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排序方式: 共有147条查询结果,搜索用时 29 毫秒
1.
电化学与核磁共振波谱联用技术(EC-NMR)可以实时监测电化学反应过程,从分子水平阐释反应机理,是一种非常有前景的无损在线检测技术。本文首次报道以硅基硼掺金刚石(Si/BDD)作为工作电极的原位EC-NMR三电极单室电解池的设计和制作。研究表明,由于尺寸12.5 mm × 1.2 mm × 0.5 mm的Si/BDD电极在核磁检测区的体积较小且电极材料厚度较薄,因此该电极对射频场的阻碍较小,对磁场均匀性破坏也相应较小。运用自制的EC-NMR电解池并以经典的对苯二酚(QH 2)电氧化生成对苯二醌(Q)作为模型体系,原位研究了该电化学反应的整个动态过程。在1.2 V恒电位下电解0.1 mol·L-1 QH2 64分钟,监测到位于6.83 ppm处的Q特征峰逐渐生成,反应过程中核磁谱峰未发生裂分或明显的展宽。结果表明,应用本文所设计并制备的原位EC-NMR电解池,可有效对电化学反应物和产物进行定性、定量分析,将可在后续的电化学原位核磁波谱研究中发挥重要作用。 相似文献
2.
采用浸渍法制备了负载型高分散纳米Ru催化剂,利用X射线衍射、X射线光电子能谱、透射电子显微镜、N2吸附-脱附实验对催化剂进行了表征,结果显示,Ru以高分散金属态存在,其平均粒径在5nm左右。考察了不同酸碱介质、催化剂与底物物质的量的比、反应温度、H2压力和反应时间对对苯二酚收率的影响。结果表明,以盐酸为反应介质,以5%Ru/AC为催化剂,nRu/AC∶n对苯醌=1∶100,反应温度30℃,H2压力3.0MPa,反应时间30min,对苯二酚的收率可达97.5%。 相似文献
3.
Mingfang Li Rong Geng Meichuan Liu Dongming Li 《International journal of environmental analytical chemistry》2013,93(8):571-582
Bovine serum albumin (BSA) was covalently attached to glassy carbon electrode (GCE) surface by the electrochemical method. An enhancement for the redox of hydroquinone (HQ) on BSA/GCE was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy measurement. The electron transfer rate constant (k s) on the BSA/GCE electrode is almost three orders of magnitude higher than that on bare GCE. The enhancing effect can be attributed to the electrostatic force between the positively charged HQ and negatively charged BSA. It is found that the enhanced redox process of HQ can be used to determine HQ sensitively. The oxidation current can reach 95% of its steady-state value within 30 s. The linear range for HQ determination is from 2.5 × 10?8 M to 1.325 × 10?6 M with a detection limit of 8.6 × 10?9 M at a signal-to-noise ratio of 3. The study may provide a simple, rapid and sensitive method for determination of HQ which is present in the natural environment and in chemical industry effluent. 相似文献
4.
A novel Pt/C‐catalyzed transfer hydrogenation reaction of p‐benzoquinone to produce p‐hydroquinone using cyclohexanone as an unexpectedly effective hydrogen source 下载免费PDF全文
A new method for the production of p‐hydroquinone via a Pt/C‐catalyzed reduction of p‐benzoquinone is developed. Different from the conventional transfer hydrogenation reactions that usually use secondary alcohols such as isopropanol as the hydrogen source, in this work, it is unexpectedly found that cyclohexanone is a more effective hydrogen source than secondary alcohols, even cyclohexanol. This reaction affords acceptable yields of p‐hydroquinone with very high turnover number (1109) of the Pt/C catalyst. A mechanism of this interesting reaction is proposed on the basis of the results of a series of control experiments, GC–MS analysis as well as dynamic studies. 相似文献
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Shengbiao Zheng Jiaqi Hu Xue Cui Tao Hu Yuyang Zhang Jiahao Guo Jing Tang Xuchun Wang 《Electroanalysis》2020,32(9):2010-2017
In the present study, we report a facile method for preparing a porous MWCNTs/ZIF‐67 nanocomposite with the help of a morphology‐maintained ZIF‐67 in situ growth on multi‐walled carbon nanotubes. Interesting, the MWCNTs/ZIF‐67 nanocomposite demonstrated excellent electrochemical activity for hydroquinone (HQ) and catechol (CC) attribute to the effective interconnections ZIF‐67 crystals and MWCNTs. The analytical curves for HQ and CC obtained by differential pulse voltammetry (DPV) were linear in the range from 0.5 to 100 μM. Benefitting from the excellent conductivity of MWCNTs as well as the high surface area and porosity of ZIF‐67, the advanced nanocomposite displayed good reproducibility, high selectivity and excellent stability, and was successfully employed to assay the content of dihydroxybenzene isomers in the lake water samples. 相似文献
8.
It is well known that pillar[5]arenes have two most stable conformations (pS and pR) in their crystal structures. Because of the intramolecular H‐bonding interactions, substituents, temperature, solvent and so on, the rotational behaviors of the phenolic units on pillararenes are also common. This paper showed some other kinds of conformations in the functionalized pillar[5]arenes and gave evidence for a bulky unit (1,4‐methoxycarbonylmethoxybenzene unit) flipping in the solid state. The presence of hydrogen bonding facilitated the intermolecular self‐assembly in terms of energy‐minimized packing in the crystals. Thus, the main driving force for the flipping of this bulky unit might be both the intramolecular hydrogen bonding between the phenolic units on pillararenes and quadrupolar hydrogen bonding between the host and water. This paper helps us to have a better understanding on the conformations of pillar[5]arenes. 相似文献
9.
制备了高岭土修饰碳糊电极(KCPE),并以氢醌(HQ)为电催化介质测定还原型谷胱甘肽(GSH)。实验结果表明,在该电极上谷胱甘肽(GSH)的加入对氢醌的电化学响应有明显提高,且电催化氧化峰电流与GSH浓度呈良好的线性关系,由此可采用差分脉冲伏安法(DPV)对GSH进行定量测定。对修饰电极的电化学性能进行了表征,测得电极有效表面积为0.118 6 cm2、电荷传递系数为0.68、表观速率常数为1.08×104cm3·mol-1·s-1。在优化条件下,测得GSH在KCPE上的线性范围为0.1~1,2.5~25μmol/L,检出限为0.073μmol/L。用该方法对含GSH的市售药进行测定,结果满意。 相似文献
10.
采用曲拉通X-100(Triton X-100)/正己醇/正庚烷/RuCl_3·3H_2O水溶液构成微乳液,以水合肼为还原剂,制备了纳米Ru颗粒,再破乳将其负载于NaY分子筛得到M-Ru/NaY催化剂.通过XRD、BET、XPS、SEM、TEM及DSC分析方法对催化剂进行了表征.表征结果表明,M-Ru/NaY催化剂具有金属钌平均粒径小,分布均匀,高度分散等优点.以对苯二酚加氢制1,4-环己二醇为探针反应,对微乳法和传统浸渍法制备的催化剂活性和选择性进行了比较,深入研究了催化剂用量,反应温度,氢气压力对对苯二酚加氢活性的影响及最佳反应时间的确定.实验结果表明,M-Ru/NaY催化剂在反应温度150℃,氢气压力4.0 MPa,m(M-Ru/NaY)∶m(对苯二酚)=0.2∶1,溶剂为异丙醇,此条件下反应30 min,对苯二酚转化率为100%,1,4-环己二醇的选择性高达92.6%.还考察了M-Ru/NaY催化剂的稳定性.最后,探讨了对苯二酚加氢反应路径. 相似文献