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The non-oxidative dehydrogenation of propane to propylene plays an important role in the light-olefin chemical industry. However, the conversion and selectivity remain a fundamental challenge at low temperatures. Here we create and engineer high-density Lewis acid sites at well-defined surfaces in porous single-crystalline Mo2 N and MoN monoliths to enhance the non-oxidative dehydrogenation of propane to propylene. The top-layer Mo ions with unsaturated Mo-N1/6 and Mo-N1/3 coordination structures provide high-density Lewis acid sites at