Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation

High-throughput synthesis of a series of monometallic and bimetallic catalysts (45 bimetallic and 50 mono-metallic samples) consisting of nickel and one of nine different metal promoters (B, Co, Cu, Fe, Mg, Mn, Sn, V and Zn) supported on one of five different metal oxides (alumina, ceria, magnesia, silica and titania) is carried out via organometallic grafting using a robotic platform. The catalysts are evaluated for their activity and selectivity for the dry reforming of methane at a feed ratio of CH4:CO2 of 1 at 650-800 degrees C in a parallel flow reactor system. The type of oxide support prevails over the type of additive for both catalyst activity and stability. On Al2O3 and MgO, Fe was found to be the best promoter; on SiO2, Cu is the best promoter at 700 degrees C and higher, while on TiO2, Mn is found to enhance the conversion at 800 degrees C. On CeO2, all additives except Fe have beneficial effects. Twenty-five catalysts show > 90% methane conversion with ten catalysts showing > 95% conversion at 800 degrees C with the H-2:CO ratios ranging from 0.8 to 1.2. Amongst the ten highest performers, NiFe/Al2O3 and NiFe/MgO are more active than Ni/Al2O3 and Ni/MgO, respectively and were stable over a period of 25 h at 800 degrees C. Characterization on the as-prepared samples reveals highly dispersed phase, while after reduction in H-2, highly dispersed and reduced nickel particles up to 10 nm are formed. The particles do not increase in size under dry reforming reaction conditions at 800 degrees C. An increased hydrogen consumption observed during H-2-TPR of the nickel particles is positively correlated with methane conversion for Al2O3-based catalysts. The resistance to deactivation by coking and variation in coke structure are investigated by spectroscopic and microscopic methods to identify the relationship between metal promoters, alloy formation, and type of surface carbon deposits. Carbon whiskers were observed on the ten selected spent samples and are preferentially deposited on Ni rather than on the promoters. Carbon nanotube formation and metal particle removal from support were not observed to cause deactivation while amorphous carbon formation was clearly linked to catalyst deactivation, as amorphous carbon could encapsulate Ni, either on the support or at the end of the carbon nanotube. The organometallic grafting technique is an efficient and suitable technique for synthesizing highly dispersed and homogeneous phases which lead to high conversion and high durability for dry reforming of methane