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1.
天然气水合物是蕴含着巨大能源潜力的非常规能源,2017年和2020年两次我国南海探索性试采的成功,加快了天然气水合物项目的进展。二氧化碳置换开采法,既能开发CH4,又能封存CO2。同时水合物法分离烟气中CO2具有很好的应用前景,而CO2在气体水合物的微观结构和特性尚不明确,实际应用存在一定的未知影响。为了考察其特性,利用13C固体核磁技术(NMR)和拉曼光谱(Raman)进行CO2置换CH4水合物、合成13CO2-H2-CP混合水合物实验表征,讨论CO2在水合物中的定量问题,研究CO2分子在笼型结构中的分布,探讨CO2分子在气体水合物中的结构类型和特性。结果表明:(1)利用Raman费米低频共振1 277.5 cm-1峰积分得到CO2在I型大笼(51262笼)的占有率为0.978 2,CH4在Ⅰ型小笼(512笼)和大笼(51262笼)的占有率为0.059 3和0.009 5,水合数7.61,Raman费米高频共振1 381.3 m-1峰积分得到CO2在51262笼的占有率为0.984 3,CH4在512笼和51262笼的占有率为0.023 7和0.003 3,水合数7.70,CO2几乎占满了大笼,CO2气体的加入会导致水合物中,CH4的大、小笼占有率均大幅度降低,置换后水合数略低于纯甲烷水合物,未标记的CO2水合物在核磁中较难测出信号,CO2气体置换后CH4在小笼的占有率仅0.097 5,大笼占有率为0.317 2,两种方法差异主要原因为核磁的CO2未出峰。(2)利用拉曼费米低频共振1 273.4 cm-1峰积分得到H2、CO2在512笼、CP在51262的占有率分别为0.124 8,0.304 2和0.997 8,水合数9.16;Raman费米高频共振1 380.6 cm-1峰积分得到H2、CO2在512笼、CP在51262的占有率分别为0.123 6,0.577 1和0.985 1,水合数7.12。13C标记CO2分子在水合物中达到较好的固体核磁分辨率,首次确认CO2在Ⅱ型小笼中的化学位移为124.8 ppm,计算得到CO2的小笼占有率为0.783 1,CP的大笼占有率为0.971 8,水合数6.70,Raman高频频费米共振峰(1 380.6 cm-1)定量计算与13C NMR结果更接近。(3)对CO2的13C NMR化学位移进行了归属,并结合Raman与13C NMR的对比分析,为CO2水合物的13C NMR研究和拉曼定量提供参考。  相似文献   
2.
为研究并解决测试生物质样品中碱金属和碱土金属含量的干扰,采用微波消解-电感耦合等离子体发射光谱(ICP-OES)法对生物质中的碱金属和碱土金属钾、钙、钠、镁元素进行测定,考察了样品消解后不同的酸体系,共存元素干扰对钾、钠、钙、镁含量测定的干扰研究。经过研究表明,接近分析标准曲线酸浓度的样品干扰小,铅、铟、钛、锰元素对钠元素测定造成干扰,砷、铜、镉对钙元素测定干扰,铝对钾元素测定有干扰,镁测定不受共存元素干扰影响,运用干扰系数法可以减少共存元素对测定元素的误差。各待测元素标准曲线相关系数大于0.9996,检出限为0.0014~0.023 mg/L,玉米芯各元素的相对标准偏差为0.98%~1.9%,加标回收率为80.2%~106%;西瓜皮的各元素相对标准偏差为0.91%~2.3%,加标回收率为85.3%~106%。方法用于测定国家标准物质GBW07603,各元素结果均在标准值参考范围内。方法用于测定生物质中碱金属和碱土金属的结果,用t检验法与离子色谱测定值进行比对,结果无显著性差异。  相似文献   
3.
Highly dispersed Co catalysts supported on SiO2 were prepared in the presence of ethylene glycol(EG)by co-impregnation and tested in the vapor-phase hydrogenolysis of ethyl lactate to 1,2-propanediol.Thesynthesis parameters of Co metal loading,ratio of EG to cobalt nitrate,type of alcohol and calcinationtemperature,which influenced the physical properties of the Co3O4 nanoparticles,were investigated throughthe use of X-ray diffraction(XRD).It revealed that the ratio of EG to cobalt nitrate and the type of alcoholsignificantly affected the particle size of Co3O4 supported on SiO2.During co-impregnation with EG,the interactionbetween Co2+ and the SiO2 support was strongly enhanced,resulting in the high dispersion of cobalt speciesand the decrease of Co3O4 particle size from 16 nm to below 5 nm;the significantly enhanced cobalt dispersionwas associated with the formation of amorphous cobalt silicate.Meanwhile the conversion of ethyl lactate wasgreatly improved to 98.6% from 69.5%,with 98.0% selectivity of 1,2-propanediol over 10%(w,mass fraction)Co/SiO2 catalysts under the given reaction conditions(2.5 MPa and 160 ℃).The obtained catalysts were characterized by X- ray diffraction(XRD),transmission electron microscopy(TEM),X- ray photoelectronspectroscopy(XPS),N2 adsorption-desorption measurements,and H2 temperature-programmed reduction(H2-TPR)methods.  相似文献   
4.
