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嵌入铂单原子的苯并咪唑基共价有机框架实现高效可见光析氢
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作者 马方沛 汤庆平 +8 位作者 席识博 李国庆 陈涛 凌星辰 吕忆农 刘云鹏 赵小龙 周瑜 王军 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第5期137-149,共13页
氢气(H_(2))是一种清洁的无碳燃料,具有很高的能量密度,是化石能源的潜在替代品之一.半导体光催化水分解反应可将取之不竭的太阳能转化为氢气中的化学能,从而提供一条有前途的、经济和环境友好的产氢路线.光催化析氢反应(HER)涉及光捕... 氢气(H_(2))是一种清洁的无碳燃料,具有很高的能量密度,是化石能源的潜在替代品之一.半导体光催化水分解反应可将取之不竭的太阳能转化为氢气中的化学能,从而提供一条有前途的、经济和环境友好的产氢路线.光催化析氢反应(HER)涉及光捕集、激发、电荷分离和传输,以及表面质子还原过程.光激发态通常在几皮秒内发生,通过辐射或非辐射复合弛豫返回到基态,然而,光生电子迁移到表面并触发两电子的质子还原是一个慢过程,时间通常在几毫秒或以上.整个过程中转换效率因光生电子极易复合而大大降低.因此,如何延长光生电子寿命,促进电子及时传递到表面析氢位点,提高催化位点的析氢速率,是设计水分解高效光催化剂的关键,也是该领域的难题.有机半导体催化剂可以从地球丰度高的轻元素制备,具有成本低、毒性小和结构多样等特点.其中一个典型代表是共价有机框架(COFs),其具有大的比表面积及丰富可调的骨架组成和孔道结构,在分子水平上的可设计性具有独特优势.苯并咪唑化合物具有较大极性和灵活可调的π共轭结构,被广泛用作光电器件的共轭辅助分子.以苯并咪唑基单体直接合成的COF种类罕见,且未见相关COF用于光催化反应的报道.本文通过选用不对称的苯并咪唑单体(2-(4-氨基苯基)-5-氨基苯并咪唑)与三醛基间苯三酚直接通过席夫碱化学反应缩合,制备了苯并咪唑基COF.该COF材料有效促进了光吸收和电荷分离/传递,以及高活性Pt单原子析氢位点的形成,在可见光驱动的析氢反应中表现出较好的析氢速率和转换频率.采用微波辅助的溶剂热策略快速合成了苯并咪唑基COF(PABZ-Tp),通过X射线衍射、傅立叶变换红外吸收光谱、13C固态核磁共振等研究其结构.光学和光电化学表征结果表明,PABZ-Tp在可见光范围.内展现出较好的光吸收,具有较低的激子解离能(17.8 meV),有效促进了长寿命自由光电子的形成.骨架中带负电荷的苯并咪唑基团不但是Pt单原子形成和稳定的主要因素,还有助于构建良好的电子迁移通道,从而有效促进了光生电子快速传递到表面Pt单原子位点,使得该催化剂在可见光驱动的析氢反应中表现出较高的催化效率,析氢速率高达115 mmol g^(-1)h^(-1),转换频率为4475.1 h^(-1).理论计算结合瞬态吸收光谱等实验结果表明,苯并咪唑COF框架是产生高活性的关键,对于光吸收、电荷分离传递以及高效析氢位点的构筑均起了重要作用.综上,本文构筑了一种高效的COF基有机光催化剂用于可见光析氢过程.展示了使用不对称咪唑基单体构筑功能化COF材料的广阔前景. 展开更多
关键词 共价有机框架 光催化 析氢 单原子催化 可持续能源
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Tunable Luminescence Properties and Elucidating the Electronic Structures of Single-Phase Spherical BaWO 4:Dy^(3+),Tm^(3+),Eu^(3+)Phosphors for Warm-White-Lighting
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作者 Zun Bi Ke Jia +1 位作者 Yunfei Liu yinong lyu 《Journal of Renewable Materials》 SCIE EI 2022年第2期431-451,共21页
A series of uniform single-phase spherical BaWO 4:Dy^(3+),Tm^(3+),Eu^(3+)phosphors were prepared via a microwave hydrothermal method by using trisodium citrate dehydrate as surfactant.The phase structure,morphology an... A series of uniform single-phase spherical BaWO 4:Dy^(3+),Tm^(3+),Eu^(3+)phosphors were prepared via a microwave hydrothermal method by using trisodium citrate dehydrate as surfactant.The phase structure,morphology and photoluminescence properties were measured by powder X-ray diffraction,scanning electron microscope and fluorescence spectrometer,respectively.The results show that uniform spherical microcrystals with diameters in the range of 2–4μm are obtained.And the phase and morphology of samples are not significantly changed by doping rare earth(RE^(3+))ions.Under the excitation wavelength of 356 and 365 nm,the samples BaWO 4:0.03Dy^(3+),yTm^(3+)can emit cold white light.In order to lower the correlated color temperature(CCT)to get a warm white light,the Eu^(3+)ions were doped into BaWO 4:0.03Dy^(3+),0.01Tm^(3+).Especially,under the excitation of 365 nm,BaWO 4:0.03Dy^(3+),0.01Tm^(3+),0.03Eu^(3+)phosphor shew a bright warm white light with color coordi-nate of(0.4013,0.3629)and CCT of 3288 K.Moreover,in the BaWO 4:Dy^(3+),Tm^(3+),Eu^(3+)phosphors,the energy transfer mechanism among Dy^(3+),Tm^(3+)and Eu^(3+)ions have been discussed and the change of electron structures have been calculated by first-principles calculations.The results shew that the uniform single-phase spherical BaWO 4:Dy^(3+),Tm^(3+),Eu^(3+)phosphors could be favorable candidates in warm white LEDs. 展开更多
