全文获取类型
收费全文 | 150147篇 |
免费 | 19284篇 |
国内免费 | 11958篇 |
专业分类
化学 | 71623篇 |
晶体学 | 1222篇 |
力学 | 6966篇 |
综合类 | 553篇 |
数学 | 11976篇 |
物理学 | 41899篇 |
综合类 | 47150篇 |
出版年
2024年 | 666篇 |
2023年 | 2789篇 |
2022年 | 4427篇 |
2021年 | 4995篇 |
2020年 | 4789篇 |
2019年 | 4354篇 |
2018年 | 3908篇 |
2017年 | 3799篇 |
2016年 | 5664篇 |
2015年 | 5867篇 |
2014年 | 7525篇 |
2013年 | 9116篇 |
2012年 | 10819篇 |
2011年 | 11192篇 |
2010年 | 7798篇 |
2009年 | 7803篇 |
2008年 | 8405篇 |
2007年 | 7854篇 |
2006年 | 6983篇 |
2005年 | 6156篇 |
2004年 | 4634篇 |
2003年 | 3654篇 |
2002年 | 3399篇 |
2001年 | 3126篇 |
2000年 | 3011篇 |
1999年 | 4509篇 |
1998年 | 4181篇 |
1997年 | 4130篇 |
1996年 | 4111篇 |
1995年 | 3457篇 |
1994年 | 3286篇 |
1993年 | 2736篇 |
1992年 | 2392篇 |
1991年 | 2146篇 |
1990年 | 1804篇 |
1989年 | 1494篇 |
1988年 | 1227篇 |
1987年 | 878篇 |
1986年 | 658篇 |
1985年 | 423篇 |
1984年 | 272篇 |
1983年 | 162篇 |
1982年 | 147篇 |
1981年 | 108篇 |
1980年 | 76篇 |
1979年 | 48篇 |
1978年 | 34篇 |
1976年 | 38篇 |
1975年 | 33篇 |
1974年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Using renewable green hydrogen and carbon dioxide (CO2) to produce methanol is one of the fundamental ways to reduce CO2 emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO2 catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO2 (Nor-CZS), co-precipitation Cu/ZnO-SiO2 (Co-CZS), and reverse precipitation Cu/ZnO-SiO2 (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO2 to methanol. The results of temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO2 interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N2O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO2 conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO2 conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO2 conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts. 相似文献
992.
Electron impact mass spectra of eight of the title compounds are reported. Abundant fragment ions were produced under electron impact (EI) conditions and, with one exception, the ($?hbox?ArC??equiv$ O) ions were the base peaks. The EI fragmentation mechanisms of two representative compounds were studied with the aid of high-resolution and mass-analyzed ion kinetic energy spectrometry (MIKES) data. The M(+) ions fragment to give both an odd-electron ion and an even-electron fragment ion. Two H-atom rearrangements proceeding via four-membered ring intermediates and three losses of CO through i- and alpha-fragmentations were observed under EI. On comparing fragmentations under EI conditions with those under FAB conditions for two of the compounds, the fragmentation mechanisms were reasonably similar, with additional fragmentations rationalized in terms of the ionization proton being located on the oxygen atom of the beta-ethoxy group. 相似文献
993.
Dr. Dingfeng Yang Junzhu Yang Xuejun Quan Bin Zhang Guoyu Wang Xu Lu Xiaoyuan Zhou 《Chemphyschem》2021,22(24):2579-2584
Understanding the correlation between crystal structure and thermal conductivity in semiconductors is very important for designing heat-transport-related devices, such as high-performance thermoelectric materials and heat dissipation in micro-nano-scale devices. In this work, the lattice thermal conductivity ( ) of the cage-like compounds Cu3VSe4 and Cu3NbSe4 was investigated by experimental measurements and first-principles calculations. The experimental of Cu3NbSe4 is approximately 25 % lower than that of Cu3VSe4 at 300 K. The relevant important physical parameters, including the sound velocity, heat capacity, weighted phonon phase space (W), and third-order force constants along with atomic mass were theoretically analyzed. It is found that W is the dominant parameter in determining the , and the other factors only play a minor role. The physical origin is the relatively “soft” lattice of Cu3NbSe4 with heavier atomic mass. This research provides deep insight into the correlation between the thermal conductivity and crystal structure and paves the way for discovering high-performance thermal management device and thermoelectric materials with intrinsically low . 相似文献
994.
