Dimensional and Optoelectronic Tuning of Lead-free Perovskite Cs3Bi2I9−nBrn Single Crystals for Enhanced Hard X-ray Detection

Inorganic Bi-based perovskites have shown great potential in X-ray detection for their large absorption to X-rays, diverse low-dimensional structures, and eco-friendliness without toxic metals. However, they suffer from poor carrier transport properties compared to Pb-based perovskites. Here, we propose a mixed-halogen strategy to tune the structural dimensions and optoelectronic properties of Cs₃Bi₂I_9−nBr_n (0≤n≤9). Ten centimeter-sized single crystals are successfully grown by the Bridgman technique. Upon doping bromine to zero-dimensional Cs₃Bi₂I₉, the crystal transforms into a two-dimensional structure as the bromine content reaches Cs₃Bi₂I₈Br. Correspondingly, the optoelectronic properties are adjusted. Among these crystals, Cs₃Bi₂I₈Br exhibits negligible ion migration, moderate resistivity, and the best carrier transport capability. The sensitivities in 100 keV hard X-ray detection are 1.33×10⁴ and 1.74×10⁴ μC Gy_air⁻¹ cm⁻² at room temperature and 75 °C, respectively, which are the highest among all reported bismuth perovskites. Moreover, the lowest detection limit of 28.6 nGy_air s⁻¹ and ultralow dark current drift of 9.12×10⁻⁹ nA cm⁻¹ s⁻¹ V⁻¹ are obtained owing to the high ionic activation energy. Our work demonstrates that Br incorporation is an effective strategy to enhance the X-ray detection performance by tuning the dimensional and optoelectronic properties.     

酶提取-单颗粒电感耦合等离子质谱法分析樱桃番茄纳米银颗粒及其吸收规律研究

为探究复合保鲜涂膜中AgNPs的迁移情况,采用酶提取的前处理方式,结合单颗粒电感耦合等离子体质谱（SP-ICP-MS）,考察了前处理方式、驻留时间、校准方式以及Ag+浓度等条件对AgNPs准确测定的影响。结果表明：0.1 g樱桃番茄样品在柠檬酸盐体系下使用0.2 g的R-10离析酶可达到消解最适酶剂量;当驻留时间小于100 μs时,测定结果有较好的积分条件以及较高的信背比;采用AgNP尺寸方式进行校准比单独用Ag+标准溶液校准方式的颗粒尺寸测定结果更加准确。采用该方法测定樱桃番茄中加标AgNPs颗粒回收率达到88.9%,粒径实测值为47.8±0.3 nm,粒径检出限为13 nm,颗粒浓度检出限为 7.5×104 particles/L。通过将樱桃番茄暴露于AgNPs涂膜中来探究AgNPs迁移行为,复合保鲜涂膜后的樱桃番茄通过三次洗涤后能够在表面去除大部分AgNPs,但仍有少量AgNPs穿过果表皮浸入果肉组织。该方法灵敏度高,操作简单,能够为揭示AgNPs在农产品及农业生产中的风险提供可靠、准确的表征方法。     

河南麦区收割对大气颗粒物及其组分特征排放的影响

农业收割期间排放的颗粒物是农忙期影响大气气溶胶组成的主要来源,因此明确农业收割期间排放的大气颗粒物排放特征具有重要意义。本实验立足河南省新乡市集约化农田实验基地,开展冬小麦区农业收割期间的大气颗粒物及其组分排放特征实验。结果表明收割期间的PMcoarse比其它时期高8.20%,农业站点收割时期的PMcoarse比其它时期高了72.22%,明确了其颗粒物污染特征为仅PM₁₀升高,而非PM₁₀和PM_2.5同时升高,同时PM₁₀的升高非PM_2.5升高引起的;含量最高的前5种元素是Al、Ca、Fe、K、Mg;收割期间,Fe的特征比值最高为0.79;Ca₂₊^和K₊^{离子百分含量在}PMcoarse中占比最高;特征值为0.81和0.78。综合水溶性离子和元素结果,Ca₂₊^、K₊^、Fe浓度协同变化可作为小麦收割过程颗粒物对大气污染影响的指纹识别,以区别于其他污染类型;便于大气污染防治行政主管部门有针对性的查污、防污、治污,提高人民群众生活环境的空气质量。     

