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1.
Angew Chem Int Ed Engl ; 53(5): 1378-81, 2014 Jan 27.
Article in English | MEDLINE | ID: mdl-24339230

ABSTRACT

Low-temperature electricity-driven water splitting is an established technology for hydrogen production. However, the two main types, namely proton exchange membrane (PEM) and liquid alkaline electrolysis, have limitations. For instance, PEM electrolysis requires a high amount of costly platinum-group-metal (PGM) catalysts, and liquid alkaline electrolysis is not well suited for intermittent operation. Herein we report a highly efficient alkaline polymer electrolysis design, which uses a membrane-electrode assembly (MEA) based on low-cost transition-metal catalysts and an anion exchange membrane (AEM). This system exhibited similar performance to the one achievable with PGM catalysts. Moreover, it is very suitable for intermittent power operation, durable, and able to efficiently operate at differential pressure up to 3 MPa. This system combines the benefits of PEM and liquid alkaline technologies allowing the scalable production of low-cost hydrogen from renewable sources.

2.
J Am Chem Soc ; 132(40): 14152-62, 2010 Oct 13.
Article in English | MEDLINE | ID: mdl-20849104

ABSTRACT

Uniform and highly dispersed γ-Fe(2)O(3) nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe(2)O(3) nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe(2)O(3)/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60,000 cm(3) g(cat)(-1) h(-1). At a space velocity of 7500 cm(3) g(cat)(-1) h(-1), complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe(2)O(3) nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe(2)O(3) and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe(2)O(3)/CMK-5 catalyst is much more active than the benchmark NiO/Al(2)O(3) catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe(2)O(3) nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity.

3.
Chem Commun (Camb) ; (34): 4022-4, 2008 Sep 14.
Article in English | MEDLINE | ID: mdl-18758613

ABSTRACT

Cubic ordered mesoporous Co3O4, prepared via the nanocasting pathway using KIT-6 as hard template, was found to be an excellent catalyst for low temperature CO oxidation, with the activity clearly depending on surface area and pore systems of the catalysts.

4.
Chem Commun (Camb) ; (19): 1916-8, 2007 May 21.
Article in English | MEDLINE | ID: mdl-17695228

ABSTRACT

Fresh commercial carbon nanotubes (CNTs) containing residual Co or Fe nanoparticles are highly active for NH3 decomposition while the microstructure of CNTs remains unchanged. The catalysts are promising for elimination of NH3 from coal gasification stream and for production of H2 from NH3.

6.
Chem Commun (Camb) ; (16): 1772-4, 2006 Apr 28.
Article in English | MEDLINE | ID: mdl-16609800

ABSTRACT

Mesoporous MgAl2O4 spinel monolith was synthesized by the nanocasting pathway; high activity in CO oxidation was observed over gold catalysts based on such monoliths as support.

7.
J Am Chem Soc ; 128(3): 917-24, 2006 Jan 25.
Article in English | MEDLINE | ID: mdl-16417382

ABSTRACT

In this work, we present a detailed study concerning the evaluation of the metal-support interaction in high activity gold catalysts for CO oxidation. Using the colloidal deposition method, model catalysts were prepared, which allow the isolation of the effect of the support on the catalytic activity. Prefabricated gold particles were thus deposited on different support materials. Since the deposition process did not change the particle sizes of the gold particles, only the influence of the support could be studied. TiO2, Al2O3, ZrO2, and ZnO were used as support materials. Catalytic tests and high resolution transmission electron microscopy clearly show that the support contributes to the activity. However, our results are not in line with the distinction between active and passive supports based on the semiconducting properties of the oxidic material. The most active catalysts were obtained with TiO2 and Al2O3, while ZnO and ZrO2 gave substantially less active catalysts. Furthermore, the effect of other important parameters on the catalytic activity (i.e., particles size distribution, calcination temperature, and aging time for a Au/TiO2 catalyst) has also been studied. Using this preparation route, the catalysts show high-temperature stability, size dependent activity, and a very good long-term stability.

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