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.

In recent times, selective hydrogenation of biomass-derived 5-hydroxymethylfurfural(5-HMF) to produce novel difuranic polyol scaffold 2,5-dihydroxymethylfuran (DHMF) has attracted the interests of the many researchers due to its peculiar symmetrical structure as well as its wide application as a monomer for the preparation of cross-linked polyesters and polyurethane. Copper-based catalysts have been explored accountable for the selective catalytic hydrogenation however the hurdles are still associated with the strongly reducing H2 atmosphere and oxidizing C-O bond that makes the Cu 0 and Cu x+ surface active species unstable, limiting the rational design of highly efficient integrated catalyst systems. To address this, herein, we built catalytic systems for 5-HMF hydrogenation with stable and balanced Cu 0 and Cu x+ active surface species inside the nanocage of catechol based Porous-Organic-Polymer (POP) endowed with large surface areas, impressive stabilities, and spatial restriction inhibiting NPs aggregation.Batch reactor screening indentified that superior catalytic performance (DHMF selectivity of 98%) has been achieved with our newly designed Cu@C-POP at 150ºC temperature and 20 bar H2 pressure, which was also higher than that of other reported copper catalysts. Comprehensive characterizations understanding with H2-TPR and XPS study revealed that substantially boosted activity is induced by the presence of bulk CuOx phase and atomically dispersed Cu species incorporating isolated Cu ions, which are further confirmed through the positive binding energy shift of Cu-2p3/2 XPS spectra (~0.4eV). The Cu environment in our catalytic systems comprises predominantly square planar (well probably Jahn-Teller distorted Oh) which we gleaned from the EXAFS analysis featuring two adjacent copper atoms with the valence state in between of 0 and +2 as validated by XANES absorption edge positions. EXAFS studies further revealed a

Porous-Organic-Polymers (POPs) constructed through covalent bonds have raised tremendous research interest because of their suitability to develop robust catalysts and their successful production with improved efficiency. In this work, we have designed and explored the properties and catalytic activity of template-free construction hydroxy (-OH) group enriched porous-organic-polymer (Ph-POP) bearing functional Pd nanoparticles (Pd-NPs) by one-pot condensation of phloroglucinol (1,3,5-trihydroxybenzene) and terephthalaldehyde followed by solid phase reduction with H 2 . The encapsulated Pd-NPs rested within welldefined POP nanocages and remained undisturbed from aggregation and leaching. This polymer hybrid nanocage Pd@Ph-POP is found to enable efficient liquid-phase hydrodeoxygenation (HDO) of acetophenone (AP) with high selectivity (99%) of ethylbenzene (EB) and better activity than its Pd@Al 2 O 3 counter-part. Our investigation demonstrates a facile, scalable, catalyst-template free methodology for developing novel porous-organic-polymer catalysts and next generation efficient greener chemical processes from platform molecules to value-added chemicals. With the aid of comprehensive in situ ATR-IR spectroscopic experiments, it is suggested that EB can be more easily desorbed in solution, reflecting from the much weaker but resolved signals at 1494 cm -1