全文获取类型
收费全文 | 280篇 |
免费 | 19篇 |
国内免费 | 26篇 |
专业分类
化学 | 298篇 |
晶体学 | 1篇 |
力学 | 1篇 |
综合类 | 2篇 |
物理学 | 23篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 15篇 |
2020年 | 20篇 |
2019年 | 9篇 |
2018年 | 13篇 |
2017年 | 4篇 |
2016年 | 4篇 |
2015年 | 8篇 |
2014年 | 9篇 |
2013年 | 8篇 |
2012年 | 27篇 |
2011年 | 12篇 |
2010年 | 17篇 |
2009年 | 23篇 |
2008年 | 24篇 |
2007年 | 27篇 |
2006年 | 10篇 |
2005年 | 15篇 |
2004年 | 20篇 |
2003年 | 8篇 |
2002年 | 5篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有325条查询结果,搜索用时 15 毫秒
1.
Lotfi Boudjema Dr. Jérôme Long Dr. Fabrice Salles Prof. Joulia Larionova Dr. Yannick Guari Prof. Philippe Trens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):479-484
Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption. 相似文献
2.
Jeffrey T. Culp Franz Frye Mark W. Meisel Daniel R. Talham 《Coordination chemistry reviews》2005,249(23):2642-2648
Studies of metal cyanide thin films prepared directly at interfaces are reviewed. The systems range from monolayers, single-layer analogs of Prussian blue-like networks, to bulk powders prepared as thin films. Monolayer networks are prepared at the air/water interface and transferred to solid supports using Langmuir-Blodgett film methods. Films of bulk materials are prepared directly on solid surfaces using a templated sequential deposition procedure. The magnetic properties of the films have been explored, and in some cases, these monolayers and surface films give rise to new behavior that is only possible because of the fabrication method or thin film architecture. The methods of synthesis can generate oriented samples, even when the materials are poorly crystalline. Furthermore, the interface-assembled networks are inherently anisotropic, leading to phenomena not present in the solid-state analogs, such as anisotropic photomagnetism in a thin film of RbjCok[Fe(CN)6]l·nH2O. 相似文献
3.
气相色谱法研究配位化合物的热稳定性——ⅩⅢ.普鲁士蓝化合物的热分解及其加氢反应研究 总被引:2,自引:0,他引:2
普鲁士蓝化合物的热分解过程,可分为三个阶段:(1)脱水;(2)Fe3+还原至Fe2+;(3)C≡N-键的断裂。H2气中的热分解由于发生了一系列的加氢反应,分解产物及所对应的分解温度都不同于He气中的情况,其产物的种类增加,C≡N-键的断裂温度降低。普鲁士蓝化合物中,CN-呈典型的双端基配位,可看作是一种双金属配位的活化模型,与CN-呈单端基配位的K3[Fe(CN)6]相比,C≡N-键的活化程度增加,不仅断裂温度降低,且能发生更深度的加氢反应。 相似文献
4.
Potentiodynamic deposition of Prussian blue from a solution containing single component of ferricyanide and its mechanism investigation 总被引:1,自引:0,他引:1
Dai?Zhang Kang?Wang Dacheng?Sun Xinghua?XiaEmail author Hongyuan?Chen 《Journal of Solid State Electrochemistry》2003,7(9):561-566
Potentiodynamic techniques were used for the direct electrodeposition of Prussian blue nano-clusters from an acidic solution of ferricyanide. Electrochemical, EQCM, IR, AFM, and UV/vis measurements were carried out to characterize deposited nano-sized Prussian blue and to explore the formation mechanism. Results showed that ferricyanide could partially dissociate to free ferric and cyanide ions. The driving force of this dissociation is the formation of PB and the evolution of HCN. The optimal potential window for the potentiodynamic formation of PB from an acidic solution (pH 1.6) is between –0.5 V and 0.4 V. In addition, the influence of surface adsorption of CN- ions on the formation of PB was discussed.Dedicated to Professor W. Vielstich on the occasion of his 80th birthday. 相似文献
5.
