Hydrogen generation using a CuO/ZnO-ZrO2 nanocatalyst for autothermal reforming of methanol in a microchannel reactor.

In the present work, a microchannel reactor for autothermal reforming of methanol using a synthesized catalyst porous alumina support-CuO/ZnO mixed with ZrO2 sol washcoat has been developed and its fine structure and inner surface characterized. Experimentally, CuO/ZnO and alumina support with ZrO2 sol washcoat catalyst (catalyst slurries) nanoparticles is the catalytically active component of the microreactor. Catalyst slurries have been dried at 298 K for 5 h and then calcined at 623 K for 2 h to increase the surface area and specific pore structures of the washcoat catalyst. The surface area of BET N2 adsorption isotherms for the as-synthesized catalyst and catalyst/ZrO2 sol washcoat samples are 62 and 108 ± 2 m²g⁻¹, respectively. The intensities of Cu content from XRD and XPS data indicate that Al2O3 with Cu species to form CuAl2O4. The EXAFS data reveals that the Cu species in washcoat samples have Cu-O bonding with a bond distance of 1.88 ± 0.02 Å and the coordination number is 3.46 ± 0.05, respectively. Moreover, a hydrogen production rate of 2.16 L h⁻¹ is obtained and the corresponding methanol conversion is 98% at 543 K using the CuO/ZnO with ZrO2 sol washcoat catalyst.

Application of flexible micro temperature sensor in oxidative steam reforming by a methanol micro reformer.

Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS) technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM), with the relevant parameters optimized as well.

Temperature-programmed reduction study on carbon-supported platinum-gold alloy catalysts.

Alloy catalysts of Pt-Au/C with different Pt/Au ratios were prepared by the precipitation-deposition of metal chlorides and reduced by H(2) at 470 K. The surface composition of alloy crystallites deposited on the prepared catalysts was characterized by a technique of temperature-programmed reduction (TPR). In the characterization, O(2) was chemisorbed on the reduced catalysts and the chemisorbed O(2) was reduced by TPR. A low-temperature routine (LT) in the temperature range between 120 and 430 K was used for the TPR characterization. Monometallic catalysts of Au/C and Pt/C showed a reduction peak in the LT-TPR at reduction temperature (T(r))=145 and 240 K, respectively. T(r) from alloyed catalysts fell in the range and increased monotonously with their Pt/Au ratios. Interior Pt atoms in deposited alloy particles tended to segregate toward their surface during oxidation treatment at elevated temperatures.

Poly(vinylpyrrolidone)-modified graphite carbon nanofibers as promising supports for PtRu catalysts in direct methanol fuel cells.

Carbon nanomaterials, including herringbone graphite carbon nanofibers (GNFH), multiwalled carbon nanotubes (MWCNT), and carbon black, were surface-modified by a new poly(vinylpyrrolidone) (PVP) grafting process as well as by the conventional acid-oxidation (AO) process, and characterized by FTIR, TGA, Raman, HRTEM, XRD, and XPS measurements. Pt nanoparticles of 1.8 nm were evenly deposited on all PVP-grafted carbon nanomaterials. The effects of the two surface modification processes on the dispersion, average Pt nanoparticle sizes, the electrocatalytic performance, and electrical conductivities of Pt-carbon nanocomposites in direct methanol oxidation were systematically studied and compared. It was found that the PVP-grafted carbon nanomaterials have much less loss in the electric conductivity and thus better electrocatalytic performance, 17-463% higher, than their corresponding acid oxidation-treated nanocomposites. The electrocatalytic performance of the Pt-carbon nanocomposites decreases in the following order: Pt-PVP-GNFH > Pt-PVP-MWCNTarc > Pt-AO-MWCNTarc > Pt-PVP-MWCNTCVD > Pt-AO-MWCNTCVD > Pt-XC-72R > Pt-AO-GNFH, with the Pt-PVP-GNFH nanocomposite having approximately 270% higher performance than that of the Pt-Vulcan XC-72R nanocomposite. In addition, PtRu-PVP-GNFH shows even better (50% higher) electrocatalytic activity than the Pt-PVP-GNFH nanocomposite at a 0.6 V applied voltage.

