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将自由基限制在污染物附近可在二硫化钼膜的间隙中实现超快类芬顿过程。

Confining Free Radicals in Close Vicinity to Contaminants Enables Ultrafast Fenton-like Processes in the Interspacing of MoS Membranes.

作者信息

Chen Yu, Zhang Gong, Liu Huijuan, Qu Jiuhui

机构信息

Key Laboratory of Drinking Water Science and Technology Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China.

University of Chinese Academy of Sciences, Beijing, 100049, China.

出版信息

Angew Chem Int Ed Engl. 2019 Jun 11;58(24):8134-8138. doi: 10.1002/anie.201903531. Epub 2019 May 8.

Abstract

Heterogenous Fenton-like reactions are frequently proposed for treating persistent pollutants through the generation of reactive radicals. Despite great efforts to optimize catalyst activity, their broad application in practical settings has been restricted by the low efficiency of hydrogen peroxide or persulfate decomposition as well as ultrafast self-quenching of the activated radicals. Theoretical calculations predicted that two-dimensional (2D) metallic 1T phase MoS materials with exposed (001) surfaces and (100) edges should have remarkable affinity towards crucial intermediates in the peroxymonosulfate (PMS) activation process. X-ray photoelectron spectroscopy and in situ Raman spectroscopy were used to show that the exposed metallic Mo sites accelerate the rate-limiting step of electron transfer. A lamellar membrane made from a stack of 2D MoS with tunable interspacing was then designed as the catalyst. The non-linear transport between the MoS nanolayers leads to high water diffusivity so that the short-lived reactive radicals efficiently oxidize contaminants.

摘要

非均相类芬顿反应常被用于通过产生活性自由基来处理持久性污染物。尽管人们为优化催化剂活性付出了巨大努力,但过氧化氢或过硫酸盐分解效率低下以及活化自由基的超快自猝灭限制了它们在实际环境中的广泛应用。理论计算预测,具有暴露的(001)表面和(100)边缘的二维(2D)金属1T相MoS材料对过一硫酸盐(PMS)活化过程中的关键中间体应具有显著的亲和力。利用X射线光电子能谱和原位拉曼光谱表明,暴露的金属Mo位点加速了电子转移的限速步骤。然后,将由具有可调间距的2D MoS堆叠制成的层状膜设计为催化剂。MoS纳米层之间的非线性传输导致高水扩散率,从而使短寿命的活性自由基能够有效地氧化污染物。

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