Perovskite solar cells (PSCs) employing formamidinium lead iodide (FAPbI_(3)) have shown high efficiency.However,operational stability has been issued due to phase instability of α phase FAPbI_(3) at ambient temperat...Perovskite solar cells (PSCs) employing formamidinium lead iodide (FAPbI_(3)) have shown high efficiency.However,operational stability has been issued due to phase instability of α phase FAPbI_(3) at ambient temperature.Excess precursors in the perovskite precursor solution has been proposed to improve not only power conversion efficiency (PCE) but also device stability.Nevertheless,there is a controversial issue on the beneficial effect on PCE and/or stability between excess FAI and excess PbI_(2).We report here extended X-ray absorption fine structure (EXAFS) of FAPbI_(3) to study local structural change and explain the effect of excess precursors on photovoltaic performance and stability.Perovskite films prepared from the precursor solution with excess PbI_(2)shows better stability than those from the one with excess FAI,despite similar PCE.A rapid phase transition from α phase to non-perovskite δ phase is observed from the perovskite film formed by excess FAI.Furthermore,the (Pb-I) bond distance evaluated by the Pb L_(III)-edge EXAFS study is increased by excess FAI,which is responsible for the phase transition and poor device stability.This work can provide important insight into local structure-stability relation in the FAPbI_(3)-based PSCs.展开更多
A new X-ray absorption fine structure(XAFS)data-collection system based on the Experimental Physics and Industrial Control System software environment has been established at the BL14W1 beamline of the Shanghai Synchr...A new X-ray absorption fine structure(XAFS)data-collection system based on the Experimental Physics and Industrial Control System software environment has been established at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facility. The system provides for automatic sequential analysis of multiple samples for continuous high-throughput(HT) measurements. Specifically, 8 sample pellets are loaded into an alumina holder,and a high-precision two-dimensional translation stage is programmed to switch these samples automatically for collecting the XAFS spectrum of each sample in sequence.Experimenters implement HT measurements via a graphical user interface developed with Control System Studio.Finally, the successful operation of the HT XAFS system is demonstrated by running experiments on two groups of copper–ceria catalysts, each of which contains 8 different powder samples.展开更多
The weak pre-edge features in the Mn K-edge X-ray absorption near-edge structure (XANES) spectrumof manganese monoxide (MnO) were investigated by comparing experimental data with dipolar and quadrupolarcross-section c...The weak pre-edge features in the Mn K-edge X-ray absorption near-edge structure (XANES) spectrumof manganese monoxide (MnO) were investigated by comparing experimental data with dipolar and quadrupolarcross-section calculations in the framework of multiple-scattering theory. We assign the first pre-edge feature to a di-rect quadrupolar transition from Is core state to 3d molecular orbitals of the central atom, e.g., the lowest in energy,due to the more effective attraction of the core hole. The second peak in this region arises unambiguously from thehybridization between p-orbitals of the central atom with higher-shell metal octahedral orbitals.展开更多
