Synthesis and characterization of a supported Pd complex on carbon nanofibers for the selective decarbonylation of stearic acid to 1-heptadecene: the importance of subnanometric Pd dispersion

Abstract

Production of linear α-olefins from renewable sources is gaining increasing attention because it allows the transition from the current petrochemical synthesis route to a more sustainable scenario. In this work, we describe the synthesis and characterization of an innovative catalyst based on a di-μ-chloro-bisijpalladiumIJII) anthranilate] complex highly dispersed by incipient wetness impregnation over acyl chlorinated carbon nanofibers. The subnanometric dispersion of the metal complex allowed higher catalytic efficiency for the selective decarbonylation of stearic acid to 1-heptadecene as compared to the reference homogenous catalyst. The best catalytic performance (90 mol% selectivity, 71 mol% conversion, and TON = 484) was achieved under mild reaction conditions (atmospheric pressure, 140°C) with a Pd loading in solution of 0.14 mol%. The post-mortem catalyst characterization and the recyclability tests evidenced the high stability of the catalyst. The highly dispersed catalyst developed in this work provides new opportunities in the rational design of more efficient catalytic systems for the sustainable transformation of fatty acids.

Bridging Platinum and Palladium to Bipyridine-Annulated Perylene for Light-Driven Hydrogen Evolution

“…42,43 The Pd 3d spectrum shows a single doublet at a BE corresponding to the oxidation state of Pd(II) (Figure 2c). 44 Similar to P-Pt, the N 1s spectrum of P-Pd is shifted to higher BE (399.7 eV) (Figure 2d). In addition to the analysis of the metal and nitrogen spectra, the Cl 2p signal for both compounds displayed a single metal-Cl component (Figure S3Ţhe quantitative analysis shows a Pt/ N/Cl ratio of 1.0:2.0 ± 0.2:2.0 ± 0.2 for P-Pt and a Pd/N/Cl ratio of 1.0:2.0 ± 0.2:2.1 ± 0.2 for P-Pd, which corresponds to the composition of both complexes very well.…”

“…For P-Pt , the single components for Pt 4f and N 1s confirm that no other species is present (Figure a) . The binding energy (BE) of the Pt 4f spectrum matches the oxidation state of Pt­(II), and the detected N 1s signal is shifted toward a higher BE of 400.1 eV in comparison to typical pyridinic nitrogen spectra (399.0 eV) (Figure b), which is typical for the formation of metal complexes with (bi)­pyridine-based ligands. , The Pd 3d spectrum shows a single doublet at a BE corresponding to the oxidation state of Pd­(II) (Figure c) . Similar to P-Pt , the N 1s spectrum of P-Pd is shifted to higher BE (399.7 eV) (Figure d).…”

Highly stable Pd2+ species anchoring on ethylenediamine-grafted-MIL-101(Cr) as a robust oxidation catalyst

“…Moreover, the Pd 2+ binding energy for the sample with ethylenediamine (0.03Pd-0.5en-MIL-101(Cr)) clearly shifted, as compared to that of 0.03Pd-MIL-101(Cr). This indicates the interaction between Pd 2+ and ethylenediamine (Pd-N), 48 as compared to Pd-O in 0.03Pd-MIL-101(Cr). In line with this view, the N 1s binding energy of ethylenediamine in 0.03Pd-0.5en-MIL-101(Cr) also shifted to a value higher than that in the Pd-free sample (0.5en-MIL-101(Cr), Fig.…”