The separation of photogenerated carriers and photocatalytic hydrogen production efficiency was greatly enhanced by the 2D/2D heterojunction of Ti3C2/g-C3N4.

Although hexagonal boron nitride (h‐BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas‐phase methyl radicals (CH3.) in the ODHP reaction over boron‐based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV‐PIMS), which uncovers the existence of gas‐phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C2 and C1 products can be formed via both surface‐mediated and gas‐phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron‐based catalysts.