Polymers are usually restricted on the high exciton binding energies and sluggish electron transfer because of the low dielectric constants. Regulating spin-polarized electrons is regarded as an attractive strategy, but often confined to the d-orbital elements. Here, the nonmetal P and N elements co-mediated the spin polarization of carbon nitrides (PCN) have been elaborately designed. The optimized PCN-3 shows an outstanding hydrogen production (22.2 mmol·g⁻¹·h⁻¹) coupled with selective benzylamine oxidation without using any solvent and cocatalysts, which is 200 times of original C₃N₄ and superior to the photocatalysts has been reported to date. Experimental and theoretical results verified that the spin-orbital coupling of N 2p and P 2p remarkably increased the parallel spin states of charge and reduced the formation of singlet excitons to accelerate exciton dissociation in carbon nitride. In addition, charge separation and surface catalysis can be significantly enhanced by the electron spin polarization of carbon nitride with the parallel arrangement, huge built-in electric field and disturbed electronic structure. Our finding deepens the insight into the charge separation and exciton dissociation in spin polarization, and offers new tactics to develop high-efficiency catalysts.

由于介电常数低，聚合物通常受限于高激子结合能和缓慢的电子转移。调节自旋极化电子被认为是一种有吸引力的策略，但通常仅限于 d 轨道元素。在这里，非金属 P 和 N 元素共同介导了氮化碳 (PCN) 的自旋极化。优化后的 PCN-3 在不使用任何溶剂和助催化剂的情况下表现出优异的氢气产量（22.2 mmol·g ^-1 ·h ^-1）和选择性苄胺氧化，是原始 C ₃ N _{4的 200 倍}迄今为止，已有报道称其优于光催化剂。实验和理论结果证实，N 2p 和P 2p 的自旋轨道耦合显着增加了电荷的平行自旋态，减少了单线态激子的形成，加速了氮化碳中激子的解离。此外，具有平行排列、巨大内建电场和扰乱电子结构的氮化碳的电子自旋极化可以显着增强电荷分离和表面催化作用。我们的发现加深了对自旋极化中电荷分离和激子离解的认识，并为开发高效催化剂提供了新的策略。