In this article, we report the preparation of a three-dimensional(3D) interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional(2D) hexagonal mes...In this article, we report the preparation of a three-dimensional(3D) interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional(2D) hexagonal mesoporous anatase 70 TiO2-30 SiO2-950 nanocomposite(crystallized at 950 °C for 2 h) as a precursor, NaO H as an etchant of SiO2 via a "creating mesopores in the pore walls" approach. Our strategy adopts mild conditions of creating pores such as diluted NaO H solution, appropriate temperature and solid/liquid ratio, etc. aiming at ensuring the integrities of mesopores architecture and anatase nanocrystals. XRD, TEM and N2 sorption techniques have been used to systematically investigate the physico-chemical properties of the nanocomposites. The results show that the intrawall mesopores are highly dense and uniform(average pore size 3.6 nm), and highly link the initial mesochannels in a 3D manner while retaining mesostructural integrity. There is no significant change to either crystallinity or size of the anatase nanocrystals before and after creating the intrawall mesopores. The photocatalytic degradation rates of rhodamine B(RhB, 0.303 min^–1) and methylene blue(MB, 0.757 min^–1) dyes on the resultant nanocomposite are very high, which are 5.1 and 5.3 times that of the precursor; even up to 16.5 and 24.1 times that of Degussa P25 photocatalyst, respectively. These results clearly demonstrate that the 3D interconnected mesopores structure plays an overwhelming role to the increments of activities. The 3D mesoporous anatase TiO2-SiO2 nanocomposite exhibits unexpected-high degradation activities to RhB and MB in the mesoporous metal oxide-based materials reported so far. Additionally, the nanocomposite is considerably stable and reusable. We believe that this method would pave the way for the preparation of other 3D highly interconnected mesoporous metal oxide-based materials with ultra-high performance.展开更多
Potassium-selenium(K-Se)batteries have attracted more and more attention because of their high theoretical specific capacity and natural abundance of K resources.However,dissolution of polyselenides,large volume expan...Potassium-selenium(K-Se)batteries have attracted more and more attention because of their high theoretical specific capacity and natural abundance of K resources.However,dissolution of polyselenides,large volume expansion during cycling and low utilization of Se remain great challenges,leading to poor rate capability and cycle life.Herein,N/O dual-doped carbon nanofibers with interconnected micro/mesopores(MMCFs)are designed as hosts to manipulate Se molecular configuration for advanced flexible K-Se batteries.The micropores play a role in confining small Se molecule(Se_(2–3)),which could inhibit the formation of polyselenides and work as physical barrier to stabilize the cycle performance.While the mesopores can confine long-chain Se(Se_(4–7)),promising sufficient Se loading and contributing to higher discharge voltage of the whole Se@MMCFs composite.The N/O co-doping and the 3D interpenetrating nanostructure improve electrical conductivity and keep the structure integrity after cycling.The obtained Se_(2–3)/Se_(4–7)@MMCFs electrode exhibits an unprecedented cycle life(395 mA h g^(−1) at 1 A g^(−1) after 2000 cycles)and high specific energy density(400 Wh kg^(−1),nearly twice the specific energy density of the Se_(2–3)@MMCFs).This study offers a rational design for the realization of a high energy density and long cycle life chalcogen cathode for energy storage.展开更多
基金supported by the National Natural Science Foundation of China(21373056)the Science and Technology Commission of Shanghai Municipality(13DZ2275200)~~
文摘In this article, we report the preparation of a three-dimensional(3D) interconnected mesoporous anatase TiO2-SiO2 nanocomposite. The nanocomposite was obtained by using an ordered two-dimensional(2D) hexagonal mesoporous anatase 70 TiO2-30 SiO2-950 nanocomposite(crystallized at 950 °C for 2 h) as a precursor, NaO H as an etchant of SiO2 via a "creating mesopores in the pore walls" approach. Our strategy adopts mild conditions of creating pores such as diluted NaO H solution, appropriate temperature and solid/liquid ratio, etc. aiming at ensuring the integrities of mesopores architecture and anatase nanocrystals. XRD, TEM and N2 sorption techniques have been used to systematically investigate the physico-chemical properties of the nanocomposites. The results show that the intrawall mesopores are highly dense and uniform(average pore size 3.6 nm), and highly link the initial mesochannels in a 3D manner while retaining mesostructural integrity. There is no significant change to either crystallinity or size of the anatase nanocrystals before and after creating the intrawall mesopores. The photocatalytic degradation rates of rhodamine B(RhB, 0.303 min^–1) and methylene blue(MB, 0.757 min^–1) dyes on the resultant nanocomposite are very high, which are 5.1 and 5.3 times that of the precursor; even up to 16.5 and 24.1 times that of Degussa P25 photocatalyst, respectively. These results clearly demonstrate that the 3D interconnected mesopores structure plays an overwhelming role to the increments of activities. The 3D mesoporous anatase TiO2-SiO2 nanocomposite exhibits unexpected-high degradation activities to RhB and MB in the mesoporous metal oxide-based materials reported so far. Additionally, the nanocomposite is considerably stable and reusable. We believe that this method would pave the way for the preparation of other 3D highly interconnected mesoporous metal oxide-based materials with ultra-high performance.
基金This work was supported by the National Key R&D Research Program of China(Nos.2018YFA0209600,2017YFA0208300)the National Natural Science Foundation of China(Nos.51925207,U1910210,51872277,52002083,22005292,51802302)+4 种基金the DNL cooperation Fund,CAS(DNL180310)the Fundamental Research Funds for the Central Universities(WK2060140026,WK3430000006,WK2060000009)the National Synchrotron Radiation Laboratoi-y(KY2060000173)the National Postdoctoral Program for Innovative Talents(BX20200318)the China Postdoctoral Science Foundation(Nos.2020M672533,2019TQ0296,2020M682012).
文摘Potassium-selenium(K-Se)batteries have attracted more and more attention because of their high theoretical specific capacity and natural abundance of K resources.However,dissolution of polyselenides,large volume expansion during cycling and low utilization of Se remain great challenges,leading to poor rate capability and cycle life.Herein,N/O dual-doped carbon nanofibers with interconnected micro/mesopores(MMCFs)are designed as hosts to manipulate Se molecular configuration for advanced flexible K-Se batteries.The micropores play a role in confining small Se molecule(Se_(2–3)),which could inhibit the formation of polyselenides and work as physical barrier to stabilize the cycle performance.While the mesopores can confine long-chain Se(Se_(4–7)),promising sufficient Se loading and contributing to higher discharge voltage of the whole Se@MMCFs composite.The N/O co-doping and the 3D interpenetrating nanostructure improve electrical conductivity and keep the structure integrity after cycling.The obtained Se_(2–3)/Se_(4–7)@MMCFs electrode exhibits an unprecedented cycle life(395 mA h g^(−1) at 1 A g^(−1) after 2000 cycles)and high specific energy density(400 Wh kg^(−1),nearly twice the specific energy density of the Se_(2–3)@MMCFs).This study offers a rational design for the realization of a high energy density and long cycle life chalcogen cathode for energy storage.