The electrochemical reduction of CO2 has gained significant interest recently as it has the potential to trigger a sustainable solar-fuel-based economy. In this Perspective, we highlight several heterogeneous and molecular electrocatalysts for the reduction of CO2 and discuss the reaction pathways through which they form various products. Among those, copper is a unique catalyst as it yields hydrocarbon products, mostly methane, ethylene, and ethanol, with acceptable efficiencies. As a result, substantial effort has been invested to determine the special catalytic properties of copper and to elucidate the mechanism through which hydrocarbons are formed. These mechanistic insights, together with mechanistic insights of CO2 reduction on other metals and molecular complexes, can provide crucial guidelines for the design of future catalyst materials able to efficiently and selectively reduce CO2 to useful products.

Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide

The past decade of organic chemistry may be charcterized as a period of violent development of new synthetic methods. This was accompained by a systematization of the analysis of synthetic problems (synthetic strategy). The planning of the synthesis of an organic target molecule is greatly facilitated by distinguishing between reagents X(C)n … with normal reactivity (acceptor properties at C1,3,5…, donor properties at X, C2,4…) and with reactivity umpolung (acceptor properties at X, C2,4…, donor properties at C1,3,5…). In this context, reactivity umpolung turned out to be useful as a heuristic principle, as a classification scheme, and as an aid for locating so-called strategic bonds (synthon, transform, and antithesis according to E. J. Corey). There are six principal methods of umpolung: 1 2n-oxidation, heteroatom exchange and modification, homologation and its reversal, the cyclopropane “trick”, use of acetylenes, and redox reactions; under certain circumstances none of these techniques is necessary in cases where direct umpolung is possible. Throughout the article, normal reactivity is indicated by green print; reactivity umpolung by red print.

Methods of Reactivity Umpolung

We have investigated the reaction mechanism of the electrochemical reduction of carbon dioxide to hydrocarbons on copper electrodes. This reaction occurs via two pathways: a C1 pathway leading to methane, and a C2 pathway leading to ethylene. To identify possible intermediates in the reduction of carbon dioxide we have studied the reduction of small C1 and C2 organic molecules containing oxygen. We followed the formation and consumption of intermediates during the reaction as a function of potential, using online mass spectrometry. For the C1 pathway we show that it is very likely that CHOads is the key intermediate towards the breaking of the C–O bond and, therefore, the formation of methane. For the C2 pathway we suggest that the first step is the formation of a CO dimer, followed by the formation of a surface-bonded enediol or enediolate, or the formation of an oxametallacycle. Both the enediol(ate) and the oxametallacycle would explain the selectivity of the C2 pathway towards ethylene. This new mechanism is significantly different from existing mechanisms but it is the most consistent with the available experimental data.

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

This Perspective illustrates the defining characteristics of free radical chemistry, beginning with its rich and storied history. Studies from our laboratory are discussed along with recent developments emanating from others in this burgeoning area. The practicality and chemoselectivity of radical reactions enable rapid access to molecules of relevance to drug discovery, agrochemistry, material science, and other disciplines. Thus, these reactive intermediates possess inherent translational potential, as they can be widely used to expedite scientific endeavors for the betterment of humankind.

Michael P. Fleming

Papers

New method for the reductive coupling of carbonyls to olefins. Synthesis of .beta.-carotene

Titanium-induced reductive coupling of carbonyls to olefins

Improved procedures for the reductive coupling of carbonyls to olefins and for the reduction of diols to olefins

Reduction of epoxides to olefins with low valent titanium

Some deoxygenation reactions with low-valent titanium (titanium trichloride/lithium tetrahydroaluminate)