Uncovering the Contributions of Charge Regulation to the Stability of Single Alpha Helices**

The single alpha helix (SAH) is a recurring motif in biology. The consensus sequence has a di-block architecture that includes repeats of four consecutive glutamate residues followed by four consecutive lysine residues. Measurements show that the overall helicity of sequences with consensus E₄K₄ repeats is insensitive to a wide range of pH values. Here, we use the recently introduced q-canonical ensemble, which allows us to decouple measurements of charge state and conformation, to explain the observed insensitivity of SAH helicity to pH. We couple the outputs from separate measurements of charge and conformation with atomistic simulations to derive residue-specific quantifications of preferences for being in an alpha helix and for the ionizable residues to be charged vs. uncharged. We find a clear preference for accommodating uncharged Glu residues within internal positions of SAH-forming sequences. The stabilities of alpha helical conformations increase with the number of E₄K₄ repeats and so do the numbers of accessible charge states that are compatible with forming conformations of high helical content. There is conformational buffering whereby charge state heterogeneity buffers against large-scale conformational changes thus making the overall helicity insensitive to large changes in pH. Further, the results clearly argue against a single, rod-like alpha helical conformation being the only or even dominant conformation in the ensembles of so-called SAH sequences.     

Determination of lanthanum and cerium in cmsx-4 nickel-based superalloys by inductively coupled plasma mass spectrometryEI北大核心CSCD

CMSX-4 is the second-generation nickel-based single crystal superalloy used widely in the world. The oxidation resistance and corrosion resistance of CMSX-4 alloy can be improved by adding trace lanthanum (La), cerium (Ce) and other rare earth elements. A method for the simultaneous determination of La and Ce in CMSX-4 nickel-based superalloy by wet dissolution-inductively coupled plasma mass spectrometry was established. The sample was heated and dissolved under normal pressure by aqua regia and hydrofluoric acid, and the interference of fluorine ion was eliminated by using perchloric acid. The amount of dissolved acid and the digestion conditions were optimized. The limits of detection were 0.23 μg/g for La and 0.85 μg/g for Ce under optimized conditions. The spiked recoveries were 95.0%–98.9% with the relative standard deviations of 1.3%–3.9%, which can meet the requirements of accurate and rapid determination of La and Ce in CMSX-4 nickel-based superalloy. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

主成份分析-偏最小二乘法分光光度法同时测定钴、镍、铜、锌四组份体系

用 PCA 及 PLS 分步处理分光光度数据,有效降低了计算的维数。以该法对不同酸度体系的5-Br-PADAP-钴、镍、铜、锌分光光度数据进行了处理,定量分析结果良好。     

Molecular speciation of microparticles: application of pattern recognition techniques to laser microprobe mass spectrometric data

Attempts were made to enhance the ability of laser microprobe mass spectrometry (LAMMS) to identify molecular species in individual microparticles by applying pattern recognition methods. Principal component analysis (PCA) and canonical discriminant analysis were applied to LAMMS data for nickel-containing environmental particles. Detailed comparison of the two statistical methods demonstrated the utility of PCA. The successful application was highly dependent on the use of appropriate spectral normalization and feature extraction techniques prior to PCA. Although the test system involved only a small number of standard compounds, the LAMMS data were complicated by the effects of intra-particle heterogeneity common to environmental samples and by instrumental limitations. Pattern recognition techniques provided more accurate quantitative assignments of molecular species than were available by qualitative inspection of characteristic cluster ions or by simple spectral subtraction to compare particle data with a library of standard compounds. Results were substantiated by comparison with bulk analysis studies using wet chemical techniques.     

