The best catalysts for promoting char gasification are Group I metals, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent metal naturally in biomass char is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. The formation of an active carbon/potassium complex is frequently proposed. Calcium is the other most common active metal found in biomass, but is far less effective and less volatile. In a gasification system the metals remain as carbonate due to the action of carbon dioxide. The alkali metals can react with silica to form silicates, which prevents catalytic action. Transition metals can also participate in catalysis of gasification; iron accelerates gasification and nickel prevents carbon deposition, which helps in conditioning biomass-derived syngas. Volatile iron pentacarbonyl has been identified as a promoter of the char gasification step, with catalytic activity related to the finely dispersed low-valency metal atoms generated during the thermo-decomposition of biomass. (C) 2013 Elsevier Ltd. All rights reserved.