Monometallic Co0–Coδ+ catalysts
have shown considerable potential in higher alcohol synthesis (HAS)
direct from syngas, however, the alcohol selectivity and catalyst
stability still need to be promoted. Here, we prepared a series of
cobalt silicate hydroxide-derived catalysts and surprisingly obtained
tetrahedrally coordinated zinc blende CoO (Z-CoO) during reduction
and reaction. The nanoscale close interacted Co0-Z-CoO
achieved an ROH selectivity of 64.4%, a higher alcohol (HA) selectivity
of 43.6%, and a space time yield (STY) toward HA of 42.0 mmol·gCo–1·h–1, which outperformed
most of the reported Co-based HAS catalysts. In addition, as a contrast,
the commonly obtained rocksalt CoO (R-CoO) with octahedral structure
was prepared. It is proved that Z-CoO serves as the CO nondissociative
adsorption site, which exhibits a much stronger adsorption capability
compared to R-CoO and Co2C, greatly facilitating the alcohol
formation. Moreover, unlike the R-CoO, there were barely no phase
transition of Z-CoO during HAS reaction, contributing to the catalyst
stability over 550 h reaction. This work offers a facile preparation
method and insights of zinc blende CoO as promising high-performance
active sites for HAS.