File Name : fig.s1.tif Caption : fig. s1. band structure of (a) pristine bp, (b) n@bp_v and (c) n₂@bp_v. File Name : fig.s2.tif Caption : fig. s2. top and side views of (a) pristine bp and (b) monatomic defective bp. File Name : fig.s4.tif Caption : fig. s4. initial adsorption configuration of co2 in horizontal (left) and vertical (right) directions (a) pristine bp, (b) n@bp_v, and (c) n₂@bp_v. File Name : fig.s3.tif Caption : fig. s3 initial and optimized structures of n₂@bp_v in three different diatomic nitrogen-doped modes, as well as corresponding formation energy values. File Name : fig.s6.tif Caption : fig. s6. the geometric structures during the overall reaction pathway of *coco conversion to ch₃cho: (a) *coco; (b) *cocho; (c) *cohcho; (d) *coch₂oh; (e) *coch₂; (f) *coch₃; (g) *ch₃cho. File Name : fig.s5.tif Caption : fig. s5. the geometric structures during the overall reaction pathway of *coco conversion to ch₂ch₂: (a) *coco; (b) *cocho; (c) *cohcho; (d) *coch₂oh; (e) *coch2; (f) *cohch₂; (g) *cch₂; (h) *chch₂; (i) *ch₂ch₂. File Name : fig.s7.tif Caption : fig. s7. (a) local atomic spin population of diatomic nitrogen-doped black phosphorus (n(1) and n(2) are used to distinguish the different n atoms). (b) schematic of activity mechanism of n(1) atom. (c) the hybrid types of different n atoms. File Name : fig.s8.tif Caption : fig. s8. density of states on (a) pristine bp and (b) n₂@bp_v. dos was obtained by the heyd−scuseria−ernzerhof (hse) functional. File Name : fig.s9.tif Caption : fig. s9. top and side views of the charge densities (a) pristine bp and (b) n₂@bp_v. the isosurface value is set to 0.0004 e/bohr3. File Name : fig.s10.tif Caption : fig. s10. (a) e-h recombination dynamics. the initial state corresponds to the electron excitation from the vbm to the cbm. populations of the excited and ground are shown by the blue and black, respectively. (b) fourier transform (ft) phonon-induced fluctuations of the energy gaps between the vbm and cbm.