The selective activation of targeted bonds in biomass-derived furfural or furfuryl alcohol with complex chemical linkages (C–C/C–H/C–O, CC/CO, or C–O–H/C–O–C) is of great challenge for biomass upgrading, expecting well-defined catalyst and definite catalytically active sites. This work demonstrates an efficient targeted activation to C–OH, C–O–C, or CC by engineering the structure of catalytic Pt sites, affording 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol (THFA), or 1,2-pentanediol (1,2-PeD) as product in the hydroconversion of furfuryl alcohol. The catalytic Pt sites have been engineered as atomic Pt, coordination unsaturated Pt–Pt in atom-thick dispersion, or coordination unsaturated 3D Pt–Pt by tailoring the Pt dispersion (single atom, 2D cluster, or 3D cluster) on Mg and Al-containing layered double oxide (Mg­(Al)­O) support. The selective activation of C–OH, C–O–C, or CC has been traced with the FT-IR spectra recorded surface reaction. On atomic Pt, C–O–H is easily activated, with the assistance of Mg­(Al)O support, with O-terminal adsorption without affecting furan C–O and CC. However, CC in the furan ring is easier to be activated on coordination-unsaturated Pt–Pt in atom-thick dispersion, resulting in a step-by-step hydrogenation to generate THFA. On coordination-unsaturated 3D Pt–Pt, the hydrogenolysis of furan ring is favored, resulting in the cleavage of furan C–O to produce 1,2-PeD. Also, the Mg­(Al)O supports derived from Mg and Al layered double hydroxides (LDHs) here also play a key role in promoting the selectivity to 1,2-PeD by providing basic sites.

Oxidation of the secondary O–H bond of glycerol to dihydroxyacetone is an important reaction in the production of high-value-added chemicals. The heterogeneous catalytic oxidation route using supported Au as a catalyst in this crucial reaction has attracted considerable attention. However, targeted activation of the secondary O–H bond and satisfactory catalytic efficacy remain considerable challenges. This work reports layered double hydroxide (LDH) supported Au catalysts for the targeted activation of the secondary O–H bond and provides deep insights into the active sites and the roles of the LDH support in glycerol selective oxidation. By virtue of the tailorable chemical composition of the LDH brucite-like layer, Zn2Fe-, Co2Al-, Zn2Al-, Zn2Ga-, and Mg2Al-LDHs, displaying varied surface basic densities and hydroxyl vacancies (VOH), were applied as supports for Au nanoparticles in this work. A glycerol conversion of 72.9 ± 0.2% and a dihydroxyacetone selectivity of 63.8 ± 0.2% were achieved on ZnGa-LDH-supported Au. In addition to Au0, surface Au n+ (Au+ and Au3+) species are abundant in the interfacial MII–O–Au n+ linkages. Detailed investigations verify the cooperation between the surface basic sites on the LDH support for the activation of the secondary O–H bonds and the interfacial MII–O–Au+ sites for the activation of the secondary C–H bonds. Significantly, on Zn-containing LDHs, an additional synergy exists between the surface VOH sites and the interfacial ZnII–O–Au3+ species to further promote catalytic activity.

Simultaneous formation of C–C/C–N bonds provides insight into the bottom-up synthesis of N-heterocycles. This work reports Ni0/Niδ+ synergistic catalysis on the surface of Ni nanoparticles for the highly efficient one-pot formation of C–C/C–N bonds, affording 1,2,3,4-tetrahydroquinoline and its derivatives from 2-amino benzyl alcohol and ethanol without any addition of liquor base or external hydrogen. Ni0/Niδ+ synergistic catalysis has been achieved by regulating the Ni particle size or activating the Ni surface with O2. In the dehydrogenation of −CH2–OH to −CHO, the formation of CC and CN bonds via concurrent cross-condensation, and the transformation of CC/CN to C–C/C–N via hydrogen transfer, ethanol dehydrogenation has been found to be the rate-determining step. Reducing the Ni particle size effectively increases the number of surface Niδ+ sites, which accelerates catalytic dehydrogenation through synergistic catalysis between surface Niδ+ and Ni0 sites. The number of surface Niδ+ sites can be further increased by appropriately activating the Ni surface with O2.

Highly efficient and enantioselective asymmetric Knoevenagel-phospha-Michael tandem reactions have been achieved on bifunctional heterogeneous catalysts with inherent silanols as acidic sites and immobilized chiral amines as basic sites. Final products were afforded in yields of up to 99% and ee values of up to 99%. The effects of substituents on benzaldehyde and molecular dimensions of phosphites have also been investigated. Larger substrates can access the catalytic site inside larger mesoporous pores, thereby improving both of yield and ee of final products.

Heterogeneous synergistic catalysis by SBA-15 immobilized chiral amines catalysts has promoted efficient aza-Michael–Henry tandem reaction for the synthesis of chiral 3-Nitro-1,2-Dihydroquinoline. Final products in the asymmetric aza-Michael–Henry cascade reactions between 2-aminobenzaldehyde and β-nitrostyrolene were afforded in a yield of 85% and an enantiomeric excess (ee) value of 98% on (S)-(–)-2-aminomethyl-1-ethylpyrrolidine immobilized SBA-15. SBA-15-AEP catalyst has been also extended to the asymmetric aza-Michael–Henry cascade reaction of substituted R1-2-aminobenzaldehyde and R2-substituted nitroolefin. The heterogeneous synergistic mechanism for both tertiary amine and secondary amine immobilized mesoporous has been proposed in detail including the geometrical constraints in the ee promotion.