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A hollow core–shell magnetic zirconium hydroxide catalyst was synthesized and employed for the catalytic transfer hydrogenation (CTH) ofnumerous biomass-derived platform molecules (furfural and other carbonyl compounds). 93.9% conversion of furfural and 97.3% selectivity of furfuryl alcohol was achieved under mild reaction conditions (160 °C, 4 h, 0.1 g catalyst) with 2-propanol as the H-donor. After 7 times of reaction cycles, the catalyst retained excellent conversion (91.1%) and selectivity (97.8%) and no structural damage was found. Furthermore, a scale-up experiment was carried out, and the results proved that the catalyst has a prospect for industrial applications in the CTH reaction. [ABSTRACT FROM AUTHOR]

In this work, a simple and economical process, the reduction preparation of the Cu/ZrOCO3 catalyst and the catalytic transfer hydrogenation (CTH)reaction of methyl levulinate (ML)were carried out simultaneously in one pot providing 89.79% product yield at 180 ° C for 7 h. Different from direct hydrogen transfer reaction catalyzed by ZrOCO3 with only valerolactone (GVL) produced, the introduction of Cu/Cu+ on ZrOCO3 carrier not only enhances the activity of the reaction, but also further converts GVL into 1,4‐pentanediol (1,4‐PDO)by indirect hydrogen transfer. In addition, we also found the copper‐loaded amphoteric carrier has better catalytic activity than the basic carrier. [ABSTRACT FROM AUTHOR]

Holey layered HEO nanocrystals with surface FLP sites have been synthesized via a temperature-variable topological transition. Merits of high-entropy oxides and nanoscale effects are favored yielding a superior catalytic performance toward the transfer hydrogenation (CTH) reaction of biomass-derived carbonyl compounds at mild conditions. Mechanistic investigation indicates that the formation of active regions between FLPs provides a stronger driving force for dissociating alcohols and activating the carbonyl groups of substrates, accounting for the enhanced catalytic activity. [Display omitted] • Holey layered high entropy oxide (HEO) nanocrystals with abundant frustrated Lewis pairs (FLPs) have been synthesized. • Combination of HEO properties and nanoscale effect drives FLPs concentrations of as-obtained catalyst up to 585.4 μmol/g. • Catalysts display superior catalytic activity and cycling performance toward the CTH reaction under mild conditions. • FLPs provide stronger driving forces for dissociating alcohols and activating the carbonyl groups of substrates. • Direct hydrogen transfer dominates the catalytic reaction over holey lamellar HEO catalysts. Creating frustrated Lewis pairs (FLPs) on stable high-entropy oxides (HEOs) is a new challenge, and also an uncultivated field in catalysis. Herein, holey layered HEO spinel nanocrystals with rich FLPs were synthesized via a temperature-driven topological transition. The FLPs on the surface of HEO spinel nanocrystals are created by oxygen vacancies (Lewis acid sites) and proximal surface hydroxyls or surface lattice oxygen (Lewis base sites). Rich FLPs furnish HEO nanocrystals a superior activity towards the catalytic transfer hydrogenation reaction of biomass-derived carbonyl compounds at mild conditions. The active regions in between FLPs provide a strong driving force for dissociating alcohols and activating carbonyl groups of substrates, as evidenced by the attenuated total reflectance-infrared spectroscopy (ATR-IR) analysis, which enhances the catalytic activity. This work develops a new kind of hydrogenation catalysts and provides a perspective for creating solid FLPs. [ABSTRACT FROM AUTHOR]

A stable and easily separable Fe 3 O 4 -12 nanoparticles exhibited the desired catalytic performance in the catalytic transfer hydrogenation reaction of furfural to furfuryl alcohol with 2-propanol as the hydrogen source. Moreover, a feasible flowchart from xylose to FOL was designed. Utilizing the process can realize the regeneration of biomass resources, the reuse and recycling of catalysts and solvents, and minimize the amount of solvents and pollutant emissions. • Magnetic Fe 3 O 4 -12 nanoparticles exhibited excellent catalytic performance for the CTH reaction of FAL to FOL. • A feasible flowchart from xylose to FOL was designed, which can realize the valorization of biomass resources. • Fe 3 O 4 -12 nanoparticles have good recyclability and universality for different carbonyl compounds. Magnetic Fe 3 O 4 -12 nanoparticles, an easily separable heterogeneous catalyst, exhibits high catalytic performance in the catalytic transfer hydrogenation (CTH) reaction of biomass-derived furfural (FAL) to furfuryl alcohol (FOL) with 2-propanol (2-PrOH) as the hydrogen source (90.1 % FOL yield at 160 °C for 5 h). Comparing Fe 3 O 4 nanoparticles with different particle sizes found that the smaller the nanoparticles, the larger the BET surface area, pore volume and pore diameter, resulting in more acid-base active sites through BET, SEM, TEM, NH 3 -/CO 2 -TPD and other characterizations. Moreover, a scaled-up CTH experiment of FAL and a stepwise reaction from xylose to FOL verified that the catalytic system has great industrial application prospects. A feasible flowchart of the chemical process from xylose to FOL was designed, which can realize the regeneration of biomass resources (xylose derived from corncob), the reuse and recycling of catalysts and solvents, and minimize the amount of solvents and pollutant emissions. [ABSTRACT FROM AUTHOR]

The transformation of lignocellulosic biomass to platform compounds (γ-valerolactone, GVL) was a significant component in biomass development. Herein, sulfonated Zr-based metal-organic frameworks (MOF-808), a bifunctional heterogeneous catalyst with Lewis and Bronsted acid sites, were prepared to catalyze the one-pot cascade reaction of furfural (FUR) to GVL. The successful modification of the sulfonic group on MOF-808 was substantiated by multiple characterization methods. By adjusting the sulfuric acid concentration to balance the Lewis acid and Bronsted acid sites of the catalyst, S-808–2.37 was confirmed as the preferred catalyst and a 60.4 % GVL yield was achieved with 99.1 % carbon balance under the optimal conditions. Moreover, the 72.8 % GVL yield reached in the 40x magnification experiment also boded well for the catalyst's application potential. The work in this paper opened up new perspectives for the application of MOF-808 porous materials in the field of selective catalytic conversion of biomass involving multi-step reactions. [Display omitted] • Strong interaction between Zr and OH of H 3 BDC led to the formation of strong Lewis acidic/basic sites in the frameworks. • The cooperative role of strong Lewis acidic/basic sites in the S-808–2.37 contributed to the excellent catalytic performance. • This work provided a promising strategy to modulate the acid-base properties of MOF-808 without affecting its structure. [ABSTRACT FROM AUTHOR]