Integrating multi-step reactions through tandem catalysis offers potential for efficient chemical engineering processes, but designing an efficient tandem catalyst is challenging. Herein, we report tailoring the d-band centers of Ni through alloying with a second metal (M = Fe/Co/Cu/Ga), which enables it to be multifunctional site for tandem reductive amination. A linear correlation of d-band center with yield of primary amine product was observed. Density functional theory and experiments revealed the upshifted d-band center strengthened the adsorption of Schiff base intermediate in advantageous di(C&N) mode, also narrowed the adsorption energy gap between NH₃ and H₂. Furthermore, the multifunctional nanoparticles provide a confined space with short diffusion pathway for NH₃* and H* to timely react with Schiff base. As a result, the NiFe/AlO_x with a d-band center nearest to the Fermi level exhibited the highest primary amine yield of 96.2% with five consecutive reusability under extremely low H₂ pressure, which is superior to other reported precious-metal-based catalysts.

中文翻译：

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定制 d 带中心使 NiM 合金成为串联还原胺化的多功能位点


通过串联催化整合多步反应为高效化学工程过程提供了潜力，但设计高效的串联催化剂具有挑战性。在此，我们报告通过与第二种金属（M = Fe/Co/Cu/Ga）合金化调整Ni的d带中心，这使其成为串联还原胺化的多功能位点。观察到 d 带中心与伯胺产物的产率呈线性相关。密度泛函理论和实验表明，上移的d带中心增强了席夫碱中间体在有利的di(C&N)模式下的吸附，也缩小了NH ₃和H ₂之间的吸附能隙。此外，多功能纳米颗粒为NH ₃ * 和H * 及时与希夫碱反应提供了短扩散路径的有限空间。结果，d带中心最接近费米能级的NiFe/AlO _x在极低的H ₂压力下表现出最高的伯胺收率，达到96.2%，并且连续五次可重复使用，优于其他报道的贵金属-基催化剂。