为了利用X射线吸收精细结构(X-ray absorption fine structure,XAFS)谱学技术开展热化学反应动力学研究,在上海光源X射线吸收精细结构谱学线站(BL14W1)开展了时间分辨热化学原位XAFS方法的研究。采用自主研制的数据采集设备解决了时间分...为了利用X射线吸收精细结构(X-ray absorption fine structure,XAFS)谱学技术开展热化学反应动力学研究,在上海光源X射线吸收精细结构谱学线站(BL14W1)开展了时间分辨热化学原位XAFS方法的研究。采用自主研制的数据采集设备解决了时间分辨XAFS技术中不同类型信号同步触发和同步采集的问题,实现了数据间的精准匹配。在单色器转速为720"/s、数据采集设备采样率为2MS/s、数据长度为1200eV的条件下,获得了一个9.6s的Cu标样的数据谱,通过与常规XAFS数据和标准XAFS数据进行对比,结果表明本文得到的时间分辨XAFS实验系统具有良好的准确性、分辨率和信噪比。在此基础上,进一步结合线站自主研制的原位装置开展了时间分辨热化学原位XAFS方法,并利用高温常压原位装置开展了CuO还原为金属Cu的验证性实验。在230℃恒温氢气气氛下30min内观测到Cu吸收边能量逐渐向低能量处偏移,同时它位于8998eV的主峰强度逐渐减弱并且劈裂为双峰结构,出现明显的金属Cu的特征。实验结果表明此方法达到了捕获物质动态演化过程的预期目的,在拓展XAFS谱学实验平台的同时,为热化学反应的动力学过程研究提供了一种强大的实验手段。展开更多
Macrocycle compounds have great importance in host-guest chemistry and moleculeidentifications. 4-acetyl-bispyrazolones are a new type of polydentate ligands. Whenthey react with diamine compounds, new compounds or co...Macrocycle compounds have great importance in host-guest chemistry and moleculeidentifications. 4-acetyl-bispyrazolones are a new type of polydentate ligands. Whenthey react with diamine compounds, new compounds or complexes containing C=O andC=N groups can be obtained. These compounds can be used to study the relationship ofcoordination structure and its properties, energy transferring processes between metal展开更多
The oxidation of antimony （Ⅲ） in soils was studied using X-ray absorption fine structure （XAFS） spectra. An andosol soft sample and artificial soil samples （SiO2 blended with iron （Ⅲ） hydroxide and manganese...The oxidation of antimony （Ⅲ） in soils was studied using X-ray absorption fine structure （XAFS） spectra. An andosol soft sample and artificial soil samples （SiO2 blended with iron （Ⅲ） hydroxide and manganese （Ⅳ） oxide） were used herein. After adding antimony （Ⅲ） oxide to all soil samples, the oxidation process was observed by recording the XAFS spectra of Sb K-edge, Fe Kedge, and Mn K-edge. The results indicated that manganese （Ⅳ） oxide played an important role in the oxidation of Sb（Ⅲ）; however iron （Ⅲ） hydroxide was not directly related to the reaction. During a 2-hr continuous Sb K-edge X-ray absorption near edge structure （XANES） measurement with an interval of I rain of one of the artificial soil samples （SiO2 ＋ MnO2 ＋ Sb2O3）, a pseudo-first-order reaction was determined with an average estimated rate of 0.52 ±0.04 hr-1. Compared to the lower oxidation rate of andosol, it is suggested that because of the low concentration of Mn（Ⅳ） in natural soils, the oxidation process of Sb（Ⅲ） might be relatively slow and require more time to convert Sb（Ⅲ） to Sb（V）.展开更多
红绿彩瓷是一种低温釉上彩瓷,从结构层次探讨其釉上红彩、绿彩、黄彩的呈色机理一直是古陶瓷研究的空白。采用X射线吸收精细结构(X-rayabsorption fine structure,XAFS)方法,测试分析红绿彩瓷中的红彩、绿彩和黄彩。结果表明,红彩中致...红绿彩瓷是一种低温釉上彩瓷,从结构层次探讨其釉上红彩、绿彩、黄彩的呈色机理一直是古陶瓷研究的空白。采用X射线吸收精细结构(X-rayabsorption fine structure,XAFS)方法,测试分析红绿彩瓷中的红彩、绿彩和黄彩。结果表明,红彩中致色元素Fe主要为+3价,其局域结构与Fe2O3相近,最近邻配位为扭曲的八面体结构。透射电子显微分析证实其物相为氧化铁晶体。黄彩中致色元素Fe主要存在+2价和+3价,绿彩中致色元素Cu主要为+2价,两者均处于无序度较高的局域环境中,最近邻配位为O原子。展开更多
由于X射线吸收精细结构（X—rayabsorption fine structure，XAFS）可以原位探测吸收原子的2～3个邻近配位壳层，获得目标元素的电子结构信息和化学结构信息，所以XAFS已成为微观领域最重要的结构分析工具，丰富了我们对元素的重要化学...由于X射线吸收精细结构（X—rayabsorption fine structure，XAFS）可以原位探测吸收原子的2～3个邻近配位壳层，获得目标元素的电子结构信息和化学结构信息，所以XAFS已成为微观领域最重要的结构分析工具，丰富了我们对元素的重要化学性质和反应过程的认识。本文简述了XAFS的基本原理，探讨了样品制备、测试及数据分析等过程需关注的问题，重点综述了应用XAFS研究土壤重金属和营养元素的形态、土壤固一液界面的反应过程和机理，并指出其应用的局限性和未来发展的前景，旨在推动我国XAFS在土壤科学中的应用。由于土壤中界面反应的复杂性，XAFS应结合其他结构分析技术，结构分析技术应结合宏观数据和计算机模拟，土壤学应与其他学科交叉、融合，只有这样，才有可能在时间和空间尺度上阐明土壤组分在环境界面上的复杂反应过程和机理。展开更多
基金supported by the(NRF)grants funded by the Ministry of Science,the ICT Future Planning(MSIP)of Korea under NRF-2016M3D1A1027663,NRF-2016M3D1A1027664(Future Materials Discovery Program),and NRF-2021R1A3B1076723(Research Leader Program)。
