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1.
Phys Chem Chem Phys ; 24(25): 15603, 2022 Jun 29.
Article in English | MEDLINE | ID: mdl-35723629

ABSTRACT

Correction for 'The synergic effect between Mo species and acid sites in Mo/HMCM-22 catalysts for methane aromatization' by Ding Ma et al., Phys. Chem. Chem. Phys., 2005, 7, 3102-3109, https://doi.org/10.1039/B502794B.

2.
Glob Chall ; 2(11): 1800032, 2018 Nov.
Article in English | MEDLINE | ID: mdl-30546916

ABSTRACT

Photocatalytic CO2 reduction with water to hydrocarbons represents a viable and sustainable process toward greenhouse gas reduction and fuel/chemical production. Development of more efficient catalysts is the key to mitigate the limits in photocatalytic processes. Here, a novel ultrathin-film photocatalytic light absorber (UFPLA) with TiO2 films to design efficient photocatalytic CO2 conversion processes is created. The UFPLA structure conquers the intrinsic trade-off between optical absorption and charge carrier extraction efficiency, that is, a solar absorber should be thick enough to absorb majority of the light allowable by its bandgap but thin enough to allow charge carrier extraction for reactions. The as-obtained structures significantly improve TiO2 photocatalytic activity and selectivity to oxygenated hydrocarbons than the benchmark photocatalyst (Aeroxide P25). Remarkably, UFPLAs with 2-nm-thick TiO2 films result in hydrocarbon formation rates of 0.967 mmol g-1 h-1, corresponding to 1145 times higher activity than Aeroxide P25. This observation is confirmed by femtosecond transient absorption spectroscopic experiments where longer charge carrier lifetimes are recorded for the thinner films. The current work demonstrates a powerful strategy to control light absorption and catalysis in CO2 conversion and, therefore, creates new and transformative ways of converting solar energy and greenhouse gas to alcohol fuels/chemicals.

3.
Angew Chem Int Ed Engl ; 56(45): 14031-14035, 2017 11 06.
Article in English | MEDLINE | ID: mdl-28981203

ABSTRACT

Fluid catalytic cracking is a chemical conversion process of industrial scale. This process, utilizing porous catalysts composed of clay and zeolite, converts heavy crude-oil fractions into transportation fuel and petrochemical feedstocks. Among other factors iron-rich reactor and feedstream impurities cause these catalyst particles to permanently deactivate. Herein, we report tomographic X-ray absorption spectroscopy measurements that reveal the presence of dissimilar iron impurities of specific localization within a single deactivated particle. Whereas the iron natural to clay in the composite seems to be unaffected by operation, exterior-facing and feedstream-introduced iron was found in two forms. Those being minute quantities of ferrous oxide, located near regions of increased porosity, and impurities rich in Fe3+ , preferentially located in the outer dense part of the particle and suggested to contribute to the formation of an isolating amorphous silica alumina envelope.

4.
ChemCatChem ; 7(3): 413-416, 2015 Feb.
Article in English | MEDLINE | ID: mdl-26191088

ABSTRACT

Porosity in catalyst particles is essential because it enables reactants to reach the active sites and it enables products to leave the catalyst. The engineering of composite-particle catalysts through the tuning of pore-size distribution and connectivity is hampered by the inability to visualize structure and porosity at critical-length scales. Herein, it is shown that the combination of phase-contrast X-ray microtomography and high-resolution ptychographic X-ray tomography allows the visualization and characterization of the interparticle pores at micro- and nanometer-length scales. Furthermore, individual components in preshaped catalyst bodies used in fluid catalytic cracking, one of the most used catalysts, could be visualized and identified. The distribution of pore sizes, as well as enclosed pores, which cannot be probed by traditional methods, such as nitrogen physisorption and isotherm analysis, were determined.

5.
Phys Chem Chem Phys ; 7(16): 3102-9, 2005 Aug 21.
Article in English | MEDLINE | ID: mdl-16186916

ABSTRACT

The acid properties of Mo/HMCM-22 catalyst, which is the precursor form of the working catalyst for methane aromatization reaction, and the synergic effect between Mo species and acid sites were studied and characterized by various characterization techniques. It is concluded that Brønsted and Lewis acidities of HMCM-22 are modified due to the introduction of molybdenum. We suggest a monomer of Mo species is formed by the exchange of Mo species with the Brønsted acid sites. On the other hand, coordinate unsaturated sites (CUS) are suggested to be responsible for the formation of newly detected Lewis acid sites. Computer modelling is established and coupling with experimental results, it is then speculated that the effective activation of methane is properly accomplished on Mo species accommodated in the 12 MR supercages of MCM-22 zeolite whereas the Brønsted acid sites in the same channel system play a key role for the formation of benzene. A much more pronounced volcano-typed reactivity curve of the Mo/HMCM-22 catalysts, as compared with that of the Mo/HZSM-5, with respect to Mo loading is found and this can be well understood due to the unique channel structure of MCM-22 zeolite and synergic effect between Mo species and acid sites.


Subject(s)
Acids/chemistry , Hydrocarbons, Aromatic/chemistry , Methane/chemistry , Models, Chemical , Models, Molecular , Molybdenum/chemistry , Zeolites/chemistry , Binding Sites , Catalysis , Computer Simulation , Hydrocarbons, Aromatic/analysis , Mass Spectrometry , Molybdenum/analysis , Spectroscopy, Fourier Transform Infrared , Zeolites/analysis
6.
Chem Commun (Camb) ; (9): 1143-5, 2005 Mar 07.
Article in English | MEDLINE | ID: mdl-15726172

ABSTRACT

Nickel phosphide on carbon is successfully synthesized by temperature-programmed reduction as verified with X-ray diffraction and extended X-ray absorption fine structure measurements; it shows superior activity, selectivity, and stability for sulfur removal from the refractory compound 4,6-dimethyldibenzothiophene with a steady-state conversion of 99%, which is much higher than that of a commercial NiMoS/[gamma]-Al2O3 catalyst of 68%.

7.
Chem Commun (Camb) ; (1): 86-7, 2003 Jan 07.
Article in English | MEDLINE | ID: mdl-12610978

ABSTRACT

Excellent stability and high catalytic activity of methane dehydrocondensation towards benzene and naphthalene on Mo/HZSM-5 were achieved at 1023-1073 K by a periodic H2 or CO2 switching operation, owing to the efficient removal of coke deposition.

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