Dimethyl ether steam reforming (DME SR) is a promising route to provide H2 for on‐board H2‐based fuel cells. Herein, we synthesized the La2O3‐modified Cu/SiO2 catalyst with dual copper species of Cu0 and Cu+ for DME SR, which exhibits both the high catalytic performance and long‐term stability. The strong electron donor‐acceptor interaction between the lanthanum and copper species occurs after reduction of the catalysts, which is an essential factor to quantitatively determine the ratio of Cu+/(Cu0+Cu+). The addition of La can improve the dispersion of both metallic Cu and Cu2O on the catalysts, as well. After modulating the ratio of Cu+/(Cu0+Cu+) to ∼0.5 by varying the La loading, we achieved the highest activity and lowest CO selectivity. After the durability tests, the results of TEM, EXAFS, and XPS reveal that the addition of La on the Cu/SiO2 catalysts not only stabilizes the copper species from aggregation, especially for the metallic Cu, but also avoids over‐reduction of the Cu+ species to Cu0. The constant ratio of Cu+/(Cu0+Cu+) on the La‐modified Cu/SiO2 catalyst ensures the high catalytic stability in DME SR.

Steam reforming of simple oxygenated hydrocarbons without CÀC bonds is suitable for small-scale decentralized H 2 production for fuel cells. However, the relatively high CO concentration in H 2 -rich reformates produced by traditional Cu-based catalysts will poison the Pt-based anode in fuel cells. Here, we describe a new approach to the design of CuÀNi bimetallic catalysts based on nickel-phyllosilicate for steam reforming of dimethyl ether (DME). With the tunable formation of the CuÀNi alloy, we can modulate the selectivity of CO and CH 4 in steam reforming and achieve H 2 -rich reformates with an ultra-low concentration of CO (below 1000 ppm). This process only requires simple and low-energy purification pretreatments to meet the requirements of commercial fuel cells. Mechanistic studies reveal that the CuÀNi alloy can adsorb CO, particularly at high temperatures, and simultaneously suppress CO dissociation to methane.

Dimethyl ether steam reforming (DME SR) is one of attractive technologies to online provide H 2 for fuel cells in vehicles. Herein, we adopt a novel sputtering method to prepare a Cu-ZnO/γ-Al 2 O 3 (CuZn− S) bifunctional catalyst with only 2.9 wt % Cu loading. The interaction between Cu and ZnO suppresses the thermal aggregation of Cu nanoparticles in DME SR. The Cu nanoparticles (methanol steam reforming sites) are highly and homogeneously dispersed and anchored on the external surface of γ-Al 2 O 3 (DME hydrolysis sites). It significantly improves the utilization efficiency of the Cu species and the mass transfer, thereby achieving high catalytic performance for DME SR. Its reaction rate per unit mass of Cu is 50 times to that of the CuZnAlO/γ-Al 2 O 3 catalyst at 300 °C. In addition, this unique structure inhibits the side reactions of methanol direct decomposition and reverse water gas shift to suppress CO production.