Lungang Chen

Selective ring-opening hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) offers a sustainable route to linear polyols, but achieving high selectivity remains challenging because of competing hydrogenation pathways and the limited understanding of how catalyst interfaces govern furanic C–O bond activation. Herein, we report an inverse ZrO2/Cu catalyst that enables highly selective conversion of HMF to linear alcohols. The optimized 5ZrO2/Cu catalyst affords an 86.53% yield of linear hexanepolyols at complete HMF conversion, exhibiting a ring-opening rate 4.23 times higher than that of the conventional 95ZrO2/Cu catalyst. Structural characterization reveals that the inverse architecture generates an extended Cu–O–Zr interfacial perimeter and abundant medium-strength basic sites. Kinetic studies show that the inverse catalyst significantly lowers the apparent activation energy for the hydrogenolysis of the key intermediate 2,5-bis(hydroxymethyl)furan. Combined in situ DRIFTS measurements and density functional theory calculations demonstrate that strong interfacial electronic interactions regulate the adsorption geometry of HMF-derived intermediates. Specifically, adsorption through hydroxymethyl groups on interfacial ZrOx sites induces a tilted configuration that weakens the furanic C–O bond and promotes selective ring opening. This work establishes a direct relationship between interfacial electronic structure, adsorption geometry, and reaction selectivity, providing mechanistic insights and a general strategy for designing interface-engineered catalysts for biomass valorization.

Engineering the local bonding environment and microscopic electronic structure of interfacial sites in metal-free carbon catalysts provides a powerful strategy for constructing active centers with tailored electronic states for selective bond activation. Herein, an N-doped carbon catalyst with tailored sp2-N configurations (NUC-c-950) is developed, in which coupled pyridinic N (Py-N) and graphitic N (Gr-N) sites create a bifunctional interfacial center for β–O–4 bond cleavage in lignin model compounds. Through the complementary electronic functions of the localized lone pair in the sp2 orbital of Py-N and the delocalized pz electron associated with Gr-N, β–C(sp3)–H deprotonation and O2 activation are coupled to generate an enolate intermediate and reactive oxygen species, respectively. The resulting N–C interfacial electronic configuration enables efficient oxidative cleavage of the lignin model compound 2-phenoxy-1-phenylethanone (PP-one) in methanol (MeOH), affording phenol and methyl benzoate (MB) in yields of 96.83 and 53.23%, respectively. More broadly, the coupled Py-N/Gr-N motif provides an effective metal-free platform for selectively cleaving lignin model compounds beyond β–O–4 ketones, including β–O–4 alcohols and β–1 model compounds, and offers a strategy for tailoring N-site electronic structures in metal-free carbon catalysts for selective lignin valorization.

A novel conversion route—depolymerization of lignocellulose, condensation of platform compounds, and selective hydrodeoxygenation and esterification (HDOE)—for the production of fatty acid methyl ester (FAME) biodiesel.

This study presents a novel photocatalytic system for the selective visible-light-driven oxidation of benzyl alcohols through the modulation of WO ₃ structure and reaction conditions.

Optimizing the selectivity of biomass-derived platform chemicals requires precise control over the geometric and electronic structures of catalytic active sites. Herein, we report the structural engineering of single-atom ruthenium (Ru1) supported on ceria (CeO2) nanocrystals with distinct crystal facets to regulate the hydrodeoxygenation of levulinic acid to 2-butanol. Using a facile photodeposition method, Ru1 species were anchored onto cubic (CeO2-C, exposing (1 0 0) facets) and sheet-like (CeO2-S, exposing (1 1 1) facets) supports. The Ru1CeO2-C catalyst exhibited superior catalytic performance, achieving an 86.9% yield of 2-butanol at 190 °C with a turnover frequency value of 157 s-1, surpassing the Ru1CeO2-S catalyst (53.5% and 111 s-1). Comprehensive characterization, including XPS, Raman spectroscopy, and EPR, revealed that the (1 0 0) facets of CeO2-C facilitate a higher concentration of surface oxygen vacancies and foster the electronic metal-support interaction. This interaction stabilizes Ru species and promotes the formation of Lewis acid sites, which are critical for the ring-opening of the key intermediate, γ-valerolactone. Kinetic studies, in situ DRIFTS, and theoretical calculations further confirmed that the facet-dependent electronic structure of Ru1CeO2-C significantly enhances hydrogen transfer capabilities and C-C bond cleavage efficiency. This work elucidates the structure-activity relationship in single-atom catalysis and offers a facet-engineering strategy for designing efficient biomass conversion catalysts.

Electrocatalytic conversion of biomass holds significant importance for alleviating environmental crises and providing renewable, green, high-value alternatives to fossil products. In this study, the structure of the catalyst was systematically optimized by regulating the formation conditions of Co-MOF structure and FeOOH through electrodeposition methods, leading to the design of the electrocatalyst (FeOOH@Co-MOF/NF) with leaf-like hierarchical composite structure. This catalyst exhibited outstanding performance in the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA). At the potential of 1.45 V vs. RHE, it achieved a 99.24% conversion rate for 5-hydroxymethylfurfural (HMF), a 96.93% FDCA yield, and a 91.51% Faradaic efficiency (FDCA). Moreover, the catalyst demonstrated superior stability over 10 cycles of HMF oxidation reaction (HMFOR). Electrochemical performance and in situ characterization revealed that in situ reconstruction of Co-MOF into the CoOOH reaction intermediates enhanced charge transfer processes. Further theoretical calculations indicated that the outer layer structure of FeOOH enhanced HMF/OH⁻ adsorption while strengthened electronic interactions between Co and Fe active sites, thereby lowering the reaction energy barrier. This study provides a novel approach for designing highly efficient HMF oxidation electrocatalysts.