The catalytic transformation of renewable fatty acids into value-added fatty alcohols without the use of gaseous hydrogen is a versatile technique for the utilization of microalgae and waste cooking oil, where Cu-based catalysts are considered to be the most suitable candidate. However, the interpretation of the structure–reactivity relationship caused by different crystal types of carriers and the metal–support interface is not well understood. Herein we synthesized ZrO2-supported Cu nanoparticle catalysts via different preparation methods and reduction temperatures under similarly exposed surface facets and Cu valency but different polymorphic phases of ZrO2 (monoclinic ZrO2: m-ZrO2; tetragonal ZrO2: t-ZrO2) and the metal–support interface. Interestingly, the as-synthesized Cu/t-ZrO2 catalysts showed remarkably better catalytic performance than Cu/m-ZrO2 for the in situ hydrogenation of lauric acid in the methanol–water system. Combined experimental and density functional theory (DFT) calculation results ascribed the lower efficiency of m-ZrO2 as a carrier to weakly adsorbed reactant and intermediate molecules as well as the absence of an oxygen vacancy in the crystal phase. The interface-rich Cu/t-ZrO2 catalysts displayed higher activity normalized to the surface-exposed Cu sites toward lauryl alcohol production than the interface-deficient counterparts. DFT calculation results further revealed that this metal–support interface plays an important role in promoting the C–O bond or H–H bond cleavage in two possible reaction routes, thus reducing the activation barrier of the overall reaction.

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Selective preparation of unsaturated alcohols via the hydrogenation of CO in α,β-unsaturated aldehydes is a challenging reaction. In this work, a nanoscale material Pt/UiO-66 catalyst with homogenously dispersed Pt nanoparticles encapsulated in UiO-66 was prepared. Its performance for the selective formation of unsaturated alcohols from unsaturated aldehydes with molecular H2 and via the catalytic transfer hydrogenation (CTH) was compared. It was found that Pt/UiO-66 was more selective and efficient for the hydrogenation of the CO bond to alcohol when isopropanol was utilized as hydrogen donors instead of molecular H2. The selectivity of unsaturated alcohols reached 94.6% at a 90.5% conversion of unsaturated aldehydes at 150 °C. At the same time, the utilization of isopropanol as hydrogen donors reached 92.6%, and a turnover frequency of 4071 h–1 was achieved. The CTH reaction mechanism over Pt/UiO-66 was suggested based on the results of several control experiments.