中国科学技术大学宋礼研究团队利用单碘原子策略操纵镍d带中心促进碱性析氢反应。相关研究成果于2024年9月19日发表于国际一流学术期刊《美国化学会杂志》。

镍基电催化剂被认为是析氢反应（HER）的高潜力候选者；然而，它们的适用性受到不利的d波段能级（Ed）的阻碍。此外，专用的合成方法和实验表征阻碍了镍基材料的精确d带结构工程。

该文中，研究人员精心合成了一种特殊的单碘原子结构（I-Ni@C)并通过共振非弹性X射线散射（RIXS）光谱表征了Ed的操纵，以填补这一空白。通过基于同步辐射的多种技术（SRMS）阐明了复杂的催化机理，包括X射线吸收精细结构（XAFS）、基于同步辐射原位傅里叶变换红外（SR-FTIR）光谱和近环境压力X射线光电子能谱（NAP-XPS）。

特别是，RIXS被创新性地应用于揭示I-Ed精确调控Ni@C。因此，这种单碘原子策略的作用被证实不仅有助于Ni位点的适度Ed，以平衡关键中间体的吸附/解吸能力，而且可以作为桥梁，增强Ni和碳壳之间的电子相互作用，形成有利于H₂O解离的局部极化电场。因此，I-Ni@C表现出增强的碱性析氢性能，在10mA/cm²下的过电势为78mV，稳定性优于大多数报道的镍基催化剂。

总的来说，该研究成功地从SRMS的角度定制了材料的d带中心，这对纳米技术、化学、催化和其他领域具有至关重要的意义。

附：英文原文

Title: Manipulating d-Band Center of Nickel by Single-Iodine-Atom Strategy for Boosted Alkaline Hydrogen Evolution Reaction

Author: Chongjing Liu, Beibei Sheng, Quan Zhou, Yujian Xia, Ying Zou, Peter Joseph Chimtali, Dengfeng Cao, Yongheng Chu, Sirui Zhao, Ran Long, Shuangming Chen, Li Song

Issue&Volume: September 19, 2024

Abstract: Ni-based electrocatalysts have been predicted as highly potential candidates for hydrogen evolution reaction (HER); however, their applicability is hindered by an unfavorable d-band energy level (Ed). Moreover, precise d-band structural engineering of Ni-based materials is deterred by appropriative synthesis methods and experimental characterization. Herein, we meticulously synthesize a special single-iodine-atom structure (I–Ni@C) and characterize the Ed manipulation via resonant inelastic X-ray scattering (RIXS) spectroscopy to fill this gap. The complex catalytic mechanism has been elucidated via synchrotron radiation-based multitechniques (SRMS) including X-ray absorption fine structure (XAFS), in situ synchrotron radiation-based Fourier transform infrared (SR-FTIR) spectroscopy, and near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). In particular, RIXS is innovatively applied to reveal the precise regulation of Ni Ed of I–Ni@C. Consequently, the role of such single-iodine-atom strategy is confirmed to not only facilitate the moderate Ed of the Ni site for balancing the adsorption/desorption capacities of key intermediates but also act as a bridge to enhance the electronic interaction between Ni and the carbon shell for forming a localized polarized electric field conducive to H2O dissociation. As a result, I–Ni@C exhibits an enhanced alkaline hydrogen evolution performance with an overpotential of 78 mV at 10 mA/cm2 and superior stability, surpassing the majority of the reported Ni-based catalysts. Overall, this study has managed to successfully tailor the d-band center of materials from the SRMS perspective, which has crucial implications for nanotechnology, chemistry, catalysis, and other fields.

DOI: 10.1021/jacs.4c07607

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c07607