A novel strategy has been adopted for the construction of a copolymer of benzene-benzylamine-1 (BBA-1), which is a porous organic polymer (POP) with a high BET surface area, through Friedel-Crafts alkylation of benzylamine and benzene by using formaldehyde dimethyl acetal as a cross-linker and anhydrous FeCl3 as a promoter. Ruthenium nanoparticles (Ru NPs) were successfully distributed in the interior cavities of polymers through NaBH4, ethylene glycol, and hydrothermal reduction routes, which delivered Ru-A, Ru-B, and Ru-C materials, respectively, and avoided aggregation of metal NPs. Homogeneous dispersion, the nanoconfinement effect of the polymer, and the oxidation state of Ru NPs were verified by employing TEM, energy-dispersive X-ray spectroscopy mapping, cross polarization magic-angle spinning (13)C NMR spectroscopy, and X-ray photoelectron spectroscopy analytical tools. These three new Ru-based POP materials exhibited excellent catalytic performance in the hydrogenation of nitroarenes at RT (with a reaction time of only ≈ 30 min), with high conversion, selectivity, stability, and recyclability for several catalytic cycles, compared with other traditional materials, such as Ru@C, Ru@SiO2, and Ru@TiO2, but no clear agglomeration or loss of catalytic activity was observed. The high catalytic performance of the ruthenium-based POP materials is due to the synergetic effect of nanoconfinement and electron donation offered by the 3D POP network. DFT calculations showed that hydrogenation of nitrobenzene over the Ru (0001) catalyst surface through a direct reaction pathway is more favorable than that through an indirect reaction pathway.

Herein we have developed a highly active, robust, and selective porous organic polymer (PPTPA-1, POP) encapsulated magnetically retrievable Pd-Fe 3 O 4 nanohybrid catalyst in a one-step solvothermal route and investigated its catalytic performance in levulinic acid (LA) hydrogenation, a key platform molecule in many biorefinery schemes, to γ-valerolactone (GVL), employing formic acid as sustainable H 2 source. The specific textural and chemical characteristics of as-synthesized nanohybrid materials were identified by XRD, XPS, FT-IR, 13 C CP MAS NMR, HR-TEM, and FE-SEM with the corresponding elemental mapping and nitrogen physisorption studies. It was found that the nanohybrid Pd-Fe 3 O 4 /PPTPA-1 catalyst exhibited a substantially enhanced activity in comparison with the monometallic catalysts (Pd/PPTPA-1 and Fe 3 O 4 /PPTPA-1). Evidence of the electronic interaction between Pd and Fe attributable to the intrinsic hybrid synergistic effect is thought to be responsible for this superior catalytic performance and improvement in catalyst stability. The recycling experiments revealed that the magnetic nanohybrid catalyst sustained remarkable recycling efficiency and magnetism after being used in 10 successive catalytic runs, which made Pd-Fe 3 O 4 /PPTPA-1 a potential catalyst for the production of GVL in industry.

A N-rich porous organic polymer-anchored bimetallic Cu–Pd nanoalloy exhibited superior catalytic activity with improved stability for biomass-derived selective hydrodeoxygenation of vanillin.

Robust nanoarchitectures based on surfactant‐free ultrafine Pd nanoparticles (NPs) (2.7–8.2±0.5 nm) have been developed by using the incipient wetness impregnation method with subsequent reduction of PdII species encaged in the 1,3,5‐triazine‐functionalized nitrogen‐rich porous organic polymer (POP) by employing NaBH4, HCHO, and H2 reduction routes. The Pd‐POP materials prepared by the three different synthetic methods consist of virtually identical chemical compositions but have different physical and texture properties. Strong metal–support interactions, the nanoconfinement effect of POP, and the homogeneous distribution of Pd NPs have been investigated by performing 13C cross‐polarization (CP) solid‐state magic angle spinning (MAS) NMR, FTIR, and X‐ray photoelectron spectroscopy (XPS), along with wide‐angle powder XRD, N2 physisorption, high‐resolution (HR)‐TEM, high angle annular dark field scanning transmission electron microscopy (HAADF‐STEM), and energy‐dispersive X‐ray (EDX) mapping spectroscopic studies. The resulting Pd‐POP based materials exhibit highly efficient catalytic performance with superior stability in promoting biomass refining (hydrodeoxygenation of vanillin, a typical compound of lignin‐derived bio‐oil). Outstanding catalytic performance (≈98 % conversion of vanillin with exclusive selectivity for hydrogenolysis product 2‐methoxy‐4‐methylphenol) has been achieved over the newly designed Pd‐POP catalyst under the optimized reaction conditions (140 °C, 10 bar H2 pressure), affording a turnover frequency (TOF) value of 8.51 h−1 and no significant drop in catalytic activity with desired product selectivity has been noticed for ten successive catalytic cycles, demonstrating the excellent stability and reproducibility of this catalyst system. A size‐ and location‐dependent catalytic performance for the Pd NPs with small size (1.31±0.36 and 2.71±0.25 nm) has been investigated in vanillin hydrodeoxygenation reaction with our newly designed Pd‐POP catalysts. The presence of well‐dispersed electron‐rich metallic Pd sites and highly rigid cross‐linked amine‐functionalized POP framework with high surface area is thought to be responsible for the high catalytic activity and improvement in catalyst stability.