pH-Dependent Degradation of Layered Black Phosphorus: Essential Role of Hydroxide Ions.
pH-Dependent Degradation of Layered Black Phosphorus: Essential Role of Hydroxide Ions.
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DOI：
10.1002/anie.201809989
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发表时间：
2018-12
影响因子：
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通讯作者：
Siyu Zhang;Xuejiao Zhang;Lei Lei-Lei;Xuefeng Yu;Jingwen Chen;Chuanxin Ma;Fengchang Wu;Qing Zhao;B. Xing
中科院分区：
文献类型：
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作者：
Siyu Zhang;Xuejiao Zhang;Lei Lei-Lei;Xuefeng Yu;Jingwen Chen;Chuanxin Ma;Fengchang Wu;Qing Zhao;B. Xing
层状黑磷（LBP）在H2 O和/或O2存在下的快速分解影响了其实际应用。h2o的作用是有争议的。在此，我们提出了一种氢氧离子（OH-）引发的LBP降解机制，以阐明H2 o的作用。我们发现LBP在碱性溶液中的降解速度比在有或没有O2的中性或酸性溶液中更快。LBP的降解率在pH 4 ~ 10范围内呈线性增加。密度泛函理论（DFT）计算表明，OH-通过破坏P-P键，形成P-O键，引发了LBP的分解。由OH-与P原子反应产生的次亚磷酸盐的检测证实了这一假设。质子的作用方式与OH-不同，通过诱导沉积/聚集或形成阳离子-π层来保护LBP免受降解。这项工作揭示了LBP的降解机理，从而促进了有效稳定技术的发展。
The practical application of layered black phosphorus (LBP) is compromised by fast decomposition in the presence of H2 O and/or O2 . The role of H2 O is controversial. Herein, we propose a hydroxide ion (OH- )-initiated degradation mechanism for LBP to elucidate the role of H2 O. We found that LBP degraded faster in alkaline solutions than in neutral or acidic solutions with or without O2 . Degradation rates of LBP increased linearly from pH 4 to 10. Density functional theory (DFT) calculations showed that OH- initiated the decomposition of LBP through breaking the P-P bond and forming a P-O bond. The detection of hypophosphite, generated from OH- reacting with P atoms, confirmed the hypothesis. Protons acted in a way distinctive from OH- , by inducing deposition/aggregation or forming a cation-π layer to protect LBP from degradation. This work reveals the degradation mechanism of LBP and thus facilitates the development of effective stabilization technologies.