Alcohol coupling, also known as the Guerbet reaction, is a potentially important process to increase the value of short chain alcohols. Metal oxides, metal phosphates, and supported transition metals, such as copper, are important components of heterogeneous catalysts for the reaction. However, the wide variety of catalyst compositions, reaction conditions, and reactor configurations used to study the reaction complicate a direct comparison of various catalysts. In this review, rates over different catalysts will be compared, the influences of the acid and base properties of the catalyst on product selectivity will be presented, and possible reaction paths to accomplish alcohol coupling will be discussed.

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To examine the promotional effect that zirconia has on magnesia in catalysis, mixed oxides were prepared by coprecipitation under controlled‐pH conditions or rising‐pH conditions. The resulting mixed oxides were characterized by using NH3 and CO2 adsorption microcalorimetry, X‐ray diffraction, and scanning electron microscopy. The samples were also tested as catalysts for transesterification of tributyrin with methanol, coupling of acetone, and conversion of ethanol to ethene, ethanal, and butanol. Zirconia promoted the activity of MgO for both transesterification and acetone coupling reactions, presumably by exposing new acid–base pairs at the surface. During ethanol conversion, however, zirconia promoted the dehydration reactions. Characterization and reactivity results suggest that a Mg‐Zr sample prepared by controlled‐pH precipitation exposes more ZrO2 than a sample prepared by the rising‐pH method.