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Adjust the oven rack to the lower third position, just below the center of the oven, and heat the oven to 350°F. Line an 8x8-inch pan with parchment paper or aluminum foil, leaving a 1-inch overhang on all sides. Spray lightly with nonstick spray and set aside.
In a medium heatproof bowl set over a pot of barely simmering water, melt the chocolate and butter, stirring constantly until the mixture is smooth. You can also microwave in 30-second intervals, stirring between each one.
Remove from heat and whisk in the cocoa powder. Set aside to cool slightly.
In a separate bowl, whisk the egg and sugar, vanilla, and salt together until well combined and the mixture is frothy.
Add the warm chocolate mixture and whisk until well combined.
Add the flour and use a silicone spatula to fold the batter together until no visible streaks of flour remain.
Spread the mixture evenly into the prepared pan and bake for 20-25 minutes or until a toothpick inserted into the center comes out with a few moist crumbs clinging to it.
Cool on a wire rack to room temperature, about 2 hours, then remove from the pan and cut into squares.