The aim of this study is to investigate the effect of atmospheric adsorbates on the electronic and optoelectronic properties of graphene/n-type Silicon (Gr/n-Si) based Schottky barrier photodiodes. Wavelength resolved photocurrent spectroscopy and transient photocurrent spectroscopy measurements conducted under high-vacuum conditions revealed that the adsorbates cause hole doping in graphene and hence increase the zero-bias Schottky barrier height of the Gr/n-Si heterojunction from 0.71 to 0.78 eV. Adsorbate induced increment in the barrier height promotes the separation of photo-excited charge carriers at the depletion region of the heterojunction and leads to an improvement in the maximum spectral response (e.g., from 0.39 to 0.46 A W^-1) and response speed of the Gr/n-Si photodiode in the near-infrared region. The experimentally obtained results are expected to give an insight into the adsorbate induced variations in the rectification and photo-response characters of the heterojunctions of graphene and other 2D materials with different semiconductors.