Theres two things in play here:
When the sun is high in the sky, the light is scattered by the air molecules in the atmosphere, but blue light is scattered more, so we see more of that color in the sky.
When the sun is low on the horizon, the light is passing through more of the atmosphere to reach your eye. So there’s more dust and smoke and pollution which absorbs the blue part of the light from reaching you, so you see more reds and yellows.
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