ZIF-8, a metal organic framework with a sodalite topological structure, is a widely studied crystalline microporous material due to its thermal and chemical stability. However, the existing studies mostly focus on understanding the porosity and bulk structure of ZIF-8, ignoring the external facets of the porous crystal, which are the first points of interaction between adsorbent and guest adsorbate. This paper reports on understanding the preferential exposure of thermodynamically stable and unstable facets as a function of synthetic methodology. The comprehensive and combinatorial investigation of experimental and theoretical studies shows that the high energy {112} facets of ZIF-8 efficiently reduce the encapsulated CO₂ to fuel compared to the {011} facets.