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Preheat a griddle or skillet over medium heat. Place a rimmed baking sheet in the oven and heat to 200 degrees F.
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In a large bowl, combine buckwheat flour, baking powder, baking soda, sugar, and sea salt. Beat egg well in a small bowl and then whisk in 1 1/4 cups milk, zest, and vanilla. Fold wet ingredients into the dry, stirring just until combined. Fold in melted butter. Batter should be thin enough to just dribble off the spoon – stir in a few more tablespoons of milk if needed.
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Add butter to the hot skillet, edge heat up just above medium. (The griddle should be hot, but not so much so that the butter smokes.) Pour 1/4 cup of batter per pancake onto griddle. Pancakes will cook quickly – 1 - 2 minutes per side; look for edges to firm up and then flip. Store cooked pancakes on prepared baking sheet in the oven.
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Meanwhile, set grapefruit segments into a sauce pan and cover with maple syrup. Warm syrup over medium-low heat. Once warm, keep syrup over low heat until ready to serve.
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I had every intention of serving these with a dollop of mascarpone and forgot, though found the pancakes to be lovely with just a pat of butter and a generous spoonful of grapefruit syrup.