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Maybe some placebo for some people? But there have been times where I couldn't figure out why I was so energetic, only to remember that I had an extra cup of coffee or drank it later than normal.
I think most regular coffee drinkers know the simulant effect is very real. And I also think that, because of the sheer number of coffee drinkers over the last several hundred years, any significant placebo would have been rooted out by now.