Hollow microspherical tungsten carbide with mesoporosity was prepared by spray-drying sphere miniaturization/gas−solid reaction, using ammonium metatungstate (AMT) as a precursor, carbon monoxide as a reducing
gas, and carbon dioxide as a carrier gas. The samples were characterized by XRD, SEM, and EDS. XRD and
EDS results show that the samples are phase pure WC, with a ratio of W/C ≈ 1. SEM results show that the
hollow microsphere forms during spray-drying sphere miniaturization, and mesoporosity forms by gas−solid
reaction during subsequent heat treatment. To investigate the phase transition during the gas−solid reaction,
the samples were monitored by in situ XRD in an Anton Paar XRX900 container. The in situ XRD results
show that when the reaction temperature is raised to 1023 K slowly and continuously, the phase transition of
the sample follows the pattern AMT → WO3 → WO2 → W2C → WC, but when the reaction temperature is
raised to 673 K slowly and then raised to 1023 K quickly, the phase transition of the sample follows AMT
→ WO3 → WO2 → WC. These results indicate that the phase transition of the sample during the heat treatment
step is connected to the temperature and the time of the reaction, as well as the rate of the temperature rise.