Nitrogen–Doped Carbon Nanotube–Supported Ni3Se4–CeO2 Heterojunctions With Multi–Orbital Hybridization for Efficient Hydrogen Evolution Reaction

en This link goes to a English section zh This link goes to a Chinese section Engineering of the catalyst interface and modulation of transition–metal d–band play critical roles in the electrocatalytic hydrogen evolution reaction (HER). Herein, a synthetic strategy is developed to fabricate nitrogen-doped carbon nanotubes (N–CNTs)–supported Ni 3 Se 4 –CeO 2 heterojunction catalysts through a facile chemical vapor deposition (CVD) process coupled with selenization. The heterojunction catalysts show excellent catalytic activity and stability for HER. Density functional theory (DFT) calculations reveal that Se modifies the electronic structure of Ni, CeO 2 regulates the interfacial charge distribution, and a multi–orbital coupling effect arises among the components. These synergistic effects collectively elevate the d–band center, thereby optimizing the free energy of the key adsorbed hydrogen intermediate (Δ G H* ) in HER. Benefiting from the synergies between interface engineering and multi–orbital hybridization, the optimized Ni 3 Se 4 –CeO 2 heterojunction delivers a low overpotential of 180 mV at 100 mA cm −2 , with a Tafel slope of 83.6 mV dec −1 . The N–CNTs substrate further reduces charge–transfer resistance, thus promoting HER performance. Moreover, the confinement effect provided by cellulose acetate (CA) and the hydrogen–bonding network formed within the cotton substrate ensure outstanding long–term durability, as evidenced by sustained catalytic activity after 100 h of continuous operation at 100 mA cm −2 . This work will offer a promising pathway toward the development of efficient heterojunction catalysts for HER via modulation of their electronic structure and interface. 摘要 en This link goes to a English section zh This link goes to a Chinese section 在电催化析氢反应(HER)中,界面工程以及过渡金属 d 带的调节发挥着关键作用。因此,我们开发了一种合成策略,通过简便的化学气相沉积过程(CVD)结合硒化,制备了氮掺杂碳纳米管(N–CNTs)负载的 Ni 3 Se 4 –CeO 2 异质结催化剂。这种异质结催化剂表现出优秀的HER活性和稳定性。密度泛函理论(DFT)计算表明,硒改变了镍的电子结构,CeO 2 使界面电荷重新分布,各成分之间产生了多轨道耦合效应。这些协同效应共同使d带中心上移,从而优化了HER中关键吸附氢中间体的自由能(Δ G H* )。得益于界面工程和多轨道杂化的协同作用,优化后的 Ni 3 Se 4 –CeO 2 异质结催化剂在 100 mA cm –2 下,过电位仅为180 mV,并且 Tafel 斜率为 83.6 mV dec –1 。N–CNTs基底进一步降低了电荷转移电阻( R ct ),从而提高了 HER 性能。此外,醋酸纤维素(CA)所提供的限域效应以及与棉基底形成的氢键网络保证了其稳定性。这一点从在 100 mA cm –2 的电流强度下连续运行 100 小时后仍保持稳定的催化活性中得到了证明。这项工作将为通过调节其电子结构和界面来开发高效的析氢反应(HER)异质结催化剂提供一条有前景的途径。