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Polyoxometalate-based metal-organic frameworks (POMOFs) with bifunctional Lewis-Brønsted acid were designed by confining polyoxometalates (POMs: phosphotungstic acid (PW), phosphomolybdic acid (PMo) or silicotungstic acid (SiW)) within the Zr-MOFs. The confined POMs not only have their own Brønsted acid, but can also regulate the Lewis acid strength of the POMOFs via charge regulation, ultimately allowing the POMOFs to display superior catalytic performance in the tandem catalysis of furfural (FAL) to γ-valerolactone (GVL). Among the three catalysts (POMOF-PW, POMOF-PMo and POMOF-SiW), a complete conversion of FAL was achieved, while POMOF-PW exhibited the highest GVL yield (58.1 %) at 160 °C within 23 h. The leaching experiment and structural characterization of the catalyst before and after recycling confirmed the stability of the catalyst structure. The humin originates from the polymerization of furan ring-containing compounds driven by Brønsted acid. The adsorption configuration of the substrate molecules on the catalyst offers a new explanation for the tandem reaction process, i.e. that perpendicular adsorption performs only the first step of the tandem reaction, while the coexistence of perpendicular and horizontal adsorption permits the entire reaction process. This work gives unique insights into the tandem reaction of FAL and can guide the design of efficient tandem reaction catalysts. A synthetic strategy has been developed to construct polyoxometalate-based metal-organic framework (POMOF) with bifunctional Lewis-Brønsted acid sites by chemically confining polyoxometalates (POM) in metal-organic framework (MOF) channels. Confined POM not only endows the catalyst with Brønsted acid sites, but also enhances the acid strength of the catalyst through charge regulation, which finally promotes the catalyst to exhibit excellent catalytic performance in the multi-step cascade catalysis from furfural (FAL) to γ-valerolactone (GVL). This work also provides insight into the origin and driving sites of the by-product humin, as well as the role of the adsorption configuration in the catalytic process. A look into the future of the multi-step tandem reaction of FAL to GVL is presented. [Display omitted] [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]