ハロゲン表面パッシベーションによる効率的メタノール光活性化を実現 (Surface Halogen Passivation Achieves Efficient Methanol Photoactivation)

026-03-10 中国科学院(CAS)

中国科学院合肥物質科学研究院・強磁場科学センター(SHMFF)のXIE Yi、ZHANG Xiaodongらの研究チームは、半導体光触媒の安定性を高める表面ハロゲン(Cl、Br、I)パッシベーション戦略を提案した。モデル触媒として硫化カドミウム(CdS)を用い、表面にハロゲン原子を導入することで光照射下で起こるCdやSの溶出を抑え、光腐食を防止できることを示した。また電荷移動速度が向上し、励起子分離や界面電子輸送が促進されることで光触媒活性も向上した。電子スピン共鳴(EPR)解析により、特にCl修飾が電荷移動促進と光腐食抑制に寄与することを確認。メタノール活性化や芳香族化合物メチル化で高い性能と耐久性を示し、太陽光化学変換や小分子活性化技術への応用が期待される。

ハロゲン表面パッシベーションによる効率的メタノール光活性化を実現 (Surface Halogen Passivation Achieves Efficient Methanol Photoactivation)
Schematic diagram of surface halogen (Cl, Br and I) passivation (Image by LI Jingxin)

<関連情報>

表面ハロゲン不動態化により、効率的なメタノール光活性化のための超安定金属硫化物を実現 Surface Halogen Passivation Enables Ultra-Stable Metal Sulfide for Efficient Methanol Photoactivation

Yi Liu,Gang Chen,Lei Li,Hanghao Ying,Hui Wang,Zongpeng Song,Haiou Zhu,Xiaodong Zhang,and Yi Xie
Journal of the American Chemical Society  Published: February 10, 2026
DOI:https://doi.org/10.1021/jacs.5c19863

Abstract

Transition metal sulfides exhibit promising photocatalytic activity for high-value-added chemical synthesis; however, they suffer from significant photocorrosion and rapid deactivation during reactions. In this study, we propose a surface halogen (Cl, Br, and I) passivation strategy to improve the stability of photocatalysts, which would provide a protective barrier against chemical attack, preventing oxidative and reductive surface degradation. By taking the typical metal sulfide catalysts of CdS as a representative model, we show that the introduced surface halogen can effectively suppress surface leakage of sulfur or cadmium ions under continuous photoirradiation, in stark contrast to the extensive structural damage observed in pristine CdS. Moreover, the halogen-passivated catalyst showed exceptional photocatalytic efficiency attributable to accelerated charge-transfer kinetics that expedite exciton dissociation and interfacial electron transport. These improvements enable effective methanol activation and selective C(sp3)–H methylation of heteroarenes even at ultralow irradiance, where the Cl-passivated CdS achieves a yield up to 90%, far exceeding the trace yield of pristine CdS. This study provides fundamental insights into the role of surface halogen passivation in optimizing photostability and electronic structure in photocatalysis.

0505化学装置及び設備
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