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Preheat the oven to 350°F. Butter three (9-inch) round cake pans or spray with baking spray, and line the bottoms with parchment paper. (I highly recommend using cake strips for a more even bake.)
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In a medium bowl, sift the cocoa powder. Whisk in the hot coffee until the cocoa is dissolved. Let cool for 10 minutes.
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Meanwhile, in a large bowl, whisk together the flour, sugar, baking soda, baking powder, and salt.
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To the cooled cocoa mixture, add the oil, buttermilk, eggs, and vanilla and whisk until well combined. Pour the mocha mixture into the flour mixture and whisk until fully incorporated. Divide the batter evenly among the cake pans.
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Bake for 30 minutes or until the cakes are springy to the touch and just starting to pull away from the sides of the pan. (If you have to bake the cakes on separate oven racks, carefully rotate them after 20 minutes of baking.) Let cool completely in the pans. Run a knife around the edge of the cakes to loosen them and invert them onto a wire rack. Remove and discard the parchment paper.