全文获取类型
收费全文 | 364篇 |
免费 | 10篇 |
国内免费 | 58篇 |
专业分类
化学 | 360篇 |
物理学 | 72篇 |
出版年
2024年 | 2篇 |
2023年 | 3篇 |
2021年 | 5篇 |
2020年 | 11篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 15篇 |
2016年 | 11篇 |
2015年 | 13篇 |
2014年 | 13篇 |
2013年 | 26篇 |
2012年 | 29篇 |
2011年 | 26篇 |
2010年 | 15篇 |
2009年 | 23篇 |
2008年 | 22篇 |
2007年 | 30篇 |
2006年 | 32篇 |
2005年 | 24篇 |
2004年 | 29篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 8篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1985年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
排序方式: 共有432条查询结果,搜索用时 15 毫秒
421.
422.
423.
424.
425.
Andreas Peter Gilles Stebens Julian F. Baumgärtner Eberhard Jacob Franz K. Mantei Mohamed Ouda Prof. Ingo Krossing 《ChemCatChem》2020,12(9):2416-2420
An efficient, biphasic route towards oxymethylene dimethyl ethers (OMEs) allowing for catalyst recycling and reuse is presented (OMEs=CH3(−OCH2−)nO−CH3, n=3–5). OMEs are an interesting novel class of non-toxic, diesel-like synthetic fuels with soot-free combustion properties. A solution of commercial OMe3+BF4− in the ionic liquid (IL) 1-ethyl-3-methylimadazolium tetrafluoroborate acts as the immobilized catalyst. Upon addition of dimethoxymethane (OME1) and anhydrous formaldehyde (FA) very pure OMEs form in the upper phase of the biphasic mixture. In the lower IL-phase, the catalyst remains immobilized. After phase separation and removal of the top OME layer, the catalytically active IL-phase is reusable for at least ten times without loss of activity and selectivity. 相似文献
426.
Jia Bin Yeo Jun Ho Jang Young In Jo Jeong Woo Koo Ki Tae Nam 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(2):e202316020
Utilizing CO2-derived formaldehyde derivatives for fuel additive or polymer synthesis is a promising approach to reduce net carbon dioxide emissions. Existing methodologies involve converting CO2 to methanol by thermal hydrogenation, followed by electrochemical or thermochemical oxidation to produce formaldehyde. Adding to the conventional methanol oxidation pathway, we propose a new electrochemical approach to simultaneously generate formaldehyde derivatives at both electrodes by partial methanol oxidation and the direct reduction of CO2. To achieve this, a method to directly reduce CO2 to formaldehyde at the cathode is required. Still, it has been scarcely reported previously due to the acidity of the formic acid intermediate and the facile over-reduction of formaldehyde to methanol. By enabling the activation and subsequent stabilization of formic acid and formaldehyde respectively in methanol solvent, we were able to implement a strategy where formaldehyde derivatives were generated at the cathode alongside the anode. Further mechanism studies revealed that protons supplied from the anodic reaction contribute to the activation of formic acid and the stabilization of the formaldehyde product. Additionally, it was found that the cathodic formaldehyde derivative Faradaic efficiency can be further increased through prolonged electrolysis time up to 50 % along with a maximum anodic formaldehyde derivative Faradaic efficiency of 90 %. 相似文献
427.
A method for the simultaneous determination of 17 phenolic compounds in infant textile products, including phenol,o-phenylphenol,alkylphenols and bisphenols,was established using gas chromatography-mass spectrometry(GC-MS). The samples were extracted by 0.1 mol/L KOH solution,derived with acetic anhydride. The derivatives were extracted with ethyl acetate,separated by HP-5MS column,and determined by gas chromatography-mass spectrometry with ion mode scanning. Under the optimized conditions,the method had a good linear relationship in the range of 0.5-6.25 mg/L(R2>0.9990),the recoveries ranged from 80% to 110%, the relative standard deviations were 1.0%-8.6%,and the limit of quantification was 1.0 mg/kg. The method can achieve the simultaneous detection of 17 phenolic compounds in infant textile products. © 2023, Youke Publishing Co., Ltd. All rights reserved. 相似文献
428.
由于甲醛在大气光化学反应中的重要性及其对环境、气候和人类健康的危害,监测、有效控制甲醛浓度已经成为一件刻不容缓的要事。目前传统的监测多局限于基于化学方法、色谱法的室内监测,或是室外较小范围的监测,室外大范围的大气中的甲醛监测往往为人们所忽视。为了有效监测大气中大范围的甲醛(HCHO)浓度,建立了地基MAX-DOAS观测系统,与主动DOAS观测系统相比,该观测系统不受光源和反射装置限制,平台搭建简单,测量范围广。2018年在合肥地区(117°17′E, 31°90′N)夏季开展了基于地基MAX-DOAS的外场连续观测实验,结合新一代光谱处理软件QDOAS利用DOAS算法的非线性最小二乘拟合反演甲醛(HCHO)的斜柱浓度,并通过大气质量因子(AMF)将甲醛(HCHO)的斜柱浓度转换为柱浓度,并分析了7月份的观测数据,结果表明,低仰角下甲醛的差分斜柱浓的值较高,说明,对流层甲醛主要集中在接近地表的位置。从实验数据还可以看到,二氧化氮与甲醛的变化趋势基本一致,说明大气中的甲醛与机动车排放或是工业排放出的的氮氧化物(NO2等)在大气的源与汇过程中具有一定的相关性。通过地基MAX-DOAS测量数据与OMI观测值的比较发现,二者的变化趋势具有良好的一致性,且相关系数为0.518 9,并分析了OMI观测值偏低的原因。研究结果表明,地基MAX-DOAS系统不仅可以对区域污染的演变进行研究,也为甲醛的测量提供了一种实时、快速的监测手段,为分析大气甲醛的来源提供了一种新的解析手段,为验证卫星观测数据提供了一种有效的手段。 相似文献
429.
Oxygen vacancy (Ov) has significant influence on physical and chemical properties of TiO2 systems,especially on surface catalytic processes.In this work,we investigate the effects of O v on the adsorption of formaldehyde (HCHO) on TiO2(110) surfaces through firstprinciples calculations.With the existence of Ov,we find the spatial distribution of surface excess charge can change the relative stability of various adsorption configurations.In this case,the bidentate adsorption at five-coordinated Ti (Ti5c) can be less stable than the monodentate adsorption.And HCHO adsorbed in Ov becomes the most stable structure.These results are in good agreement with experimental observations,which reconcile the long-standing deviation between the theoretical prediction and experimental results.This work brings insights into how the excess charge affects the molecule adsorption on metal oxide surface. 相似文献
430.
As the photo-dissociation product of methanol on the TiO2(110) surface,the diffusion and desorption processes of formaldehyde (HCHO) were investigated by using scanning tunneling microscope (STM) and density functional theory (DFT).The molecular-level images revealed the HCHO molecules could diffuse and desorb on the surface at 80 K under UV laser irradiation.The diffusion was found to be mediated by hydrogen adatoms nearby,which were produced from photodissociation of methanol.Diffusion of HCHO was significantly decreased when there was only one H adatom near the HCHO molecule.Furthermore,single HCHO molecule adsorbed on the bare TiO2(110) surface was quite stable,little photo-desorption was observed during laser irradiation.The mechanism of hydroxyl groups assisted diffusion of formaldehyde was also investigated using theoretical calculations. 相似文献