Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts.

New and sustainable energy vectors are required as a consequence of the environmental issues associated with the continued use of fossil fuels. H is a potential clean energy source, but as a result of problems associated with its storage and transport as a gas, chemical H storage (CHS), which involves the dehydrogenation of small molecules, is an attractive alternative. In principle, formic acid (FA, 4.4 wt % H) and methanol (MeOH, 12.6 wt % H) can be obtained renewably and are excellent prospective liquid CHS materials. In addition, MeOH has considerable potential both as a direct replacement for gasoline and as a fuel cell input. The current commercial syntheses of FA and MeOH, however, use nonrenewable feedstocks and will not facilitate the use of these molecules for CHS. An appealing option for the sustainable synthesis of both FA and MeOH, which could be implemented on a large scale, is the direct metal catalyzed hydrogenation of CO. Furthermore, given that CO is a readily available, nontoxic and inexpensive source of carbon, it is expected that there will be economic and environmental benefits from using CO as a feedstock. One strategy to facilitate both the dehydrogenation of FA and MeOH and the hydrogenation of CO and H to FA and MeOH is to utilize a homogeneous transition metal catalyst. In particular, the development of catalysts based on first row transition metals, which are cheaper, and more abundant than their precious metal counterparts, is desirable. In this Account, we describe recent advances in the development of iron and cobalt systems for the hydrogenation of CO to FA and MeOH and the dehydrogenation of FA and MeOH and provide a brief comparison between precious metal and base metal systems. We highlight the different ligands that have been used to stabilize first row transition metal catalysts and discuss the use of additives to promote catalytic activity. In particular, the Account focuses on the crucial role that alkali metal Lewis acid cocatalysts can play in promoting increased activity and catalyst stability for first row transition metal systems. We relate these effects to the nature of the elementary steps in the catalytic cycle and describe how the Lewis acids stabilize the crucial transition states. For all four transformations, we discuss in detail the currently proposed catalytic pathways, and throughout the Account we identify mechanistic similarities among catalysts for the four processes. The limitations of current catalytic systems are detailed, and suggestions are provided on the improvements that are likely required to develop catalysts that are more stable, active, and practical.