Cats have several unique personality traits that make them more likely to purposefully knock things over. Cats are naturally curious and intelligent animals. Knocking things over can satisfy their curiosity on how things move or work. They are running their own little diagnostic test in order to see how something reacts to their touch.
Cats particularly enjoy pushing things like cups off countertops, because these objects can roll or bounce. They are typically playing and just want to see what will happen with a particular object from a high surface.
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