稀土掺杂Mg₂Si的光催化、机械和光学性能增强:第一性原理计算和机器学习

IF 3.7 2区 化学 Q2 CHEMISTRY, APPLIED
Jianfeng Ye, Xinhai Wang, Dahai Yu, Fuqiang Ai, Songguo Yu, Jiayi Shen, Shenshang Lu, Qingquan Xiao, Shen Li, Quan Xie
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引用次数: 0

摘要

宽带光吸收、机械弹性和有效的表面催化都是光催化半导体的关键,但它们很少在一种材料中得到改善。我们将第一性原理计算与机器学习可解释性和Pearson相关分析相结合,揭示了稀土(La, Er)掺杂Mg₂Si可以协同增强其光电,机械和析氢性能。La掺杂通过La-5d/Si-3p轨道杂化引入了导带杂质态,将亚带隙(红外)吸收提高了60倍(~0.6 × 105 cm−1),并将吸收边缘扩展到近红外转换,太阳能-氢转换效率高达39.86%。它还渗透出一种金属键网络,使泊松比(0.23→0.46)加倍,使Mg₂Si从脆性变为延展性。相比之下,铒掺杂使4f轨道局域化,在紫外线下产生激子样吸收峰(~105 cm−1),并诱导出明显的电子和机械响应。两种掺杂剂都将费米能级推入导带(简并n型掺杂),从根本上改变了载流子的特性。在催化上,La掺杂产生离域sp3d2轨道,产生近热中性氢吸附(ΔGH*≈−0.04 eV),优于贵金属催化剂,而Er的扩展电子密度增强了H结合,但代价是较慢的H₂脱附。SHAP (SHapley加性解释)分析进一步确定了控制这些趋势的关键轨道和弹性描述符,提供了一个机制蓝图。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Enhanced Photocatalytic, Mechanical, and Optical Performance of Rare-Earth–Doped Mg₂Si: First-Principles Calculations and Machine Learning

Enhanced Photocatalytic, Mechanical, and Optical Performance of Rare-Earth–Doped Mg₂Si: First-Principles Calculations and Machine Learning

Broadband light absorption, mechanical resilience, and efficient surface catalysis are all crucial for photocatalytic semiconductors, yet they are rarely improved together in one material. We combine first-principles calculations with machine-learning interpretability and Pearson correlation analyses to reveal that rare-earth (La, Er) doping of Mg₂Si can synergistically enhance its optoelectronic, mechanical, and hydrogen-evolution performance. La doping introduces conduction-band impurity states via La-5d/Si-3p orbital hybridization, boosting sub-bandgap (infrared) absorption by 60-fold (~0.6 × 105 cm−1) and extending the absorption edge into the near-infrared—translating to a solar-to-hydrogen conversion efficiency of up to 39.86%. It also percolates a metallic bond network that doubles the Poisson's ratio (0.23 → 0.46), transforming Mg₂Si from brittle to ductile. Er doping, in contrast, localizes 4f orbitals, yielding exciton-like absorption peaks (~105 cm−1) in the ultraviolet and inducing a distinct electronic and mechanical response. Both dopants push the Fermi level into the conduction band (degenerate n-type doping), fundamentally altering carrier characteristics. Catalytically, La doping generates delocalized sp3d2 orbitals that give near-thermoneutral hydrogen adsorption (ΔGH* ≈ −0.04 eV), outperforming noble-metal catalysts, whereas Er's extended electron density enhances H binding at the cost of slower H₂ desorption. SHAP (SHapley Additive exPlanations) analysis further identifies the key orbital and elastic descriptors governing these trends, providing a mechanistic blueprint.

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来源期刊
Applied Organometallic Chemistry
Applied Organometallic Chemistry 化学-无机化学与核化学
CiteScore
7.80
自引率
10.30%
发文量
408
审稿时长
2.2 months
期刊介绍: All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.
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