制备了1-甲基-3-丙基咪唑硫离子液体电解质,并应用在量子点敏化太阳能电池中。通过优化S和Na2S的浓度,电解质的电导率在25°C下达到了12.96 m S?cm~(-1)。差示扫描量热法分析表明离子液体电解质的玻璃化转变温度为-85°C。采用该电解质的量子点敏化太阳能电池在25°C下达到了3.03%的光电转化效率(η),与采用水基电解质的电池的效率3.34%接近。由于本文中的离子液体电解质具有低玻璃化转变温度和不易挥发的优点,采用离子液体电解质的量子点敏化太阳能电池在-20°C(η=2.32%)及80°C(η=1.90%)的温度下表现出了比水基电解质优异的光电转化性能。  相似文献   
5.
We report on the first use of clathrate hydrates as electrolyte additive in the electrochemical reduction of carbon dioxide. Clathrate hydrates allow the enrichment of significantly larger volumes of gas than liquids can usually dissolve. Electrolyte solutions containing 10%mass THF with and without CO2 containing clathrate hydrates were investigated with a copper-foam working electrode. Our results show that at − 1.0 V vs Ag/AgCl the Faradaic efficiency for the production of CO and further reduced carbonaceous products was 80% with clathrates vs 20% with non-clathrate electrolytes of identical chemical composition at nearly equal temperature.  相似文献   
6.
This study investigated the effect of annealing temperature on the precipitation behavior of Crofer® 22 H at 600 °C, 700 °C, and 800 °C. The grain size distribution, precipitate phase identification, and microstructure were analyzed using electron backscatter diffraction (EBSD) and energy dispersive X-ray spectroscopy (EDS). The morphology of Laves phase (Fe,Cr,Si)2(Nb,W) precipitates having the Cr2Nb structure changed from strip-like to needle-shaped as the annealing temperature was increased. The precipitates of the Laves phase also shifted from the grain boundaries to the grain interiors when the temperature was increased. However, the average grain size (150 μm) of the ferritic matrix did not significantly change at 600 °C, 700 °C, and 800 °C for 10 h.  相似文献   
7.
In this work, the performance of nine ionic liquids (ILs) as thermodynamic hydrate inhibitors is investigated. The dissociation temperature is determined for methane gas hydrates using a high pressure micro deferential scanning calorimeter between (3.6 and 11.2) MPa. All the aqueous IL solutions are studied at a mass fraction of 0.10. The performance of the two best ILs is further investigated at various concentrations. Electrical conductivity and pH of these aqueous IL solutions (0.10 mass fraction) are also measured. The enthalpy of gas hydrate dissociation is calculated by the Clausius–Clapeyron equation. It is found that the ILs shift the methane hydrate (liquid + vapour) equilibrium curve (HLVE) to lower temperature and higher pressure. Our results indicate 1-(2-hydroxyethyl) 3-methylimidazolium chloride is the best among the ILs studied as a thermodynamic hydrate inhibitor. A statistical analysis reveals there is a moderate correlation between electrical conductivity and the efficiency of the IL as a gas hydrate inhibitor. The average enthalpies of methane hydrate dissociation in the presence of these ILs are found to be in the range of (57.0 to 59.1) kJ  mol−1. There is no significant difference between the dissociation enthalpy of methane hydrate either in the presence or in absence of ILs.  相似文献   
8.
基于气体产物在线分析, 搭建了光催化反应体系, 实现了多反应通道的批次实时在线色谱分析, 建立了光催化剂活性评价系统.通过与实验装置连接, 实现在线色谱分析, 可以实时定性定量检测催化反应产物, 提高分析效率, 为科研工作提供高效、便捷、系统的服务.同时, 在此基础上建立的光催化剂活性评价系统, 可为太阳能光化学转换利用及环保技术的研究奠定试验基础.光催化剂活性评价系统拓展了仪器的使用功能, 应用范围得到提升, 可为化工合成催化剂评价系统的研发提供借鉴.  相似文献   
9.
利用自主研发的水合物沉积物原位合成与力学性质测试的高压低温三轴仪,通过多级加荷的试验方法,以不同粒径的砂粒作为沉积物骨架进行三轴压缩试验,得到了剪切过程的应力-应变关系曲线,以及不同粒径尺寸沉积物的强度,还有剪切过程中的体积变化关系。结果表明:含水合物沉积物强度随着沉积物粒径尺寸的增大而增强;在降压剪切过程中,所有粒径的水合物沉积物式样均有明显的剪缩现象。  相似文献   
10.
《中国化学快报》2020,31(8):2099-2102
In this work, the two-dimensional MoS2 film was prepared by sulfuring the molybdenum atomic layer on SiO2/Si substrate. The reaction temperature, heating rate, holding time and carrier gas flow rate were investigated comprehensively. The quality of MoS2 film was characterized by optical microscopy, atomic force microscopy, Raman and photoluminescence spectroscopy. The characterization results showed that the optimum synthesis parameters were heating rate of 25 °C/min, reaction temperature of 750 °C, holding time of 30 min and carrier gas velocity of 100 sccm. The MoS2 gas sensor was fabricated and its gas sensing performance was tested. The test results indicated that the sensor had a good response to both reducing gas (NH3) and oxidizing gas (NO2) at room temperature. The sensitivity to 100 ppm of NO2 was 31.3%, and the response/recovery times were 4 s and 5 s, respectively. In addition, the limit of detection could be as low as 1 ppm. This work helps us to develop low power and integrable room temperature NO2 sensors.  相似文献   
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