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The amino-functionalization alters the microenvironment over three-dimensional nanosized mesoporous silica spheres, which is beneficial to stabilize and disperse Cu clusters. The catalyst delivers a high performance for the hydrogenation of levulinic acid into γ-valerolactone, achieving a maximum yield of 98% at relatively mild conditions. [Display omitted] • Ultrafine Cu clusters confined into amino-functionalized NMSSs were developed. • The surface amino functionalization is critical to immobilizing Cu clusters. • A prominent LA hydrogenation activity with GVL yield of 98% was achieved. • This work unlocks the potential of Cu cluster catalyst in biomass valorization. The development of noble-metal-free catalysts for upgrading biomass feedstocks to chemicals and fuels remains a crucial and challenging target. Catalytic hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) is one of the essential reactions for biomass valorization. Herein, we report a confined Cu cluster catalyst, Cu/NMSSs-NH 2 , in which ultrafine Cu nanoclusters are uniformly encapsulated in the channels of amino-functionalized nanosized mesoporous silica spheres (NMSSs-NH 2). The surface amino functionalization of NMSSs plays a critical role in dispersing and stabilizing Cu species. The obtained Cu/NMSSs-NH 2 affords an excellent LA hydrogenation performance, with a GVL yield as high as 98% achieved, much higher than that of unconfined Cu particles in pristine NMSSs (Cu/NMSSs, 42%). Comprehensive characterization studies including X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy reveal that the modified microenvironment of NMSSs could not only offer a confined space but also induce an electronic interaction between metal species and the support, which effectively restrains the Cu nanoclusters from aggregation. This study unlocks the potential of inexpensive Cu cluster-based catalysts for the hydrogenation of renewable biomass to high-value chemicals. [ABSTRACT FROM AUTHOR]

The as-prepared Cu/NC@SBA-15 composites are highly active for the hydrogenation of levulinic acid to γ-valerolactone, giving a maximum yield as high as 92 % at 140 ºC in a continuous-flow fixed-bed reactor. [Display omitted] • Fine Cu clusters anchored on g-C 3 N 4 nanoconfined into SBA-15 were developed. • The defect N sites were crucial to anchor and disperse Cu nanoclusters. • An excellent GVL yield of 92 % was achieved, comparable to that of the Ru/AC. • DFT revealed that the reaction barrier of the nanoconfined Cu clusters was reduced. • The anchoring strategy prevents the sintering of Cu clusters during the reaction. The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a common reaction that is critical to biomass transformation. However, it is a great challenge to employ non-noble metal catalysts in realizing highly effective conversion from LA to GVL. Herein, we report an efficient strategy for anchoring highly active copper nanocluster catalysts on the defect sites of graphitic carbon nitride (g-C 3 N 4) and dispersing in mesoporous silica (SBA-15). The combination of g-C 3 N 4 and SBA-15 stabilized the copper clusters, leading to a high GVL yield of 92 % and excellent stability in 100 h. This result is comparable to that of the Ru/AC catalyst but much more economically favorable. Density functional theory calculations revealed that the reaction barrier of the new catalyst was reduced from 1.93 to 1.12 eV compared with those of unconfined copper particles. This research provides a simple anchoring strategy for constructing highly active and inexpensive copper nanocluster catalysts. [ABSTRACT FROM AUTHOR]