Applied Catalysis A: General, Vol.550, 236-244, 2018
The effect of the hydrotalcite structure and nanoparticle size on the catalytic performance of supported palladium nanoparticle catalysts in Suzuki cross-coupling
An uncalcined HT supported Pd-NP catalyst was synthesized via co-precipitation, i.e., PdHT_100RED_20, and benchmarked against a Pd impregnated HT catalyst, i.e., Pd@HT_500RED_20. TEM analysis pointed out that the largest NPs (6.5 nm) were found in the co-precipitated catalyst because of its weaker steric NP confinement, compared to the benchmark catalyst (3.2 nm). The PdHT_100RED_20 had a significantly higher catalytic performance (60% conversion, 1.85% leaching) than Pd@HT_500RED_20 (19%, 0.98%) due to lack of calcination resulting in an ordered, and thus, more accessible HT structure in combination with its high support basicity. Both catalysts showed low Pd leaching confirming the suitability of HTs as NP support. Focusing on PdHT_100, the effect of the reduction temperature on the NP size and catalytic performance was investigated. NP size distribution analysis showed that the smallest NPs were found in PdHT_100RED_0 (5.3 nm), resulting in a higher catalytic performance (67%, 2.28%) when compared to PdHT_100RED_20 (6.5 nm). Performing the reduction at higher temperatures, i.e., at 60 degrees C (5.7 nm), caused an extremely low catalytic performance (13%, 0.20%) due to the less efficient reduction reaction with NaBH4 at higher reduction temperatures. Reusing PdHT_100RED_20, a decrease in catalytic performance (45%) was observed. However, this decrease was less pronounced (50%) when a re-activation of the catalyst with Na2CO3 between consecutive runs was performed. Moreover, it was shown that the leached Pd species were able to re-deposit onto the support if high conversions were obtained, and thus, an almost quantitatively recovery from the reaction mixture can be achieved with retention of its catalytic activity (> 99%).
Keywords:Hydrotalcites;Palladium nanoparticles;in-situ' preparation methodologies;Heterogeneous catalysis;Suzuki cross-coupling reaction