Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2

•Mn-catalysts were covalently grafted onto activated carbon and pyrolytic carbon from recycled-tire char.•These catalysts were effective and selective towards epoxides with H2O2 and CH3COONH4.•The catalyst grafted onto pyrolytic carbon was kinetically faster, however was practically no recyclable.•This phenomenon is discussed in a mechanistic context.

Two types of heterogeneous catalytic materials, MnII-L3imid@Cox and MnII-L3imid@PCox, have been synthesized and compared by covalent grafting of a catalytically active [MnII-L3imid] complex on the surface of an oxidized activated carbon (Cox) and an oxidized pyrolytic carbon from recycled-tire char (PCox). Both hybrids are non-porous bearing graphitic layers intermixed with disordered sp2/sp3 carbon units. Raman spectra show that (ID/IG)activatedcarbon > (ID/IG)pyrolyticcarbon revealing that oxidized activated carbon(Cox) is less graphitized than oxidized pyrolytic carbon (PCox). The MnII-L3imid@Cox and MnII-L3imid@PCox catalysts were evaluated for alkene oxidation with H2O2 in the presence of CH3COONH4. Both showed high selectivity towards epoxides and comparing the achieved yields and TONs, they appear equivalent. However, MnII-L3imid@PCox catalyst is kinetically faster than the MnII-L3imid@Cox (accomplishing the catalytic runs in 1.5 h vs. 5 h). Thus, despite the similarity in TONs MnII-L3imid@PCox achieved extremely higher TOFs vs. MnII-L3imid@Cox. Intriguingly, in terms of recyclability, MnII-L3imid@Cox could be reused for a 2th run showing a ∼20% loss of its catalytic activity, while MnII-L3imid@PCox practically no recyclable. This phenomenon is discussed in a mechanistic context; interlinking oxidative destruction of the Mn-complex with high TOFs for MnII-L3imid@PCox, while the low-TOFs of MnII-L3imid@Cox are preventive for the oxidative destruction of the Mn-complex.

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