ; 39:3, s. 446-452
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Tidskriftsartikel (refereegranskat)abstract
- Binuclear ruthenium complexes bearing the 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant. However, the catalytic properties of ruthenium dimers have not yet been explored for visible light-driven water oxidation. Herein, the photocatalytic performance of a dipyridyl propane-bridged ruthenium dimer 2 was investigated in comparison with its monomeric precursor, [Ru(bda)(pic)2] (1), in CH3CN/phosphate buffer mixed solvent in a three-component system including a photosensitizer and a sacrificial electron acceptor. Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer, which not only affected the driving force for water oxidation, but also altered the kinetics of the reaction, probably through different mechanisms associated with the O–O bond formation. As a result, dimer 2 showed significantly higher activity than monomer 1 in the solvent containing a low content of CH3CN, and comparable activities were attained with a high content of CH3CN in the solvent. Under the optimal conditions, complex 2 achieved a turnover number of 638 for photocatalytic O2 evolution.
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| 7. |
- Li, Jiayuan, et al.
(författare)
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Dye-sensitized photoanode decorated with pyridine additives for efficient solar water oxidation
- 2021
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Ingår i: Cuihuà xuébào. - : Elsevier BV. - 0253-9837 .- 1872-2067. ; 42:8, s. 1352-1359
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Tidskriftsartikel (refereegranskat)abstract
- Splitting water into hydrogen and oxygen by dye-sensitized photoelectrochemical cell (DSPEC) is a promising approach to solar fuels production. In this study, a series of pyridine derivatives as surface additives were modified on a molecular chromophore and water oxidation catalyst co-loaded TiO2 photoanode, TiO2 vertical bar RuP, 1 (RuP = Ru(4,4'-(PO3H2)(2)-2,2'-bipyridine)(2,2'-bipyridine)2, 1 = Ru(bda)(L)(2), (bda = 2,2'-bipyridine-6,6'-dicarboxylate, L = 10-(pyridin-4-yloxy)decyl)phosphonic acid). The addition of pyridine additives was found to result in up to 42% increase in photocurrent. Under simulated sun-light irradiation, TiO2 vertical bar RuP, 1, P-1 (P-1 = 4-Hydroxypyridine) produced a photo-current density of 1 mA/cm(2) at a bias of 0.4 V vs. NHE in acetate buffer. Moreover, the observed photocurrents are correlated with the electron-donating ability of the substituent groups on pyridine ring. Transient absorption measurements and electrochemical impedance spectroscopy revealed that surface-bound pyridine can effectively retard the back-electron transfer from the TiO2 conduction band to the oxidized dye, which is a major process responsible for energy loss in DSPECs.
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| 8. |
- Shang, Yu, et al.
(författare)
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Pyrrolic N or pyridinic N : The active center of N-doped carbon for CO2 reduction
- 2022
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Ingår i: Cuihuà xuébào. - : Elsevier BV. - 0253-9837 .- 1872-2067. ; 43:9, s. 2405-2413
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Tidskriftsartikel (refereegranskat)abstract
- Pyridinic N is widely regarded as the active center while pyrrolic N has low-activity in metal-free N-doped carbon for electrocatalytic CO2 reduction reaction (CO2RR) to CO, but this viewpoint remains open to question. In this study, through density functional theoretical calculations, we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO2RR, however, due to the interplay with the neighboring pyridinic N sites, the activity of pyrrolic N is dramatically suppressed. Then, experimentally, metal-free N-doped carbon spheres (NCS) electrocatalysts without significant pyridinic N content are prepared for CO2RR. The pyrrolic N in NCS shows a direct-positive correlation with the performance for CO2RR, representing the active center with high activity. The optimum NCS could produce syngas with a wide range of CO/H-2 ratio (0.09 to 12) in CO2RR depending on the applied potential, meanwhile, the best selectivity of 71% for CO can be obtained. Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO2RR, further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites. This work reveals the interaction between a variety of N species in N-doped carbon, and the potential of pyrrolic N as the new type of active site for electrocatalysts, which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high-efficient electrocatalysts.
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| 9. |
- Wang, Shuai, et al.
(författare)
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Size-control growth of thermally stable Au nanoparticles encapsulated within ordered mesoporous carbon framework
- 2016
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 37:1, s. 61-72
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Tidskriftsartikel (refereegranskat)abstract
- Simultaneously controlling the size of Au nanoparticles and immobilizing their location to specific active sites while hindering migration and sintering at elevated temperatures is a current challenge within materials chemistry. Typical methods require the use of protecting agents to control the properties of Au nanoparticles and therefore it is difficult to decouple the influence of the protecting agent and the support material. By functionalizing the internal surface area of mesoporous carbon supports with thiol groups and implementing a simple acid extraction step, we are able to design the resulting materials with precise control over the Au nanoparticle size without the need for the presence of any protecting group, whilst simultaneously confining the nanoparticles to within the internal porous network. Monodispersed Au nanoparticles in the absence of protecting agents were encapsulated into ordered mesoporous carbon at various loading levels via a coordination-assisted self-assembly approach. The X-ray diffractograms and transmission electron microscopy micrographs show that the particles have controlled and well-defined diameters between 3 and 18 nm at concentrations between 1.1 and 9.0 wt%. The Au nanoparticles are intercalated into the pore matrix to different degrees depending on the synthesis conditions and are stable after high temperature treatment at 600 degrees C. N-2 adsorption-desorption isotherms show that the Au functionalized mesoporous carbon catalysts possess high surface areas (1269-1743 m(2)/g), large pore volumes (0.78-1.38 cm(3)/g) and interpenetrated, uniform bimodal mesopores with the primary larger mesopore lying in the range of 3.4-5.7 nm and the smaller secondary mesopore having a diameter close to 2 nm. X-ray absorption near extended spectroscopy analysis reveals changes to the electronic properties of the Au nanoparticles as a function of reduced particle size. The predominant factors that significantly determine the end Au nanoparticle size is both the thiol group concentration and subjecting the as-made materials to an additional concentrated sulfuric acid extraction step.
