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I'm baking cupcakes and the recipe calls for espresso but I was wondering if I could substitute decaf coffee instead since it's for children.

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Yes, probably. I've substituted decaf coffee in a number of recipes that called for regular coffee or espresso, particularly when it might be served to kids. (And frankly, also for myself, because I don't like to consume caffeine late in the day anymore either.)

Some substitution guides will tell you to brew the coffee a little stronger than usual, which might imitate the stronger flavor of espresso. The problem with that is twofold: (1) the high-pressure espresso extraction process highlights different flavor components compared to just a normal strongly brewed coffee, and (2) decaf coffee often has unbalanced notes to begin with, given the processing necessary to remove the caffeine. By brewing it stronger, you risk bringing out the unpleasant "stereotypical decaf coffee" flavors even more.

Of course, in many recipes the amount of coffee is minimal, so this may not matter. But unless you're certain your decaf coffee is pleasant when brewed strong and will complement the other flavors in the recipe, I might just brew it as usual, rather than trying to "amp it up" to make it more like espresso.

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    In a recipe, which tends to add fat, sugar, and often chocolate, the clean espresso flavour is somewhat masked. And without a reasonably strong brew is hardly worth putting the coffee in at all. As I have one, I'd brew decaff in my moka pot if making a cofee cake without caffeine. But the caffeine per portion is very low anyway. – Chris H Nov 10 '16 at 7:40
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    @ChrisH - agreed. I've done that myself (with a moka pot). I just cautioned about the flavor because I once did this with what I thought was a relatively small proportion of coffee given the size of the recipe, and not only did the coffee flavor shine through, but the result tasted way too much of "bad decaf coffee." Since then, I've been much more careful of the decaf I use in recipes. – Athanasius Nov 10 '16 at 18:52
  • That wouldn't surprise me. Unless specially bought for something any decaff in my house would be stale even if unopened. That wouldn't help the flavour – Chris H Nov 10 '16 at 19:17

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