石墨消解-ICP-MS法同时测定铜精矿中4种有害元素

为弥补标准检测方法的不足,建立了石墨消解-ICP-MS法同时检测铜精矿中Pb、Cd、As 和Hg等4种有害元素。确定了样品前处理和仪器分析条件。用铜精矿标准样品和参考样品分别进行7次重复实验,Pb、Cd和As的检测结果均在标准值范围内,Hg的检测结果与参考值基本一致。7次重复检测结果的变异系数符合GB/T 27417-2017《合格评定 化学分析方法确认和验证指南》要求。选择5种不同物相铜精矿作为待测样品,通过与标准方法比对,两种方法检测结果的绝对差符合标准方法的再现性要求,说明本方法适用于不同种类的铜精矿。本方法操作简单,可同时测定多种有害元素,实用性强。     

自动快速燃烧－离子色谱测定铜精矿中的氟

建立了自动快速燃烧（AQF）－离子色谱联用测定铜精矿中氟的方法。将 AQF 的自动化特性和离子色谱的灵敏度高、准确性好的特点结合起来,能够实现操作过程的连续自动化。结果表明,线性范围内（1.0?50.0 μg )校准曲线相关系数 r >0. 999,氟的检出限为0.0004%。按照实验方法测定铜精矿样品中氟,结果的相对标准偏差（ RSD ,n =6)为2.14 % ?4.24 %。将实验方法用于铜精矿标准样品氟含量测定,测定值与认定值吻合较好;方法对照试验表明,实验方法对氟含量的测定值与国家标准 GB/T 3884. 12—2010的测定值基本一致。     

对电极材料对非贵金属电催化剂耐久性评价的影响

质子交换膜燃料电池(PEMFCs)环境友好,具有高的能量转换效率,已受到了广泛的关注.目前,铂基电催化剂广泛使用在 PEMFCs中,但铂的储量有限,活性低,耐久性差,成本高,急需开发高性能的非贵金属电催化剂替代铂基电催化剂.非贵金属电催化剂的电化学表征基本上都沿用了铂基电催化剂的评价体系和方法,不一定适用于非贵金属电催化剂的表征.
　　本文选用铂和石墨为对电极考察其对非贵金属电催化剂在酸性电解质中耐久性测试的影响.当使用铂对电极时,商业 Pt/C电催化剂的氧还原(ORR)活性随着耐久性测试圈数的增加而降低,而非贵金属电催化剂的氧还原活性在耐久性测试过程中的变化规律与商业 Pt/C不同,呈现先降低,后升高的规律.耐久性测试前后的透射电镜(TEM)分析表明非贵金属电催化剂经过耐久性测试后,在电催化剂表面生长了铂纳米颗粒.高分辨透射电镜(HRTEM)和能量色散 X射线光谱(EDX)进一步证明以铂为对电极的三电极体系,在进行非贵金属电催化剂耐久性测试的过程中,非贵金属电催化剂表面生长了铂纳米颗粒,使得非贵金属电催化剂的 ORR活性在耐久性测试后得到显著提高.耐久性测试前后,非贵金属电催化剂氧还原过程的电子转移数由3.7变为4.0,再次证明了耐久性测试过程中铂颗粒的生成.在三电极电化学体系中,当工作电极发生阴极反应时,对电极为阳极反应,反之亦然,即在工作电极上发生的任何电化学过程,都会在对电极上完成相反的电化学过程.在循环电位扫描过程中,当铂对电极的电压高于1.0 V (vs RHE)时,开始发生铂的溶解现象,并且当电压高于1.2 V (vs RHE)时,铂的溶解量会急剧增加,部分溶解的铂会扩散到工作电极附近,并在工作电极的非贵金属电催化剂表面发生沉积作用.随着扫描圈数的增加,沉积的铂纳米颗粒的数量增加,颗粒变大,从而使非贵金属电催化剂的表观 ORR活性显著提高.该现象使得非贵金属电催化剂在酸性电解质中无法表现出其真实的耐久性.当选用石墨棒为对电极材料时,非贵金属电催化剂在酸性电解质中的 ORR活性不会受到对电极材料的影响.
　　通过考察对电极材料对非贵金属电催化剂在酸性电解质中耐久性能的影响,可以得出结论,即对非贵金属电催化剂在酸性电解质中的耐久性测试中,不宜使用铂对电极,应该使用石墨为对电极材料,以防止对电极材料干扰耐久性测试.     

