Sun and sky appear to be red during sunset and sunrise because
Light travels through a large layer of atmosphere during sunset and sunrise and hence shorter wavelengths like violet light are scattered out to a greater extent
As the sun begins to set (or even rise), the light from the sun has to travel farther through the atmosphere before it gets to you. More of the light is reflected and scattered. As less light reaches you directly, the sun appears less bright. The colour of the sun itself appears to change, first to orange and then to red. This is because even more of the short wavelength blues and greens are scattered away even before they reach you. Only the longer wavelengths (i.e. yellow, orange and red) are left in the direct beam that reaches your eyes. Thus giving the sky and the sun reddish appearance. In other words: At sunset and sunrise the light from the sun reaching the observer travels through the atmosphere to a very large extent as compared to other timings of the day and thus most of the blue component of the white light is scattered resulting in predominantly red light reaching the observer directly from the sun.