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1.
Optimization of the Heck reaction of 4-bromoacetophenone with styrene by a polymer supported, sulfur-containing palladacycle, varying 6 factors at a total of 28 different levels, corresponding to 5760 different possibilities was undertaken. Conversion improved from 34%, with large observable leaching to 88% with no leaching. This was accomplished using a Design of Experiments approach facilitated by the Statistical Design Package, MODDE 7.0TM. 相似文献
2.
A photoemission study of molybdenum hexacarbonyl adsorption and decomposition on TiO2(1 1 0) surface
The adsorption and decomposition of molybdenum hexacarbonyl on (1 1 0) TiO2 surfaces were studied using both core levels and valence band photoemission spectroscopies. It was found that after an adsorption at 140 K, when going back to room temperature, only a small part of molybdenum compounds, previously present at low temperature, remained on the TiO2 surface. This indicates that the desorption temperature on such a surface is lower than the decomposition one. The use of photon irradiation to decompose the hexacarbonyl molecule was also studied. It was shown that during such a decomposition molecular fragments were chemisorbed on the surface allowing a higher amount of metal to remain on the surface. It was also shown that it was possible to get rid of adsorbed subcarbonyl groups and to organize the metal atoms by thermal treatments at temperatures as low as 400 K, i.e. much lower than the one needed to obtain the same structures using physical vapour deposition (PVD). Moreover, due to lower used temperatures, this chemical way of deposition allows a better control of the interface than during PVD growth. 相似文献
3.
Sølvi Storsæter 《Surface science》2006,600(10):2051-2063
The heats of adsorption of different C1 and C2 molecules assumed to be present during the initial steps of the Fischer-Tropsch synthesis and activation energies for elementary steps envisioned to occur in the synthesis are calculated for Co by using the unity bond index-quadratic exponential potential (UBI-QEP) method. The preexponential factors for the elementary steps are calculated from transition-state theory, and the rate constants are calculated according to the Arrhenius equation. The activation barrier for hydrogenation of CO is found to be lower compared to hydrogen assisted dissociation of CO, which has a smaller activation barrier than direct dissociation of CO. The reaction steps with high activation barriers are eliminated. Based on this elimination two sets of elementary steps for formation of C1 and C2 alkenes and alkanes in the Fischer-Tropsch synthesis are established: one based on hydrogen assisted CO dissociation (carbide mechanism) and one based on CO hydrogenation (CO insertion mechanism). In addition, one mechanism of producing CO2 from the water-gas shift reaction is proposed. The resulting mechanisms are combined and used in the microkinetic model, which are fitted to experimental results at methanation conditions (T = 483 K or 493 K, p = 1.85 bar and H2/CO = 10) over a Co/Al2O3 Fischer-Tropsch catalyst. A good tuning is obtained by adjusting the C-Co and H-Co binding strengths. The microkinetic modelling based on these assumptions indicates that CO is mainly converted through hydrogenation of CO and that C2 compounds are mainly produced by insertion of CO into a metal-methyl bond. Thus, from the surface coverages and reaction rates predicted by the microkinetic modelling the mechanism can be further reduced to only include the CO insertion mechanism. Hydrogenation of CHO to CH2O is found to be the rate determining initiation step, and insertion of CO into a metal-methyl bond is found to be the rate determining step for chain growth. By using the UBI-QEP method for calculation of activation energies, the activation barriers for dissociation of CO and hydrogenation of surface carbon are found to be too large for the carbide mechanisms to occur. However, experimental data or another theoretical method is necessary in order to support or disprove the calculated activation energies in this work. 相似文献
4.
E. Maria Claesson Nilesh C. Mehendale Robertus J.M. Klein Gebbink Gerard van Koten Albert P. Philipse 《Journal of magnetism and magnetic materials》2007
Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further use. 相似文献
5.
CuO—ZnO/Al2O3—TiO2催化剂中TiO2的结构和电子效应 总被引:6,自引:0,他引:6
采用XPS,XRD,TPR,TPD和指标反应等方法研究了TiO_2在负载型CuO-ZnO/Al_2O_3-TiO_2催化剂中所起的作用.发现TiO_2起双重作用,即结构效应和电子效应,TiO_2的结构效应主要表现为它改善了CuO在载体上的分布.TiO_2的电子效应表现为它对Cu~0具有吸电子的作用,从而削弱了Cu和S之间的吸附力,使S容易脱除.另外,部分还原形成的Ti~(3+)具有促进CuS中的Cu~(2+)还原为Cu~0的能力,TiO_2的上述效应的综合结果使催化剂的抗硫中毒性能大大增强. 相似文献
6.
7.
负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶,李晔(内蒙古工业大学化学工程系,呼和浩特010062)殷元骐,金道森(中国科学院兰州化学物理研究所,兰州730000)关键词一氧化碳加氢,多相催化,双金属簇催化剂,钾效应。1.引言异核金属羰基簇作... 相似文献
8.
9.
Zhengping Hao Lidun An Junling Zhou Hongli Wang 《Reaction Kinetics and Catalysis Letters》1996,59(2):295-300
Supported gold catalyst for eliminating hydrogen from CO2 feed gas in the production of urea is found to be superior to other industrial catalysts (e.g. Pt/Al2O3 and PdPt/Al2O3) in catalytic activity and resistance to sulfur poisoning. 相似文献
10.
甲烷部分氧化制合成气 Ⅰ.甲烷在过渡金属上的活化 总被引:1,自引:0,他引:1
文中用同位素交换(D_2─CH_4)反应来测量四种过渡金属负载型催化剂对甲烷的活化能力,并与Svensson等从头算的计算结果作了比较,表明最有效活化甲烷分子的C─H键的金属是铑(Rh).文中还测定了在甲烷部分氧化制合成气反应中,四个不同催化剂的催化活性与选择性,并与它们对甲烷的活化能力进行对比,可以看出甲烷部分氧化反应中,反应活性高的催化剂有效地活化甲烷,断裂C─H键,而且氘代甲烷产物分布以形成CD_4产物为主要成份. 相似文献