Solvothermal Fabrication of Mesoporous Pd Nano-Corals at Mild Temperature for Alkaline Hydrogen Evolution Reaction.

Porous metallic nanomaterials exhibit interesting physical and chemical properties, and are widely used in various fields. Traditional fabrication techniques are limited to metallurgy, sintering, electrodeposition, etc., which limit the control of pore size and distribution, and make it difficult to achieve materials with high surface areas. On the other hand, the chemical preparation of metallic nanoparticles is usually carried out with strong reducing agents or at high temperature, resulting in the formation of dispersed particles which cannot evolve into porous metal. In this study, we reported the simple fabrication of coral-like mesoporous Pd nanomaterial (Pd NC) with a ligament size of 4.1 nm. The fabrication was carried out by simple solvothermal reduction at a mild temperature of 135 °C, without using any templates. The control experiments suggested that tetrabutylammonium bromide (TBAB) played a critical role in the Pd(II) reduction into Pd nanoclusters and their subsequent aggregation to form Pd NC, and another key point for the formation of Pd NC is not to use a strong reducing agent. In alkaline water electrolysis, the Pd NC outperforms the monodisperse Pd NPs and the state-of-the-art Pt (under large potentials) for H2 evolution reaction, probably due to its mesoporous structure and large surface area. This work reports a simple and novel method for producing porous metallic nanomaterials with a high utilization efficiency of metal atoms, and it is expected to contribute to the practical preparation of porous metallic nanomaterials by solvothermal reductions.

Pd-Based Nano-Catalysts Promote Biomass Lignin Conversion into Value-Added Chemicals.

Lignin, as a structurally complex biomaterial, offers a valuable resource for the production of aromatic chemicals; however, its selective conversion into desired products remains a challenging task. In this study, we prepared three types of Pd-based nano-catalysts and explored their application in the depolymerization of alkali lignin, under both H2-free (hydrogen transfer) conditions and H2 atmosphere conditions. The materials were well characterized with TEM, XRD, and XPS and others, and the electronic interactions among Pd, Ni, and P were analyzed. The results of lignin depolymerization experiments revealed that the ternary Pd-Ni-P catalyst exhibited remarkable performance and guaiacols could be produced under H2 atmosphere conditions in 14.2 wt.% yield with a selectivity of 89%. In contrast, Pd-Ni and Pd-P catalysts resulted in a dispersed product distribution. Considering the incorporation of P and the Pd-Ni synergistic effect in the Pd-Ni-P catalyst, a possible water-involved transformation route of lignin depolymerization was proposed. This work indicates that metal phosphides could be promising catalysts for the conversion of lignin and lignin-derived feedstocks into value-added chemicals.