It is crucial to explore the best active center for a catalyst in heterogeneous catalysis. Here we probe the performance of B single-atom doped Cu catalyst and the corresponding pure metal catalyst in water-gas shift reaction (WGSR) through density functional theory (DFT). The results show that Cu catalyst modified by B single-atom obtained unprecedented catalytic property compared to the corresponding pure metal catalyst, which is due to the special active site for water dissociation that the embedded B single-atom creates two heterogeneous Cu atoms with different electronic structures. Moreover, due to its charming electronic property, B atom can act as a charge transfer medium, freely switching between anionic and cationic states. More importantly, the synergy of heterogeneous Cu atoms reduces the activation energy barrier of the rate-limiting step (water dissociation) by 0.11 eV on B-doped Cu surface in WGSR. Electronic structure analysis emerges a downshifted d-band center of surface Cu atoms coordinated with B atom and an upshifted d-band center of those by Cu-Cu coordination originated from strain and ligand effects. The findings aim to provide deep insights for people to design new catalysts using earth-abundant elements in WGSR.

探索非均相催化中催化剂的最佳活性中心至关重要。在这里，我们通过密度泛函理论（DFT）探讨了B单原子掺杂Cu催化剂和相应的纯金属催化剂在水煤气变换反应（WGSR）中的性能。结果表明，与相应的纯金属催化剂相比，经B单原子修饰的Cu催化剂具有空前的催化性能，这是由于嵌入的B单原子产生了两个电子不同的异质Cu原子而具有特殊的水离解活性位点。结构。此外，由于其迷人的电子性能，B原子可以充当电荷转移介质，在阴离子和阳离子状态之间自由切换。更重要的是，在WGSR中，B掺杂Cu表面上异质Cu原子的协同作用将限速步骤（水离解）的活化能垒降低了0.11 eV。电子结构分析出现了降级d波段与乙原子和换高档协调表面Cu原子的中心d波段那些由铜-铜协调的中心源自菌株和配体的效果。这些发现旨在为人们提供深厚的见识，使人们能够使用WGSR中的地球上丰富的元素设计新的催化剂。