文摘Perovskite solar cells (PSCs) employing formamidinium lead iodide (FAPbI_(3)) have shown high efficiency.However,operational stability has been issued due to phase instability of α phase FAPbI_(3) at ambient temperature.Excess precursors in the perovskite precursor solution has been proposed to improve not only power conversion efficiency (PCE) but also device stability.Nevertheless,there is a controversial issue on the beneficial effect on PCE and/or stability between excess FAI and excess PbI_(2).We report here extended X-ray absorption fine structure (EXAFS) of FAPbI_(3) to study local structural change and explain the effect of excess precursors on photovoltaic performance and stability.Perovskite films prepared from the precursor solution with excess PbI_(2)shows better stability than those from the one with excess FAI,despite similar PCE.A rapid phase transition from α phase to non-perovskite δ phase is observed from the perovskite film formed by excess FAI.Furthermore,the (Pb-I) bond distance evaluated by the Pb L_(III)-edge EXAFS study is increased by excess FAI,which is responsible for the phase transition and poor device stability.This work can provide important insight into local structure-stability relation in the FAPbI_(3)-based PSCs.
基金supported by the National Natural Science Foundation of China under Grant No.21373259
文摘A new X-ray absorption fine structure(XAFS)data-collection system based on the Experimental Physics and Industrial Control System software environment has been established at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facility. The system provides for automatic sequential analysis of multiple samples for continuous high-throughput(HT) measurements. Specifically, 8 sample pellets are loaded into an alumina holder,and a high-precision two-dimensional translation stage is programmed to switch these samples automatically for collecting the XAFS spectrum of each sample in sequence.Experimenters implement HT measurements via a graphical user interface developed with Control System Studio.Finally, the successful operation of the HT XAFS system is demonstrated by running experiments on two groups of copper–ceria catalysts, each of which contains 8 different powder samples.
基金One of the authors(WU Zi-Yu)acknowledges the financial support of the 100-Talent Research Program of the Chinese Academy of Sciences and of the Outstanding Youth Fund(10125523)the Key Important Nano-Research Project(90206032)of the National Natural Science Founda tion of China.
文摘The weak pre-edge features in the Mn K-edge X-ray absorption near-edge structure (XANES) spectrumof manganese monoxide (MnO) were investigated by comparing experimental data with dipolar and quadrupolarcross-section calculations in the framework of multiple-scattering theory. We assign the first pre-edge feature to a di-rect quadrupolar transition from Is core state to 3d molecular orbitals of the central atom, e.g., the lowest in energy,due to the more effective attraction of the core hole. The second peak in this region arises unambiguously from thehybridization between p-orbitals of the central atom with higher-shell metal octahedral orbitals.
文摘为了利用X射线吸收精细结构(X-ray absorption fine structure,XAFS)谱学技术开展热化学反应动力学研究,在上海光源X射线吸收精细结构谱学线站(BL14W1)开展了时间分辨热化学原位XAFS方法的研究。采用自主研制的数据采集设备解决了时间分辨XAFS技术中不同类型信号同步触发和同步采集的问题,实现了数据间的精准匹配。在单色器转速为720"/s、数据采集设备采样率为2MS/s、数据长度为1200eV的条件下,获得了一个9.6s的Cu标样的数据谱,通过与常规XAFS数据和标准XAFS数据进行对比,结果表明本文得到的时间分辨XAFS实验系统具有良好的准确性、分辨率和信噪比。在此基础上,进一步结合线站自主研制的原位装置开展了时间分辨热化学原位XAFS方法,并利用高温常压原位装置开展了CuO还原为金属Cu的验证性实验。在230℃恒温氢气气氛下30min内观测到Cu吸收边能量逐渐向低能量处偏移,同时它位于8998eV的主峰强度逐渐减弱并且劈裂为双峰结构,出现明显的金属Cu的特征。实验结果表明此方法达到了捕获物质动态演化过程的预期目的,在拓展XAFS谱学实验平台的同时,为热化学反应的动力学过程研究提供了一种强大的实验手段。
基金Project supported by the National Natural Science FoundationNational Climbing Programme of China.
