I don't think the trick is the Rayleigh scattering, I think it's the parallel rays. Notice how all the pictures have well defined shadows of parallel rays?
It's quite ingenious, the aerogel consists of silica nanoparticles with a size distribution smaller than the wavelength of the light, leading to Rayleigh scattering to dominate. The non-uniformity of the aerogel structure is what gives it the more nuanced lighting, it lets a bit of yellow light, a bit of this and that, making a non-monochromatic source that resembles sunlight very well.