Ni/PiNe Heterogeneous Catalyst from Biomass Waste: Low-Loading, Ligand-Free Suzuki-Miyaura Cross-Coupling.

An efficient Ni-based heterogeneous catalyst from pine needles urban waste valorization was designed and developed with a resource recycling strategy. The Ni/PiNe catalyst was fully characterized and tested in the Suzuki-Miyaura coupling under microwave irradiation. Although Ni is a promising candidate for replacing Pd-based catalytic systems, it generally requires a high catalyst amount and the exploitation of ligands and additives to enhance the reaction rate. On the contrary, with our new Ni/PiNe, 30 different products were efficiently synthesized with an isolated yield of up to 93%, using a very low catalyst amount and in the absence of ligands. Furthermore, the Ni/PiNe catalyst also showed good durability for consecutive cycles and an impressive TON value (1140). In addition to the catalytic efficiency in short reaction time and to the stability and durability under MW irradiation, the Ni/PiNe allowed for further optimization, achieving a low E-factor value (14.0), thus highlighting the potential in further reducing the waste and costs associated to the process.