Efficient and selective photocatalytic CH(4) conversion to CH(3)OH with O(2) by controlling overoxidation on TiO(2).
Efficient and selective photocatalytic CH(4) conversion to CH(3)OH with O(2) by controlling overoxidation on TiO(2).
复制标题
通过控制 TiO2 的过度氧化，高效、选择性地光催化 CH4 与 O2 转化为 CH3OH
DOI：
10.1038/s41467-021-24912-0
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发表时间：
2021-08-02
影响因子：
16.6
通讯作者：
Ye J
中科院分区：
文献类型：
--
作者：
Feng N;Lin H;Song H;Yang L;Tang D;Deng F;Ye J
由于不可避免的过氧化，光催化甲烷高收率、高选择性地转化为甲醇仍然是一个巨大的挑战。在这里，光催化氧化CH 4到CH 3OH由O2进行Ag修饰的面为主的TiO 2。{001}主导的TiO 2显示出4.8 mmol g−1 h−1的持久的CH 3OH产率和约80%的选择性，这代表比最近研究中报道的值高得多的值，并且优于{101}主导的TiO 2获得的值。傅里叶变换红外光谱，电子自旋共振和核磁共振技术被用来全面阐明潜在的机制。光生空穴直接在{001}面上产生氧空位，对于避免形成·CH 3和·OH起着关键作用，·CH 3和·OH是导致过氧化的主要因素，并且通常形成在{101}面上。{001}面上氧空位的产生导致不同的中间体和反应路径（氧空位→ Ti-O2· → Ti-OO-Ti和Ti-（OO）→ Ti-O·对），从而实现CH 4光氧化为CH 3OH的高选择性和产率。高活性和高选择性的光催化转化CH 4为CH 3OH必须避免产物的过氧化。在这里，作者通过使用（001）占主导地位的TiO 2纳米片来规避CH 4过氧化中间体加上发生在（101）面上的反应途径来最大限度地减少过氧化。
The conversion of photocatalytic methane into methanol in high yield with selectivity remains a huge challenge due to unavoidable overoxidation. Here, the photocatalytic oxidation of CH4 into CH3OH by O2 is carried out on Ag-decorated facet-dominated TiO2. The {001}-dominated TiO2 shows a durable CH3OH yield of 4.8 mmol g−1 h−1 and a selectivity of approximately 80%, which represent much higher values than those reported in recent studies and are better than those obtained for {101}-dominated TiO2. Operando Fourier transform infrared spectroscopy, electron spin resonance, and nuclear magnetic resonance techniques are used to comprehensively clarify the underlying mechanism. The straightforward generation of oxygen vacancies on {001} by photoinduced holes plays a key role in avoiding the formation of •CH3 and •OH, which are the main factors leading to overoxidation and are generally formed on the {101} facet. The generation of oxygen vacancies on {001} results in distinct intermediates and reaction pathways (oxygen vacancy → Ti–O2• → Ti–OO–Ti and Ti–(OO) → Ti–O• pairs), thus achieving high selectivity and yield for CH4 photooxidation into CH3OH. The photocatalytic conversion of CH4 into CH3OH with high activity and selectivity must avoid product overoxidation. Here, authors minimize overoxidation by using a (001)-dominated TiO2 nanosheet to circumvent CH4 overoxidation intermediates plus reaction pathways that occur on (101) facets.
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影响因子：
64.8
作者：
ITO, T;LUNSFORD, JH
通讯作者：
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影响因子：
41.2
作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
12.9
作者：
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通讯作者：
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作者：
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通讯作者：
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