If V/Q = 0, that means ventilation is zero. This means that inhaled oxygen is not becoming involved in gas exchange because it is not coming into contact with perfused areas. The lungs will respond by vasconstricting pulmonary vasculature in poorly ventilated areas, thus shunting blood to well ventiliated areas so they can participate in gas exchange. The purpose of shunting is to help improve V/Q mismatch by not wasting perfusion to areas that are not ventilated.
A way you can think of it....If you have an obstruction, areas of the lung will not be ventilated (V=0), but will be perfused. Stating the obvious, no air/oxygen is getting through to participate in gas exchange. So no matter what percentage of oxygen you give, its not going to be able to hit perfused areas and improve oxygenation.