Effectiveness of linearization of calibration curves in Zeeman graphite furnace atomic absorption spectrometry

A theoretical analysis is made of the effect of analytical line broadening and of non-absorbable radiation in the light source on the shape of concentration curves in Zeeman graphite furnace atomic absorption spectrometry. These results have been used in a systematic study of the effect of spectrometer slit width and hollow-cathode lamp (HCL) current on linearization of calibration graphs for 11 elements: Ag, Au, Bi, Cd, Co, Cu, Fe, Mn, Ni, Pb, and Sb. The effectiveness of linearization throughout the analytical range covered was estimated experimentally on series of 25–30 solutions. Three solutions in each series were used as standards for constructing the calibration graph, the others serving to evaluate the linearization effectiveness. Increasing the slit width and decreasing the HCL current compared to the standard measurement conditions have permitted us to reach a sufficiently high effectiveness of linearization for all the elements studied, with the exception of Ni. The maximum deviation of experimental points from the linear graph under optimum conditions does not exceed 6%. The effect of the Δ parameter used in the computational algorithm on linearization effectiveness is investigated.     

超级微波消解－石墨炉原子吸收光谱法测定香菇中的镉

为建立一种快速批量检测香菇中镉的方法,建立了超级微波消解－石墨炉原子吸收光谱法测定香菇中镉含量的方法。分别采用湿法消解、普通微波消解和超级微波、传统微波和湿法消解技术前处理香菇标准物质样品,对比消解效果,优化超级微波消解技术的酸体系和消解最终温度。;采用石墨炉原子吸收光谱仪法测定,优化基体改进剂、灰化温度等工作参数,确定仪器最佳检测条件,验证分析方法的准确性和稳定性。结果表明,超级微波消解优于湿法消解和传统微波消解技术,准确性和重复性最佳,大幅减少用酸量的同时更加安全、高效,避免样品污染。在最优分析方法条件下,镉在0~4.0 μg/L范围内所得回归方程线性关系良好,相关系数(R)为0.9994,方法检出限为0.001 mg/kg,精密度RSD为1.4%~2.5%。超级微波消解－石墨炉原子吸收光谱法检测的探索与应用超级微波消解优于湿法消解和传统微波消解技术,大幅减少用酸量的同时更加安全、高效,避免样品污染,为农产品镉含量批量检测提供可靠的方法支撑。     

石墨炉原子吸收光谱法测定茶叶中的铅

采用石墨炉原子吸收光谱法测定茶叶中铅,以NH4H2PO4作为基体改进剂,提高了测定的灰化温度,消除了基体干扰.方法简便,快速,准确度高.通过对标准物质的多次测定,结果均在其保证值范围内,相对标准偏差为2.8%.对样品进行加标回收试验,回收率为96%～105%,方法检出限为0.12μg/L.     

新型成膜电解液添加剂亚硫酸丁烯酯的电化学行为

合成制备了一种新的环状亚硫酸酯类有机溶剂——亚硫酸丁烯酯(BS). 量子化学计算结果表明, 亚硫酸丁烯酯有机溶剂分子的总能、LUMO值比碳酸丙烯酯有机溶剂的低, 具有较强的得电子能力, 不易被氧化. 其作为添加剂与碳酸丙烯酯(PC)混合应用于锂离子电池中, 可有效地抑制PC在石墨电极中的共插入, 能显著改善循环性能.     

Research Progress of Lithium Plating on Graphite Anode in Lithium‐Ion Batteries

Lithium plating on graphite anode is triggered by harsh conditions of fast charge and low temperature, which significantly accelerates SOH (state of health) degradation and may cause safety issues of lithium ion batteries (LIBs). This paper has reviewed recent research progress of lithium plating on graphite anode. Firstly, we summarize the forming mechanisms of Li plating with corresponding influence factors, the detecting methods and hazard of Li plating. Then, approaches to suppress Li plating are discussed, including anode surface modification, electrolyte composition optimization and development of optimal charge strategies. Finally, we conclude and propose the remaining challenges and prospects in terms of mechanism research, detecting approaches, and suppressing methods of Li plating. This review highlights the development of Li plating research and plays a guiding rule of further study on Li plating in LIBs.     

Preparation and characterization of Pt-supported porous graphite nanofibers

In this work, porous graphite nanofibers (PGNFs) were manufactured as promising catalyst supporter by a physical activation method for direct methanol fuel cells, and Pt nanoparticles were loaded on the PGNFs in order to prepare electrode materials by a chemical reduction method. The pore structures of the Pt/PGNFs were analyzed by N₂ adsorption isotherms at 77 K. Electrocatalytic activities of final products were investigated by voltammetry and conductivity measurements in a 1.0 M CH₃OH/0.5 M H₂SO₄. As a result, electrocatalytic activities of Pt/PGNFs were increased in the presence of Pt particles on the PGNFs and with increasing the specific surface area of the carbons.     

石墨炉原子吸收法测定食品中镍的研究

建立了测定食品中镍的石墨炉原子吸收法，方法的最低检出限为１．６０μｇ／Ｌ，标准参考物牡蛎镍的测定值怀保证值偏差小于５％，回收率在８６．０％￣１０３．０％之间，并对我国八大类食品中镍含量本底值作了调查。