Nanostructured carbide catalysts for the hydrogen economy

The above quote, taken from the executive summary of the Report from the US DOE Basic Energy Sciences Workshop held August 6–8, 2007,[1] places in context the research carried out at the University of California, Santa Barbara, which is reported in this document. The enormous impact of heterogeneous catalysis is exemplified by the Haber process for the synthesis of ammonia, which consumes a few % of the world’s energy supply and natural gas, and feeds as many as a third of the world’s population. While there have been numerous advances in understanding the process,[2] culminating in the awarding of the Nobel Prize to Gerhard Ertl in 2007, it is interesting to note that the catalysts themselves have changed very little since they were discovered heuristically in the the early part of the 20th century. The thesis of this report is that modern materials chemistry, with all the empirical knowledge of solid state chemistry, combined with cutting edge structural tools, can help develop and better heterogeneous catalysis. The first part of this report describes research in the area of early transition metal carbides (notably of Mo and W), potentially useful catalysts for water gas shift (WGS) and related reactions of use to the hydrogen economy. Although these carbides have been known to be catalytically useful since the 1970s,[3] further use of these relatively inexpensive materials have been plagued by issues of low surface areas and ill-defined, and often unreactive surfaces, in conjunction with deactivation. We have employed for the first time, a combination of constant-wavelength and time-of-flight neutron scattering, including a total scattering analysis of the latter data, to better understand what happens in these materials, in a manner that for the first time, reveals surface graphitic carbon in these materials in a quantitative manner. Problems of preparation, surface stability, and irreversible reactivity have become manifest in this class of materials that discourage us from pursuing these materials further