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
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引用次数: 0
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.
镍基电催化剂被认为是氢进化反应(HER)中极具潜力的候选催化剂;然而,不利的 d 带能级(Ed)阻碍了它们的应用。此外,适当的合成方法和实验表征也阻碍了镍基材料的精确 d 波段结构工程。在此,我们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)光谱对 Ed 操作进行了表征,从而填补了这一空白。通过同步辐射多技术(SRMS),包括 X 射线吸收精细结构(XAFS)、原位同步辐射傅立叶变换红外光谱(SR-FTIR)和近环境压力 X 射线光电子能谱(NAP-XPS),阐明了复杂的催化机理。其中,RIXS 被创新性地用于揭示 I-Ni@C 中 Ni Ed 的精确调节。因此,这种单碘原子策略的作用得到了证实,它不仅促进了镍位点的适度 Ed,以平衡关键中间产物的吸附/解吸能力,而且还充当了加强镍与碳壳之间电子相互作用的桥梁,以形成有利于 H2O 解离的局部极化电场。因此,I-Ni@C 表现出更强的碱性氢气进化性能,在 10 mA/cm2 的过电位为 78 mV,而且稳定性极佳,超过了大多数已报道的镍基催化剂。总之,这项研究从 SRMS 的角度成功地定制了材料的 d 波段中心,对纳米技术、化学、催化等领域具有重要意义。
期刊介绍:
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