Critical Factors Affecting the Selective Transformation of 5‐Hydroxymethylfurfural to 3‐Hydroxymethylcyclopentanone Over Ni Catalysts

The ring‐rearrangement of 5‐hydroxymethylfurfural (HMF) to 3‐hydroxymethylcyclopentanone (HCPN) was investigated over Ni catalysts supported on different carbon supports and metallic oxides with different structure and acid‐base properties. Their catalytic performance was tested in a batch stirred reactor in aqueous solution at 180 °C and 30 bar of H2. Under these conditions, the HMF hydrogenation proceeds through three possible competitive routes: (i) a non‐water path leading to the total hydrogenation product, 2,5‐di‐hydroxymethyl‐tetrahydrofuran (DHMTHF), and two parallel acid‐catalyzed water‐mediated routes responsible for (ii) ring‐opening and (iii) ring‐rearrangement reaction products. All catalyst systems primarily produced HCPN, but reaction rates and product distribution were influenced by several variables, some of them intensely analyzed in this work. The most proper conditions resulted to be the presence of the medium/strong Lewis's acidity of a Ni/ZrO2 catalyst (initial TOF=5.99 min−1 and 73 % HCPN selectivity) or the Brønsted acidity originated by an oxidized high surface area graphite, Ni/HSAG‐ox (initial TOF=5.92 min−1 and 87 % HCPN selectivity). However, too high density of acidic sites on the catalyst support (Ni/Al2O3) and sulfur impurities from the HMF feedstock led to catalyst deactivation by coke deposition and Ni poisoning, respectively. While HCPN emerged as the primary product, the reaction rate and products distribution during the aqueous‐phase HMF hydrogenation over Ni‐supported catalysts were influenced by the acid properties of the catalytic system, the structural properties and hydrothermal stability of the support, as well as the purity level of the HMF feedstock.