文摘Macrocycle compounds have great importance in host-guest chemistry and moleculeidentifications. 4-acetyl-bispyrazolones are a new type of polydentate ligands. Whenthey react with diamine compounds, new compounds or complexes containing C=O andC=N groups can be obtained. These compounds can be used to study the relationship ofcoordination structure and its properties, energy transferring processes between metal
基金XAFS measurements were carried out at Photon Factory,Tsukuba,Japan(Nos.2014G066,2016G086).
文摘The oxidation of antimony （Ⅲ） in soils was studied using X-ray absorption fine structure （XAFS） spectra. An andosol soft sample and artificial soil samples （SiO2 blended with iron （Ⅲ） hydroxide and manganese （Ⅳ） oxide） were used herein. After adding antimony （Ⅲ） oxide to all soil samples, the oxidation process was observed by recording the XAFS spectra of Sb K-edge, Fe Kedge, and Mn K-edge. The results indicated that manganese （Ⅳ） oxide played an important role in the oxidation of Sb（Ⅲ）; however iron （Ⅲ） hydroxide was not directly related to the reaction. During a 2-hr continuous Sb K-edge X-ray absorption near edge structure （XANES） measurement with an interval of I rain of one of the artificial soil samples （SiO2 ＋ MnO2 ＋ Sb2O3）, a pseudo-first-order reaction was determined with an average estimated rate of 0.52 ±0.04 hr-1. Compared to the lower oxidation rate of andosol, it is suggested that because of the low concentration of Mn（Ⅳ） in natural soils, the oxidation process of Sb（Ⅲ） might be relatively slow and require more time to convert Sb（Ⅲ） to Sb（V）.
文摘红绿彩瓷是一种低温釉上彩瓷,从结构层次探讨其釉上红彩、绿彩、黄彩的呈色机理一直是古陶瓷研究的空白。采用X射线吸收精细结构(X-rayabsorption fine structure,XAFS)方法,测试分析红绿彩瓷中的红彩、绿彩和黄彩。结果表明,红彩中致色元素Fe主要为+3价,其局域结构与Fe2O3相近,最近邻配位为扭曲的八面体结构。透射电子显微分析证实其物相为氧化铁晶体。黄彩中致色元素Fe主要存在+2价和+3价,绿彩中致色元素Cu主要为+2价,两者均处于无序度较高的局域环境中,最近邻配位为O原子。
基金supported by the National Natural Science Foundation of China(21373251)Main Direction Program of Knowledge Innovation of Chinese Academy of Sciences,China(KZCX2-EW-307)~~
文摘由于X射线吸收精细结构（X—rayabsorption fine structure，XAFS）可以原位探测吸收原子的2～3个邻近配位壳层，获得目标元素的电子结构信息和化学结构信息，所以XAFS已成为微观领域最重要的结构分析工具，丰富了我们对元素的重要化学性质和反应过程的认识。本文简述了XAFS的基本原理，探讨了样品制备、测试及数据分析等过程需关注的问题，重点综述了应用XAFS研究土壤重金属和营养元素的形态、土壤固一液界面的反应过程和机理，并指出其应用的局限性和未来发展的前景，旨在推动我国XAFS在土壤科学中的应用。由于土壤中界面反应的复杂性，XAFS应结合其他结构分析技术，结构分析技术应结合宏观数据和计算机模拟，土壤学应与其他学科交叉、融合，只有这样，才有可能在时间和空间尺度上阐明土壤组分在环境界面上的复杂反应过程和机理。