A simple approach for deriving expressions for the limiting steady-state response of the open tubular electrode, under conditions of intermediate electrolytic yields, is described. This approach couples the principles of laminar fluid dynamics with the theory of the porous electrode reactor. The dependence of the limiting current, I1, on flow rate, Vf, has the form of I1 α Vmf , with m ? , depending upon the electrolytic yield. The effects of electroactive species depletion upon the detector response are discussed. Experimental results are incorporated to support the theoretical conclusions. For a tubular electrode (4-cm long) the degree of conversion decreases from 0.21 to 0.03 and m decreases from 0.42 to 0.32 as the flow rate increases from 0.15 to 3.5 ml min-1. 相似文献
995.
F W Wang 《Macromolecules》1976,9(1):97-101
An equation for the translational diffusion coefficient of block copolymers in dilute solution has been obtained by modifying Zimm's equation for homopolymers to take into account the existence of dissimilar segments in block copolymers. Illustrative calculations for homopolymers and block copolymers have been made and the results for homopolymers have been compared with experiments and with the calculations of Yamakawa and Fujii. A procedure has been proposed to determine the molecular weight of a block copolymer from measurements of its limiting viscosity number and its sedimentation coefficient or translational diffusion coefficient. 相似文献
996.
According to the new method of preparing core-shell nanospheres developed by our group, by using two monomers, 2-hydroxypropyl
methacrylate(HPMA) and vinyl acetate(VAc), two kinds of core-shell nanospheres with poly(ɛ-caprolactone) (PCL) as the core
and crosslinked poly(2-hydroxypropyl methacrylate) (PHPMA) or poly(vinyl acetate) (PVAc) as the shell were successfully prepared
under similar conditions. After degrading the PCL cores of the two kinds of nanospheres by lipase, the corresponding crosslinked
poly(methyl acrylic acid) hollow spheres and crosslinked poly(vinyl alcohol) hollow spheres were obtained. Results indicate
that the new method we proposed for preparing core-shell polymeric nanospheres via in-situ polymerization can be generalized to a certain extent, and it is suitable for many systems provided the monomer used is soluble
in water, while its corresponding polymer is insoluble in water.
Translated from Chemical Journal of Chinese University, 2006, 27(9): 1762–1766 [译自: 高等学校化学学报] 相似文献
997.
Xiufang Xu Guichang Wang Xuezhuang Zhao Yinming Pan Yunxiao Liang Zhenfeng Shang 《Journal of mathematical chemistry》2007,41(2):143-160
In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular
orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond
to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes,
although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions
of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic
molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space
translation may exist, and thus a significant effect on their properties can be expected. 相似文献
998.
Xu-Chun Wang Jian-Feng Li He-Ping Chen Jie-Ying Wu Hong-Ping Zhou Jia-Xiang Yang Bao-Kang Jin Yu-Peng Tian 《Transition Metal Chemistry》2007,32(5):551-557
The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, 1H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL)
measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups
are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron
system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized
over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV
absorption and large optical limiting effect, indicating promising potential applications as useful OL materials. 相似文献
999.
Xianmei Xie Xiurong Ren Jinping Li Xiaojun Hu Zhizhong Wang 《天然气化学杂志》2006,15(2):100-104
Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnAl-HTLcs). Samples with high crystallinity, small particle size and narrow particle size distribution were obtained and fully characterized using conventional techniques of XRD, FT-IR and TGDTA. The results prove that both ultrasonic frequency and ultrasonic power have effects on the sizes of the product particles. By varying the ultrasonic power from 250 W to 88 W, with the ultrasonic frequency fixed at 59 kHz, the median particle size of the samples increased from 0.37 μm to 0.82 μm. By altering the hydrothermal treatment time from 1 h to 5 h at 110℃, the median particle size of ZnAl-HTLcs synthesized via ultrasonic crystallization increased from 0.88 μm to 1.11 μm. 相似文献
1000.
Chaowei Yuan Wen Cui Yanjuan Sun Jiadong Wang Ruimin Chen Jin Zhang Yuxin Zhang Fan Dong 《中国化学快报》2020,31(3):751-754
It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification. 相似文献