轨道对称性匹配:MXene基体上的单原子催化以实现优异的氮还原反应

氨作为一种可被植物直接吸收用以合成其他有机物的重要成分,在化学化工及含氮化合物的生产当中起着至关重要的作用.传统工业生产氨气采用Haber-Bosch工艺,将空气中丰富的氮气转化为氨气,但该工艺需要较高的压强和温度来促进氮气分解,因此会消耗大量能源.近年来,电催化反应发展迅速.在电催化工艺中,通过控制操作电位及电解质便可提高生产效率,降低能源消耗.基于这种策略,各种针对能源环境的催化研究应运而生,如二氧化碳还原、水分解反应等.其中,对于氮还原的催化研究尤其是电催化设计领域研究相对较少.研究发现,在电催化剂中,异构掺杂及原子尺度的调控可以极大地影响催化剂的催化活性.其中,单原子催化(SAC)因其在催化活性和催化选择性上的优势受到广泛关注.MXene是一种二维过渡金属碳化物或氮化物,其优异的化学性能和稳定的表面构型可以对单原子起到良好的锚定与支撑作用,是一种更具潜力的单原子催化基体.本文基于上述思想,利用密度泛函第一性原理等模拟软件,设计并研究了以MXene为基体的28种过渡金属单原子催化体系,计算并分析了各SAC@MXene体系对氮还原反应的催化效果,从限制电势、催化路径、反应机制等方面探索了其催化性能.并对体系进行了态密度、晶体轨道哈密顿量、差分电荷密度等电子结构分析,找到了适用于MXene体系的单原子催化设计原则.通过对限制电势的计算表明,Ni@MXene和Co@MXene体系具有很低的限制电势(-0.13和-0.17 V),说明这些体系在较低的启动电压下即可发生氮还原反应.研究发现了一种新型适用于SAC@MXene氮催化体系的酶促-远端反应机制.电子结构分析得到SAC原子与MXene基体的Ti原子在催化过程中存在一种协同作用.态密度及晶体轨道哈密顿量也显示出SAC原子与MXene基体Ti之间的一种轨道对称性匹配关系,揭示了这种协同作用对催化反应的积极作用.计算的氢析出反应(HER)结果也显示,在相同化学环境下,SAC@MXene体系氮还原反应相对于氢析出反应更易发生.     

Ni-N-C单原子催化剂活化过硫酸盐降解苯酚

采用煅烧法制备了以木质素生物炭为载体的单原子催化剂(Ni-N-C-10), 用于高效活化过硫酸盐(PMS)降解苯酚. 利用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 经球差校正的高角度环形暗场扫描透射电子显微镜(AC-HAADF-STEM)、 X射线粉末衍射仪(XRD)以及X射线光电子能谱仪(XPS)等对材料进行了表征分析, 证明合成了原子分散的催化剂Ni-N-C-10. 探究了制备过程中双氰胺的投加量和降解实验中催化剂投加量、 PMS投加量、 pH值以及温度对苯酚降解的影响. 结果表明, 在催化剂制备过程中, 加入10倍质量比的双氰胺更有利于实现原子分散. Ni-N-C-10/PMS体系在较低的催化剂和PMS投加量、 以及较宽的pH值范围(3~9)内都能有效活化PMS降解苯酚. 此外, 该体系的稳定性好且应用范围广, 除了能高效降解苯酚外还能快速降解双酚A、 四环素和亚甲基蓝. 电子顺磁共振检测和自由基淬灭实验结果表明, Ni-N-C-10/PMS体系降解苯酚为SO₄^?-、 ·OH和¹O₂ 3种主要活性物种共同作用的结果, 其中¹O₂起主导作用. 反应前后Ni-N-C-10催化剂的XPS分析结果表明, 催化降解苯酚的效率与Ni位点呈正相关.     

多孔有机盐单晶的合成及各向异性质子导电性能

以cis,cis-1,3,5-三氨基环己烷·3HBr和均苯四甲酸在室温下通过离子键构筑了具有规整形貌和大尺寸的晶态多孔有机盐CPOS-10, 其具有较好的热稳定性和永久多孔性. 得益于规整形貌及大尺寸单晶, 首次实现了对多孔有机盐单晶各向异性质子导电性能的研究, 并结合晶体结构探索了各向异性质子导电的机理. 结果表明, 水分子浓度对CPOS-10质子电导率的大小具有重要作用, 骨架内水分子浓度高的晶面更易于与极性基团构成氢键网络, 促进质子传导, 利用此网络的质子传导具有更高的质子电导率. 因此, 骨架内水分子的不均匀分布是导致单晶各向异性质子导电的主要原因. 对CPOS-10单晶各向异性质子导电性能的探索可为研究多孔有机盐的质子导电机理提供重要的依据.