Hydrogen Evolution Reaction (HER) is an attractive technology for chemical conversion of energy. Replacement of platinum with inexpensive and stable electrocatalysts remains a major bottleneck hampering large-scale hydrogen production by using clean and renewable energy sources. Here, we report electrocatalytically active and ultra-stable Polymer-Derived Ceramics towards HER. We successfully prepared ultrathin silicon and carbon (Si-C) based ceramic systems supported on electrically conducting

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... D reduced graphene oxide (rGO) nanosheets with promising HER activity by varying the nature and the composition of the ceramic with the inclusion of nitrogen, boron and oxygen. Our results suggest that oxygen-enriched Si-B-C-N/rGO composites (O-SiBCN/rGO) display the strongest catalytic activity leading to an onset potential and a Tafel slope of - 340 mV and ~ 120 mV dec-1 respectively. O-SiBCN/rGO electrodes display stability over 170 h with minimal increase of 14% of the overpotential compared to ~ 1700% for commercial platinum nanoparticles. Our study provides new insights on the performance of ceramics as affordable and robust HER catalysts calling for further exploration of the electrocatalytic activity of such unconventional materials.