Influence of the Intrinsic Nanocore Environment in a Pd-Metalated Porous Organic Polymer for Catalytic Biomass-Derived Furfural Upgrading

Abstract

Metalated nanoporous organic polymers (M-POPs) combine covalent bonds and open metal sites to enable structural stability and single-site catalysis. In this work, we constructed two single-site Pd-metalated knitting aromatic polymers (Pd@KAP-1 and Pd@KAP-2) and explored their catalytic activity in lignocellulosic biomass-derived furfural (FFR) upgrading to tetrahydrofurfuryl alcohol (THFAL), a green industrial solvent. Pd@KAP-1 exhibits superior catalytic performance compared to Pd@KAP-2 toward FFR conversion, resulting in 80% conversion with a 95% selectivity toward THFAL. Using in situ DRIFTS analysis, we find that FFR strongly adsorbs on Pd@KAP-1, which is a key determining factor in its higher catalytic efficiency. Our X-ray photoelectron spectroscopic (XPS) measurements show a lower (∼0.3 eV) binding energy displacement of Pd-3d5/2 in Pd@KAP-1 compared to Pd@KAP-2. We attribute this to the presence of a biphenyl ring that enables partial charge transfer between the P and the Pd atoms inside the nanocavity of Pd@KAP-1 to facilitate catalytic hydrogenation. We also carried out a kinetic analysis showing that Pd@KAP-1 has a lower activation barrier than Pd@KAP-2 for the FFR hydrogenation process. Our study demonstrates a novel concept for designing efficient, robust, and sustainable metalated porous organic polymer-based heterogeneous nanocatalysts in biomass refinery industries.

Composite Metal–Organic Framework-Derived NiCoP/MoS2 Heterostructure with Superior Electrocatalytic Credentials for Urea and Methanol Oxidation

“…MOF-based catalysts have particularly received attention as they offer impressive amplifications in the catalytic performance because of a high surface area that in turn ensures a high density of exposed active sites. The recent reports from Mondal and co-workers have employed this concept to achieve impressive performance for organic transformation. , MOF degradation has been recognized as a versatile route as some of the MOF features are retained in the degradation product. ,, Thus, the adoption of the MOF degradation route for the synthesis of TM phosphide electrocatalysts has been advocated vehemently of late.…”

“…The recent reports from Mondal and co-workers have employed this concept to achieve impressive performance for organic transformation. 40,41 MOF degradation has been recognized as a versatile route as some of the MOF features are retained in the degradation product. 32,42,43 Thus, the adoption of the MOF degradation route for the synthesis of TM phosphide electrocatalysts has been advocated vehemently of late.…”

A critical review on emerging photoactive porous materials for sulfide oxidation and sulfur mustard decontamination

“…Many materials have been employed to detoxify sulfur mustard and its analogous derivatives; in this context, owing to its attenable functionality, superior chemical and thermal stability, and enhanced porosity, POPs emerge as a judicious choice. 97 POPs are a class of advanced functional materials with structural tailorability, inherent porosity, and high flexibility, which have served for several applications like CO 2 capture, 98,99 CO 2 reduction to solar fuels, 100,101 biomass valorisation, 102,103 organic transformation reactions, 104,105 CO 2 fixation, 99 gas and liquid separation, 106 water purification, 107,108 energy storage, 109 chemo-and biosensing 110 and HD decontamination [111][112][113][114][115] etc. (Fig.…”

Dual Active Sites Engineering on Sea Urchin‐Like CoNiS Hollow Nanosphere for Stabilizing Oxygen Electrocatalysis via a Template‐Free Vulcanization Strategy

“…[13,14] In addition, many studies have proved that the introduction of transition metal sulfide to the carbon skeleton can effectively adjust the electronic structure of carbon (with defects) to improve the electrochemical performance. [15][16][17][18][19][20] Based on these principles, Wei et al synthesize graded C/ NiCo 2 S 4 nanospheres by a template-assisted hydrothermal method. [21] Benefited from the compositional features, the asprepared C/NiCo 2 S 4 electrode shows a high capacitance and satisfactory cycling stability.…”