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| 10. |
- Wang, Zhendong, et al.
(författare)
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Controllable direct-syntheses of delaminated MWW-type zeolites
- 2020
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 41:7, s. 1062-1066
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Tidskriftsartikel (refereegranskat)abstract
- A method for the direct syntheses of partially and fully delaminated MWW zeolites is reported herein. Two organic amines were introduced into the hydrothermal synthetic system: hexamethyleneimine (HMI), which acted as the structure-directing agent for the MWW layered structure; and dicyclohexylamine (DCHA), in the role of an in-situ delaminating agent. By varying the amount of DCHA, partially and fully delaminated MWW zeolites having two MWW structure layers and one single layer, respectively, were obtained. These were denoted as SCM-1 (Sinopec Composite Material) and SCM-6, respectively. The delaminated materials possess ultra-large external surface areas, and the transmission electron microscopy images illustrated their layered nature. In the reaction of liquid phase benzene alkylation with ethylene, SCM-1, the double-layered MWW zeolite, exhibited far superior catalytic performance compared to zeolite MCM-22.
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| 11. |
- Xia, Changjiu, et al.
(författare)
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Heterogeneous oxidation of cyclohexanone catalyzed by TS-1 : Combined experimental and DFT studies
- 2015
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 36:6, s. 845-854
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Tidskriftsartikel (refereegranskat)abstract
- The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite Received 26 February 21515 TS-1 using aqueous H2O2 as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H2O2 was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H2O2 was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H2O2 catalyzed by a hollow TS-1 zeolite were epsilon-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite.
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| 12. |
- Zhang, Bo, et al.
(författare)
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Rational design of bismuth-based catalysts for electrochemical CO2 reduction
- 2022
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Ingår i: Cuihuà xuébào. - : Elsevier BV. - 0253-9837 .- 1872-2067. ; 43:12, s. 3062-3088
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Forskningsöversikt (refereegranskat)abstract
- Sustainable conversion of carbon dioxide (CO2) to high value-added chemicals and fuels is a promising solution to solve the problem of excessive CO2 emissions and alleviate the shortage of fossil fuels, maintaining the balance of the carbon cycle in nature. The development of catalytic system is of great significance to improve the efficiency and selectivity for electrochemical CO2 conversion. In particular, bismuth (Bi) based catalysts are the most promising candidates, while confronting challenges. This review aims to elucidate the fundamental issues of efficient and stable Bi-based catalysts, constructing a bridge between the category, synthesis approach and electrochemical performance. In this review, the categories of Bi-based catalysts are firstly introduced, such as metals, alloys, single atoms, compounds and composites. Followed by the statement of the reliable and versatile synthetic approaches, the representative optimization strategies, such as morphology manipulation, defect engineering, component and heterostructure regulation, have been highlighted in the discussion, paving in-depth insight upon the design principles, reaction activity, selectivity and stability. Afterward, in situ characterization techniques will be discussed to illustrate the mechanisms of electrochemical CO2 conversion. In the end, the challenges and perspectives are also provided, promoting a systematic understanding in terms of the bottleneck and opportunities in the field of electrochemical CO2 conversion. Published by Elsevier B.V. All rights reserved.
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| 13. |
- Zhuo, Q., et al.
(författare)
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Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering
- 2021
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Ingår i: Cuihuà xuébào. - : Science Press. - 0253-9837 .- 1872-2067. ; 42:3, s. 460-469
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Tidskriftsartikel (refereegranskat)abstract
- A molecular [Ru(bda)]-type (bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand (Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene (3F) or styrene (St) blocking units on the surface of glassy carbon (GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via (1) the radical coupling interaction between the two metallo-oxyl radicals (I2M) in the homo-coupling polymer (poly-1), and (2) the water nucleophilic attack (WNA) pathway in poly-1+P3F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.
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| 14. |
- Guo, X. W., et al.
