Applied Catalysis B: Environmental 99 (2010) 257–264 Contents lists available at ScienceDirect Applied Catalysis B: Environmental journal homepage: www.elsevier.com/locate/apcatb A highly active, selective and stable copper/cobalt-structured nanocatalyst for methanol decomposition Gregorio Marbán ∗ , Alba López, Irene López, Teresa Valdés-Solís Instituto Nacional del Carbón (INCAR), CSIC – c/Francisco Pintado Fe, 26, 33011 Oviedo, Spain article info Article history: Received 4 May 2010 Received in revised form 10 June 2010 Accepted 17 June 2010 Available online 25 June 2010 Keywords: Methanol decomposition Hydrogen CO Co3O4 Cobalt Cu2O Copper Spinel Catalytic activity Selectivity Stability Microreactor abstract A structured catalyst prepared by copper doping a support composed of mesoporous Co(OH) 2 /Co 3 O 4 nanowire arrays hydrothermally grown on a stainless steel mesh was used for the methanol decompo- sition reaction. When copper doping was applied to an uncalcined cobalt-based support, followed by calcination in air, the catalytic activity of the resulting bimetallic catalyst was observed to increase by about one order of magnitude with respect to that of the catalyst obtained by copper doping a calcined support. This high activity, which is accompanied by a very high selectivity to CO and a fair stability, is thought to be due to the transformation of a large proportion of the copper precursor into Cu 2 O of a low crystal size during calcination. Comparison with other catalysts reported in the literature shows that the most active catalysts prepared in this work are better than the most active, selective and stable transition metal catalysts described in the reviewed literature. © 2010 Elsevier B.V. All rights reserved. 1. Introduction Biomethanol is a fuel that is often overlooked in reports dealing with biomass as a source of energy in favor of more popular bio- fuels such as bioethanol made from corn/sugar cane or biodiesel produced from oil seed/algae. However, in terms of biomass avail- ability for energy purposes, biomethanol is the only liquid vector that could totally substitute fossil fuels in the transport sector [1,2], an event that would have a tremendous impact on global CO 2 emissions. Biomethanol can be burnt directly in an internal combustion engine [3] or be converted onboard into hydrogen for fuel cell-based electric cars. This second option has several advan- tages over the onboard storage of hydrogen [1], such as reduced storage costs, safer storage, easier and cheaper fuel distribution and supply, etc. Endothermic reactions such as methanol steam reforming or methanol decomposition are possible routes for pro- ducing hydrogen onboard. Compared to methanol decomposition, methanol steam reforming requires a substantially higher amount of heat to vaporize the reactants, conduct the reaction, and com- ∗ Corresponding author. Tel.: +34 985119090; fax: +34 985297662. E-mail address: greca@incar.csic.es (G. Marbán). pensate for heat loss from the reactor and the effluent streams. It is therefore more applicable to large scale systems, in which volumetric heat losses are lower than in small scale devices [4]. For the decomposition of methanol, the heat for the reaction can be obtained by burning the carbon monoxide released, either in a preferential oxidation step or after it has been separated from the hydrogen stream in a catalytic membrane reactor [4]. Decom- posed methanol could also be used as a source of synthesis gas for a number of chemical processes. A large number of works have been devoted in recent years to the methanol decomposition reac- tion. The following references indicate the most relevant works published over the last ten years [5–28]. As methanol decompo- sition is an endothermic reaction to which heat must be supplied, it must be performed in reactors in which heat transfer is opti- mised, such as plate-type microchannel reactors [29,30]. In this work we employ a structured reactor based on a novel concept, initially developed for the preferential oxidation of carbon monox- ide [31]. The reactor consists of a very fine stainless steel wire mesh, coated with mesoporous Co 3 O 4 nanowires (catalyst), and rolled up inside a stainless steel pipe (1/4 in. o.d.). In this kind of micro- reactor, the metal wire mesh provides a high geometric surface area for holding the catalyst. It also guarantees a negligible pres- sure drop and a good heat transfer through the reactor. To use this 0926-3373/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.apcatb.2010.06.028