Electronic-State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO2 Near Room Temperature
Electronic-State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO2 Near Room Temperature
复制标题
表面钛的电子态操纵可在室温附近激活 TiO2 的去磷酸化
DOI：
10.1002/anie.202104397
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Peng Yung-Kang
中科院分区：
文献类型：
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作者：
Wang Quan;Yi Xianfeng;Chen Yu-Cheng;Xiao Yao;Zheng Anmin;Chen Jian Lin;Peng Yung-Kang
从底物中去除磷酸基团的脱磷酸不仅对于生物体而且对于环境保护来说都是重要的反应。尽管 CeO2 已被证明可以催化该反应，但作为稀土元素之一，铈的自然丰度较低且全球分布范围狭窄（超过 90% 的储量位于六个国家）。因此，迫切需要找到另一种在全球范围内具有高丰度的元素/材料，该元素/材料也可以有效地从农业废物中提取磷酸盐以进行磷回收。使用磷酸对硝基苯酯（p-NPP）作为模型化合物，我们在此证明具有F修饰（001）表面的TiO2可以在低至40℃的温度下激活p-NPP去磷酸化。通过探针辅助核磁共振（NMR）发现，氟的强吸电子作用使（001）表面的Ti原子（即活性位点）呈酸性。 p-NPP 在该表面上的双齿吸附进一步促进了其随后的活化，其势垒比原始 (001) 和 (101) 表面低约 20 kJ/mol，从而允许该反应在接近室温（> 80 °C）下活化。
Dephosphorylation that removes a phosphate group from substrates is an important reaction for not only living organisms but also environmental protection. Although CeO2 has been shown to catalyze this reaction, as one of the rare earth elements, cerium is low in natural abundance and has a narrow global distribution (> 90% of these reserves are located within six countries). It is thus imperative to find another element/material with high worldwide abundance that can also efficiently extract the phosphate out of agricultural wastes for phosphorus recycle. Using para-nitrophenyl phosphate (p-NPP) as the model compound, we demonstrate herein that TiO2 with F-modified (001) surface can activate p-NPP dephosphorylation at temperature as low as 40 °C. By probe-assisted nuclear magnetic resonance (NMR), it was revealed that the strong electron withdrawing effect of fluorine makes Ti atoms (i.e., the active sites) on (001) surface very acidic. The bidentate adsorption of p-NPP on this surface further promotes its subsequent activation with barrier ~20 kJ/mol lower than that of pristine (001) and (101) surfaces, allowing the activation of this reaction at nearly room temperature (from > 80 °C).