The rational design of highly active and stable atomically dispersed M-X4 (M =Fe,Co,Ni,etc.,X =C,N)-based catalysts holds promises for wide application in almost all realms of catalysis.Despite great effort in the construction of specific M-X4 centers,the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored.Herein,we develop a new type of M-X4 catalyst composed of Fe-N4 canters and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N4 centers in tailoring their electron density and final catalytic selectivity.The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines.As a reusable heterocatalyst,the state-of-the-art FeNC+B catalyst provides a tum-over frequency (TOF) value of 21.6 molbenzonitrile·molFe-1·h-1 (100 ℃),outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.