Promotion of the electrochemical activity of a bimetallic platinum-ruthenium catalyst by oxidation-induced segregation.

An alloy catalyst of 15 wt % Pt(50)Ru(50)/C was prepared by the method of incipient wetness impregnation and activated by hydrogen reduction at 620 K. Physical characterization of the freshly reduced catalyst indicated that bimetallic crystallites, Pt rich in the shell and Ru rich in the core, were finely dispersed in a diameter of dPtRu approximately 2 nm on carbon support. The reduced catalyst was subsequently modified by oxidization in air. On increasing the temperature of oxidation (T(o)), atoms of Ru in the core were found segregated to the surface of bimetallic crystallites and oxidized to amorphous RuO(2). Crystalline RuO(2) (RucO(2)) was formed on extensive segregation at To > 520 K. Catalytic activity of the alloy catalyst for electro-oxidation of methanol was examined by cyclic voltammetry. Electrochemical activity of the Pt-Ru/C catalyst was found to be significantly enhanced by oxidation treatments. The enhancement was, therefore, attributed to the segregation of Ru and the formation of RucO(2). Extensive oxidation treatment at elevated temperatures of To > 600 K, however, caused the deactivation of the electroactivity. The deactivation should be the result of excessive oxidation of the carbon support.

Chemical activity of palladium clusters: Sorption of hydrogen.

Samples of Pd/SiO2 with average cluster size of palladium (d(Pd)) ranging from 1 to 10 nm were prepared by different methods, such as incipient wetness impregnation (IW), ion exchange (IE), and sol-gel (SG). The dispersion (D(Pd)) for prepared Pd/SiO2 samples varied with the method of preparation and showed a trend of IW < IE < SG. Chemical interaction between the dispersed nanopalladium and hydrogen gas was calorimetrically studied as a function of hydrogen uptake. Measured profiles of interaction energy vary with the d(Pd) of studied samples. The initial heat of hydrogen chemisorption (Q(Hi)) also steeply increases for particles with d(Pd) smaller than 2 nm.

Characterization of surface composition of platinum and ruthenium nanoalloys dispersed on active carbon.

Supported samples of 8 wt % monometallic Pt/C and Ru/C, as well as 12 wt % bimetallic Pt50Ru50/C, were prepared by the method of incipient wetness impregnation. Impregnated samples were subsequently reduced by hydrogen and then oxidized in air at different To temperatures. TEM and XRD examinations indicated that metal crystallites were finely dispersed with a diameter of dM < or = 3 nm on the reduced samples. Reductive behavior of the oxidized samples by hydrogen was pursued with the technique of temperature programmed reduction (TPR). The temperature of the reduction peaks (Tr) noticed in the TPR profiles varied with the metal composition of catalysts and To temperature of oxidation. At To = 300 K, oxidation was confined to the surface layer of metallic crystallites. As a result, Pts O (with a peak at Tr = 230 K) or PtsO2 (Tr = 250 K) was formed on monometallic Pt/C while RusO2 (Tr approximately 380 K) was formed on Ru/C. A reductive peak with Tr = 250 K was found from the bimetallic sample from Pt50Ru50/C oxidized at To = 300 K. The reductive peak suggests bimetallic crystallites were dispersed with cherry type structure, with Pt exposed at the surface and Ru in the core. On increasing the To temperature of oxidation treatment to 370 K and higher, Tr peaks between 270 and 350 K were gradually noticed on the oxidized bimetallic sample. Peaks in this Tr region are assigned to reduction of the oxidized alloy surface (AsO). Evidently, a segregation of Ru to the surface of the bimetallic crystallites is indicated upon oxidation at To > 380 K.

Selective production of hydrogen from partial oxidation of methanol over silver catalysts at low temperatures.

Hydrogen can be effectively and selectively produced from the partial oxidation of methanol over Ag/CeO(2)-ZnO catalyst at low temperatures (T(r) < 200 degree C).