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Gas storage and recovery processes in shales critically depend on nano-scale porosity and chemical composition, but information about the nanoscale pore geometry and connectivity of kerogen, insoluble organic shale matter, is largely unavailable. Using adsorption microcalorimetry, we show that once strong adsorption sites within nanoscale network are taken, gas adsorption even at very low pressure is governed by pore width rather than chemical composition. A combination of focused ion beam with scanning electron microscopy and transmissio