徐肖邢 《理化检验(化学分册)》2004,40(12):697-699
制备了普鲁士蓝修饰的丝网印刷过氧化氢传感器,研究了过氧化氢在该修饰电极上的电催化还原特性,考察了有关修饰膜制备和试验条件对传感器性能的影响。结果表明,pH4.0的0.2mol·L-1KH2PO4 K2HPO4缓冲溶液(PBS)中,修饰电极对过氧化氢显示出快速的电化学响应,较高的稳定性、重现性和催化活性,测定的线性范围为1.0×10-5~1.0×10-3mol·L-1,相关系数为0.999,检出限为6.0×10-6mol·L-1(3σ)。电极制作方法简便,可用于实际样品的测定。 相似文献
6.
A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived
Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction
of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian
blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme
is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated. 相似文献
7.
《Electroanalysis》2005,17(3):210-222
Presented in this work is the first step towards an enzymeless/mediatorless glucose sensor. We first observed remarkable electrocatalytic oxidation of glucose using combinative ruthenium oxide (RuOx)‐Prussian blue (PB) analogues (designated as mvRuOx‐RuCN, mv: mixed valent) at ca. 1.1 V (vs. Ag/AgCl) in acidic media (pH 2 Na2SO4/H2SO4). Individual RuOx and PB analogs failed to give any such catalytic response. A high ruthenium oxidation state (i.e., oxy/hydroxy‐RuVII, E°≈1.4 V vs. RHE), normally occurring in strong alkaline conditions at RuOx‐based electrodes, was electrogenerated and stabilized (without any conventional disproportionation reaction) in the mvRuOx‐RuCN matrix for glucose catalysis. Detail X‐ray photoelectron spectroscopic studies can fully support the observation. The catalyst was chemically modified onto a disposable screen‐printed carbon electrode and employed for the amperometric detection of glucose via flow injection analysis (FIA). This system has a linear detection range of 0.3–20 mM with a detection limit and sensitivity of 40 μM (S/N=3) and 6.2 μA/(mM cm2), respectively, for glucose. Further steps towards the elimination of interference and the extendibility to neutral pHs were addressed. 相似文献
8.
将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系DA为4.0×10-6~8.0×10-4mol·L-1,VC为6.0×10-5~1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%~101.0%及95.0%~102.5%. 相似文献
9.
An amperometric cholesterol biosensor based on immobilization of cholesterol oxidase in a Prussian blue (PB)/polypyrrole (PPy) composite film on the surface of a glassy carbon electrode was fabricated. Hydrogen peroxide produced by the enzymatic reaction was catalytically reduced on the PB film electrode at 0 V with a sensitivity of 39 μA (mol/L)?1. Cholesterol in the concentration range of 10?5 ? 10?4 mol/L was determined with a detection limit of 6 × 10?7 mol/L by amperometric method. Normal coexisting compounds in the bio‐samples such as ascorbic acid and uric acid do not interfere with the determination. The excellent properties of the sensor in sensitivity and selectivity are attributed to the PB/PPy layer modified on the sensor. 相似文献
10.
Mariusz?T.?Galkowski Pawel?J.?KuleszaEmail author Krzysztof?Miecznikowski Malgorzata?Chojak Henryk?Bala 《Journal of Solid State Electrochemistry》2004,8(6):430-434
We propose a novel composite organic-inorganic coating in the form of a redox polymer film for protection of stainless steel against general corrosion in strong acid medium (2 M H2SO4). We utilize an anion exchange polymer, protonated poly(4-vinylpyridine), into which hexacyanoferrate anions have been introduced. Owing to the presence of Fe(CN)63–/4– at the interface formed by the film and the steel, a sparingly soluble metal hexacyanoferrate (mostly Prussian blue, PB) is formed as an overcoating on the steels surface, presumably on the passive (metal oxide) layer. The redox polymer film on the steel seems to act as a composite three-dimensional bilayer-type coating in which hexacyanoferrate(III,II) anions (that are capable of effective charge storage) exist in the outer portions of the film, whereas the inner PB layer improves the systems overall adherence and stability. By analogy to a conducting polymer (e.g. polyaniline, polypyrrole), introduction of the redox polymer composite film leads to stabilization of the steel substrates potential within the passive range.Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003) 相似文献