Despite
the widespread interest in the examinations of catalytic
and facet-dependent properties of Cu2O crystals, it was
still difficult to grow ultrasmall Cu2O cubes and octahedra
with tunable sizes at a large scale. In this work, CuSO4, NaOH, and sodium ascorbate of varying volumes were added to an
aqueous sodium dodecyl sulfate (SDS) solution to generate Cu2O nanocubes with average edge lengths of 16, 25, 29, 36, 51, 63,
72, and 86 nm in just 10 min. Another series of Cu2O cubes
with wide size tunability in the range of 27–200 nm is accomplished
by simply adjusting the NaOH volume. Similar reaction conditions can
also be used to make a large quantity of Cu2O octahedra
with opposite corner distances of just 34, 41, and 49 nm. Remarkably,
production of these small Cu2O cubes and octahedra is scalable to 500 mL in one reaction. UV–vis
absorption and photoluminescence spectra establish their size and
facet-dependent optical properties, and a modified band diagram of
Cu2O is presented. Recognizing Cu2O nanocrystal
shape evolution is possible by changing the cell potential, we have
proven this concept to yield cubic to truncated octahedral and octahedral
structures by varying the CuSO4 volume. Finally, the tiny
Cu2O cubes and octahedra were pseudomorphically converted
to Cu cubes and octahedra via the introduction of ammonia borane,
so these small copper polyhedra become readily accessible for diverse
catalytic and plasmonic applications.