Jianfeng Ye, Xinhai Wang, Dahai Yu, Fuqiang Ai, Songguo Yu, Jiayi Shen, Shenshang Lu, Qingquan Xiao, Shen Li, Quan Xie
{"title":"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","authors":"Jianfeng Ye, Xinhai Wang, Dahai Yu, Fuqiang Ai, Songguo Yu, Jiayi Shen, Shenshang Lu, Qingquan Xiao, Shen Li, Quan Xie","doi":"10.1002/aoc.70396","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>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 × 10<sup>5</sup> cm<sup>−1</sup>) 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 (~10<sup>5</sup> cm<sup>−1</sup>) 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 sp<sup>3</sup>d<sup>2</sup> orbitals that give near-thermoneutral hydrogen adsorption (Δ<i>G</i><sub><i>H*</i></sub> ≈ −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.</p>\n </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7000,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhanced Photocatalytic, Mechanical, and Optical Performance of Rare-Earth–Doped Mg₂Si: First-Principles Calculations and Machine Learning\",\"authors\":\"Jianfeng Ye, Xinhai Wang, Dahai Yu, Fuqiang Ai, Songguo Yu, Jiayi Shen, Shenshang Lu, Qingquan Xiao, Shen Li, Quan Xie\",\"doi\":\"10.1002/aoc.70396\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>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 × 10<sup>5</sup> cm<sup>−1</sup>) 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 (~10<sup>5</sup> cm<sup>−1</sup>) 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 sp<sup>3</sup>d<sup>2</sup> orbitals that give near-thermoneutral hydrogen adsorption (Δ<i>G</i><sub><i>H*</i></sub> ≈ −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.</p>\\n </div>\",\"PeriodicalId\":8344,\"journal\":{\"name\":\"Applied Organometallic Chemistry\",\"volume\":\"39 10\",\"pages\":\"\"},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2025-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Organometallic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/aoc.70396\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/aoc.70396","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
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.
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.