关键词 Barium tungstate microwave hydrothermal method SPHERICAL warm white lighting electron structures
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Atomic-scale insight into the epitaxial growth mechanism and interfacial coupling of BNT film prepared by hydrothermal synthesis
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作者 Fujun Chen Hao Qian +4 位作者 Xiaoyuan Sun Tianyang Zheng Yunfei Liu Jin Luo yinong lyu 《Journal of Materials Science & Technology》 SCIE EI CAS CSCD 2023年第33期198-204,共7页
Revealing the epitaxial growth mechanism and the interfacial coupling effect between oxide films will help to build a“structure-property”bridge for the design of microelectronic devices.Here,the epitaxial growth mec... Revealing the epitaxial growth mechanism and the interfacial coupling effect between oxide films will help to build a“structure-property”bridge for the design of microelectronic devices.Here,the epitaxial growth mechanism and the interfacial coupling in Bi_(0.5)Na_(0.5)TiO_(3)/SrTiO_(3)(BNT/STO)heterointerfaces are investigated by the aberration-corrected scanning transmission electron microscopy,which is synthesized by a hydrothermal method.The results illustrate that 4 mol/L NaOH leads to not only the epitaxial growth of the BNT film but also the mutual diffusion of elements.The uneven distribution of local elements in BNT films is observed and confirmed to impact the cation displacements of B-site and lattice distortion.However,the overall trend of B-site cation displacement at the BNT/STO heterointerfaces is dominated by the interfacial strain.Additionally,the oxygen octahedral tilt exhibits continuous tilt patterns of a^(0)a^(0)a^(0)-a−b^(0)c−-a^(0)a^(0)c−-a^(0)b−c−-a−b−c−from the substrate to BNT film due to the constraint of the substrate and presents a strong correlation with cation displacement.These results are helpful to understand the underlying atomic structures and physical properties of BNT epitaxial thin films. 展开更多
关键词 Hydrothermal synthesis Growth mechanism Interfacial coupling AC-STEM Octahedral tilt
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Robust perfluorinated porous organic networks: Succinct synthetic strategy and application in chlorofluorocarbons adsorption 被引量:2
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作者 Yali Luo Zhenzhen Yang +7 位作者 Xian Suo Hao Chen Tao Wang Ziqian Wang Yunfei Liu yinong lyu llja Popovs Sheng Dai 《Nano Research》 SCIE EI CSCD 2021年第9期3282-3287,共6页
Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free... Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene(PDVB)as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Bronsted acid(trifluoromethanesulfonic acid).The afforded material(F-PDVB)featured high fluorine content(22 at.%),large surface area(771 m^(2)·g^(-1)),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO_(2),hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.%being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers(F-HCPs)from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications. 展开更多
关键词 FLUORINATED porous organic networks Friedel-Crafts reaction hyper-crosslinked polymers CHLOROFLUOROCARBONS
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