Novel synthesis of dispersed molybdenum and nickel phosphides from thermal carbonization of metal- and phosphorus-containing resins.

Dispersed pure phases of MoP and Ni2P nanoparticles supported by carbon were synthesized by carbonization of metal- and phosphorus-containing resins under an inert atmosphere. The solid products and the evolution of gases during the carbonization process were investigated by various techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), N2 adsorption-desorption analysis, and mass spectrometry (MS). The resins underwent two carbonization stages: the low-temperature carbonization stage (<650 °C) and the high-temperature carbonization stage (≥650 °C). There was an initial reduction of Mo and Ni precursors in the low-temperature region. However, the formation of phosphides was observed in the high-temperature carbonization stage, in which Mo(Ni) and POx species were further reacted with the carbonization products (C, H2 and CH4) to yield Mo(Ni) phosphide. Note that compared with the traditional H2-temperature-programmed reduction (H2-TPR) method, this novel synthesis route produced a large amount of CO(x) besides H2O, leading to a lower water vapor pressure. In addition, the residual carbon produced from resin can play a role in bonding of nanoparticle aggregation. Therefore, the better dispersions and higher surface areas of the as-prepared phosphide nanoparticles were attributed to the mitigation of hydrothermal sintering and the intimate contact between phosphide nanoparticles and carbon species.