(författare)
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Methylation of 4-methylbiphenyl with methanol over metal oxide-modified HZSM-5 zeolite catalysts
- 2003
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 24:5, s. 333-337
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Tidskriftsartikel (refereegranskat)abstract
- A series of HZSM-5 zeolite catalysts modifed with metal oxides (MgO, CaO, SrO, BaO, ZnO, La2O3 and CeO2) were prepared by impregnation method and characterized by XRD, TPD and N-2-adsorption. Methylation of 4-methylbiphenyl (4-MBP) with methanol to 4,4'-dimethylbiphenyl (4,4'-DMBP) was carried out over the prepared catalysts under fixed-bed down-flow conditions. The results showed that the MgO-modified HZSM-5 can significantly improve the selectivity for target product 4,4'-DMBP (up to 80 % vs only 13 % over the parent HZSM-5). The effects of metal oxides on 4,4'-DMBP selectivity are arranged in the following order: MgO>SrOapproximate toZnOapproximate toCaOapproximate toLa(2)O(3)>BaO>CeO2. The effects of MgO contents, precursor-salt types, and loading methods were further investigated, and the results revealed that during 4-MBP conversion, proper MgO loading (5.6 %) can be more effective, and the ion-exchange methed is much better than the impregnation method. However, it is difficult to get higher metal oxide loading by using the ion-exchange method. The high selectivity over HZSM-5 modified with MgO largely results from the depression of 4,4-DMBP second reactions such as isomerization, dealkylation and alkylation, as demonstrated by the reaction of 4,4'-DMBP as reactant over MgO/ZSM-5 catalyst and HZSM-5 zeolite.
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| 15. |
- Qiu, Chun-Yu, et al.
(författare)
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Revealing the concentration of hydrogen peroxide in fuel cell catalyst layers by an in-operando approach
- 2022
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Ingår i: Chinese Journal of Catalysis. - 1872-2067. ; 43:7, s. 1918-1926
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Tidskriftsartikel (refereegranskat)abstract
- To evaluate the H2O2-tolerance of non-Pt oxygen reduction reaction (ORR) catalysts as well as investigate the H2O2-induced decay mechanism, the selection of an appropriate H2O2 concentration is a prerequisite. However, the concentration criterion is still unclear because of the lack of in-operando methods to determine the actual concentration of H2O2 in fuel cell catalyst layers. In this work, an electrochemical probe method was successfully established to in-operando monitor the H2O2 in non-Pt catalyst layers for the first time. The local concentration of H2O2 was revealed to reach 17 mmol/L, which is one order of magnitude higher than that under aqueous electrodes test conditions. Powered by the new knowledge, a concentration criterion of at least 17 mmol/L is suggested. This work fills in the large gap between aqueous electrode tests and the real fuel cell working conditions, and highlights the importance of in-operando monitoring methods.
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| 16. |
- Elming, Sten-åke, et al.
(författare)
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Proterozoic Basic dykes in the Ukrainian Shield: A palaeomagnetic, geochronologic and geochemical study-The accretion of the Ukrainian Shield to Fennoscandia
- 2010
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Ingår i: Precambrian Research. - : Elsevier BV. - 0301-9268 .- 1872-7433. ; 178:1-4, s. 119-135
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Tidskriftsartikel (refereegranskat)abstract
- A palaeomagnetic, geochronologic and geochemical study of basic dykes in the Ukrainian Shield has been undertaken with the purpose of testing a hypothesis for timing of accretion of the Ukrainian Shield with Fennoscandia. On the basis of geological data it has been suggested that the two shields amalgamated at ca. 1900-1800 Ma. With this study of 11 basic dykes the palaeomagnetic database for the Ukrainian Shield is extended. The palaeomagnetic data indicate three generations of dykes. This is supported by the age data and the difference in geochemical compositions. Ages of two ca. 25 m wide dykes (Susly) in the North-Western Block of the shield have been determined, one for which a positive palaeomagnetic field test is demonstrated. The lower of the two Ar-40/Ar-39 hornblende ages of this dyke, 2061 +/- 20 Ma, is similar to the U-Pb, zircon age of the granitic host rock (ca. 2067 Ma, U-Pb, zircon), which suggests that the dyke intruded shortly after crystallization of the granite. Combined with the magnetization of the baked contact and that of another dyke a new ca 2060 Ma pole is presented (Plat. = 15.7 degrees, Plon. = 182.9 degrees, A(95) = 13.7 degrees). which may be regarded as a VGP. An U-Pb age of 1722 +/- 12 Ma of baddeleyite from the Khmelnik dyke, which yields a well-defined VGP, is similar to the age of nearby anorthosite complexes. A new 1740-1770 Ma key pole for the Ukranian Shield is also presented (Plat. = 26.5 degrees, Plon. = 169.1 degrees, A(95) = 3.9 degrees). On the basis of palaeomagnetic and geochronological data a 2060-1720 Ma apparent polar wander for the Ukrainian Shield is defined. This apparent polar wander is significantly different from that of Fennoscandia during the same time interval and indicates that the two shields were not in their present relative positions at ca. 1770 Ma. A scenario is here proposed where the Ukrainian Shield (and Sarmatia) collided with Fennoscandia at ca. 1900-1800 Ma and after that event, at ca. 1720-1660 Ma, it rotated approximately 43 degrees into its present position. (C) 2010 Elsevier B.V. All rights reserved.
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