全文获取类型
收费全文 | 304篇 |
免费 | 13篇 |
国内免费 | 9篇 |
专业分类
化学 | 312篇 |
物理学 | 14篇 |
出版年
2023年 | 5篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 8篇 |
2018年 | 2篇 |
2017年 | 8篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 12篇 |
2012年 | 26篇 |
2011年 | 19篇 |
2010年 | 20篇 |
2009年 | 14篇 |
2008年 | 19篇 |
2007年 | 31篇 |
2006年 | 18篇 |
2005年 | 24篇 |
2004年 | 23篇 |
2003年 | 14篇 |
2002年 | 9篇 |
2001年 | 2篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 6篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有326条查询结果,搜索用时 234 毫秒
1.
《Electroanalysis》2006,18(22):2218-2224
This article deals with the development of a method for the determination of osmium at a carbon paste electrode (CPE) modified with cationic surfactants of the quaternary ammonium salt type; namely, cetyltrimethylammonium bromide (CTAB) and 1‐(ethoxycarbonyl)‐pentadecyltrimethyl‐ammonium bromide (Septonex); both being added in situ and serving for preconcentration of osmium via its hexachloroosmate(IV) anion. The proper electrochemical detection was performed by cathodic scanning in the differential pulse voltammetric mode. Optimization studies concerning important experimental parameters also included a specially performed potentiometric titration, helping to define the actual stoichiometry for the ion‐pairing process, the main principle and driving force of the accumulation step. In a chloride/acetate buffer based supporting medium and with Septonex as the modifier of choice, the reduction signal for osmium was found to be proportional to the Os(IV) concentration in a range from 5×10?9 to 5×10?7 mol L?1 with a limit of detection close to 5×10?9 mol L?1 (with preconcentration for 60 s). The method capable to determine Os(IV) in the presence of both Pt(IV) and Ir(III) was tested on model solutions as well as with real sample of industrial waste water (spiked with the analyte); both yielding the recovery rates within 88–99%. 相似文献
2.
壁喷电池在流动注射阳极溶出伏安法中的应用 总被引:2,自引:0,他引:2
在流动注射阳极溶出伏安法中应用壁喷电池,探讨了非稳定态电积过程的溶出峰电流理论方程,预言了峰电流正比于R~(3/4)(R为工作电极半径),并对有关参数进行了实验验证。对5×10~(-7)mol/L Cd(Ⅱ)连续测定40次,表明相对标准偏差为0.94%。 相似文献
3.
There is a need to develop reliable portable analytical systems for on-site and real-time biomonitoring of lead (Pb) from both occupational and environmental exposures. Saliva is an appealing matrix since it is easily obtainable, and therefore a potential substitute for blood due to existing reasonably good correlation between Pb levels in blood and saliva. The microanalytical system is based on flow-injection/stripping voltammetry with a wall-jet (flow-onto) microelectrochemical cell. Samples that contain as little as 1% saliva can cause electrode fouling, resulting in significantly reduced responsiveness and irreproducible quantitations. In addition, incomplete Pb release from salivary protein can also yield a lower Pb response than expected. This paper evaluates the extent of in vitro Pb-protein binding and the optimal pretreatment for releasing Pb from the saliva samples. Even in 50% by volume of rat saliva, the electrode fouling was not observed, due to the appropriate sample pretreatment and the constant flow of the sample and acidic carrier that prevented passivation by the protein. The system offered a linear response over a low Pb range of 1-10 ppb, low detection limit of 1 ppb, excellent reproducibility, and reliability. It also yielded the same Pb concentrations in unknown samples as did the ICP-MS. These encouraging results suggest that the microanalytical system represents an important analytical advancement for real-time non-invasive biomonitoring of Pb. 相似文献
4.
本文测定了20°~-60℃Te(Ⅳ)/Te(0)在金电极和HClO_4水溶液中的循环伏安图,证明了在常温下受吸附和扩散控制的还原过程在凝固介质中发生了变化,温度低于介质的凝固点时吸附作用受到抑止,扩散控制成为唯一的还原过程。根据不可逆循环伏安响应和Tafel作图,测定了还原阶的电荷传输系数α和速率常数k_s。碲的低温阳极溶出伏安法不仅能在液态溶液也能在凝固的电解质中进行。 相似文献
5.
《Electroanalysis》2006,18(21):2115-2120
A new type of voltammetric sensor, Langmuir–Blodgett film of p‐tert‐butylthiacalix[4]arene modified glassy carbon electrode, was advanced and used for determining copper at trace levels by differential pulse stripping voltammetry. Calibration plot was found to be linear in the range of 2×10?8 M to 5×10?6 M; the detection limit was 2×10?9 M. Possible recognition mechanism was also discussed. From determination of Copper in real samples (river, lake and tap water) it can be concluded that the method is rapid, sensitive in determining of copper and can be used in the analysis of natural water samples. 相似文献
6.
碳纤维微电极已被广泛应用于电化学研究和分析测定,该电极尺寸极小,在分析性能上与常规电极有显著不同,在不镀汞的情况下,用碳纤维电极直接测定金属离子几乎没有明显的伏安响应,本文提出用+2.5 V恒电位预先活化碳纤维电极,使测定灵敏度大为提高,在双电极体系和静止溶液中,采用溶出伏安法可测定10~(-9)级金属离子,以同样的方法清洗电极,测定结果重现性良好,由于分析过程中不使用汞,该电极的测定范围大大增加,特别是用于氧化还原电位较正的金属离子测试,根据循环伏安法、扫描电镜和电子能谱的研究,发现碳纤维表面状况在处理前后有很大变化,并与测定灵敏度密切相关。 相似文献
7.
The experimental parameters of cathodic stripping chronopotentiometry of chloride at a silver-film electrode are investigated and optimized. The chloride preconcentration is achieved in the form of silver chloride by a controlled potential oxidation of the working electrode under vigorous stirring. Cathodic stripping of the deposit is obtained by the constant current, under the condition of diffusive mass transfer. Deaeration of the solution is not necessary. A detection limit of 35 μ dm−3 (10−6 mol dm−3) is obtained at a deposition time of 180 s, with a reproducibility of 6.7 % (expressed as relative standard deviation, RSD). 相似文献
8.
本文对在玻璃碳电极上不可逆溶出催化的理论进行了研究,推导了溶出催化过程的电流方程,峰电流和峰电势方程,并用微计算机模拟出各种关系曲线,从理论方程得知溶出催化伏安法所得的峰电流比溶出伏安法的峰电流提高了二个数量级。本文还用钯的溶出催化实验验证理论方程,所得的实验结果均与理论方程相吻合。 相似文献
9.
Christos Kokkinos Anastasios Economou Ioannis Raptis Constantinos E. Efstathiou Thanasis Speliotis 《Electrochemistry communications》2007,9(12):2795-2800
This work describes a novel type of bismuth electrode for stripping voltammetry based on coating a silicon substrate with a thin bismuth film by means of sputtering. The bismuth-based sensors were characterized by optical methods (scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD)) and as well as by linear sweep voltammetry. Subsequently, the electrodes were tested for the detection of low concentrations of trace metals (Cd(II), Pb(II) and Ni(II)) by stripping voltammetry. Well-formed stripping peaks were observed for trace concentrations of the target analytes demonstrating “proof-of-principle” for these sensors. This type of electrochemical device, utilizing thin-film technology for the formation of the bismuth film, holds promise for future applications in trace metal analysis. 相似文献
10.
聚酰胺修饰碳糊电极测定槲皮素的研究 总被引:10,自引:0,他引:10
用聚酰胺修饰碳糊电极在pH360的Briton-Robinson缓冲溶液中,将槲皮素开路富集一定时间后,从045V(vs.Ag/AgCl)向阴极化扫描至-055V获得I-E曲线。槲皮素的峰电位为018V。峰电流与槲皮素浓度在10~400μmol/L范围内呈良好的线性关系。所拟定方法用于芦丁水解产物测定,结果满意。 相似文献