全文获取类型
收费全文 | 2927篇 |
免费 | 190篇 |
国内免费 | 340篇 |
专业分类
化学 | 1170篇 |
晶体学 | 6篇 |
力学 | 88篇 |
综合类 | 34篇 |
数学 | 888篇 |
物理学 | 1271篇 |
出版年
2024年 | 14篇 |
2023年 | 37篇 |
2022年 | 132篇 |
2021年 | 137篇 |
2020年 | 124篇 |
2019年 | 67篇 |
2018年 | 90篇 |
2017年 | 80篇 |
2016年 | 84篇 |
2015年 | 89篇 |
2014年 | 137篇 |
2013年 | 247篇 |
2012年 | 119篇 |
2011年 | 180篇 |
2010年 | 147篇 |
2009年 | 200篇 |
2008年 | 210篇 |
2007年 | 216篇 |
2006年 | 150篇 |
2005年 | 116篇 |
2004年 | 84篇 |
2003年 | 97篇 |
2002年 | 74篇 |
2001年 | 82篇 |
2000年 | 94篇 |
1999年 | 41篇 |
1998年 | 58篇 |
1997年 | 49篇 |
1996年 | 42篇 |
1995年 | 25篇 |
1994年 | 23篇 |
1993年 | 25篇 |
1992年 | 19篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 19篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 16篇 |
1984年 | 11篇 |
1983年 | 5篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1976年 | 3篇 |
1973年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有3457条查询结果,搜索用时 0 毫秒
81.
湿混法制备甲醇氧化重整制氢CuZnAlZr催化剂 总被引:3,自引:1,他引:3
用简易湿混法制备了用于甲醇氧化重整制氢的CuZnAlZr催化剂,与共沉淀法制备的催化剂比较,结果表明,湿混法制备的催化剂具有相当的中高温活性和略低的低温活性,有较高的CO2选择性。XRD、TPR、TG-DSC等表征结果显示,湿混法制备的催化剂中铜组分易于向表面迁移和富集,并可能与氧化铝作用生成铜铝复合氧化物,具有了更高的Cu分散度和Cu0比表面浓度。湿混法制备的催化剂对甲醇氧化重整反应有较好的稳定性,经100 h的连续反应,在275 ℃时甲醇转化率在90%以上,重整气中氢气体积分数大于60%,CO2选择性接近99%。 相似文献
82.
蜂窝催化剂上甲醇自热重整制氢的动力学研究 总被引:5,自引:2,他引:5
400 ℃~460 ℃,400 h-1~1 600 h-1,O2/CH3OH(mol ratio)=0.10~0.25,H2O/CH3OH (mol ratio) =1.0~1.8下,通过正交实验设计方法,用BSD-2A型内循环无梯度反应器研究了Zn-Cr/CeO2-ZrO2蜂窝催化剂上甲醇自热重整制氢反应的宏观动力学。以甲醇水蒸气重整反应、甲醇分解反应和甲醇完全氧化反应为独立反应进行了研究,得出了幂指数型反应速率表达式,并根据实验结果,利用最小二乘法求解了动力学参数值。F检验表明该动力学模型是高度显著的。该多重反应动力学方程的得出为蜂窝反应器的进一步模拟、优化和设计提供了数据。 相似文献
83.
84.
生物柴油作为可再生的清洁能源,已在美国、欧盟等多个国家和地区推行使用。在生物柴油的生产过程中,最高可得到约10%的副产物甘油,副产物甘油的去向将成为生物柴油大规模产业化发展所面临的严峻问题。1,3-丙二醇是一种重要的化工原料,作为合成新型聚酯PTT的原料,1,3-丙二醇已引起人们的广泛关注。以生物柴油副产物甘油为原料耦合生产1,3-丙二醇,不仅解决了生物柴油副产物甘油的出路问题,同时降低了1,3-丙二醇的生产成本。本文详细介绍了生物柴油及1,3-丙二醇生产技术及联产工艺的研究进展,并对其应用前景进行了展望。 相似文献
85.
86.
The aim of this work was to establish optimal conditions for the maximum production of endo-β-1,4 mannanases using cheaper
sources. Eight thermotolerant fungal strains were isolated from garden soil and compost samples collected in and around the
Gulbarga University campus, India. Two strains were selected based on their ability to produce considerable endo-β-1,4 mannanases
activity while growing in liquid medium at 37 °C with locust bean gum (LBG) as the only carbon source. They were identified
as Aspergillus niger gr and Aspergillus flavus gr. The experiment to evaluate the effect of different carbon sources, nitrogen sources, temperatures and initial pH of the
medium on maximal enzyme production was studied. Enzyme productivity was influenced by the type of polysaccharide used as
the carbon source. Copra meal defatted with n-hexane showed to be a better substrate than LBG and guar gum for endo-β-1,4 mannanases production by A. niger gr (40.011 U/ml), but for A. flavus gr (33.532 U/ml), the difference was not significant. Endo-β-1,4 mannanases produced from A. niger gr and A. flavus gr have high optimum temperature (65 and 60 °C) and good thermostability in the absence of any stabilizers (maintaining 50%
of residual activity for 8 and 6 h, respectively, at 60 °C) and are stable over in a wide pH range. These new strains offer
an attractive alternative source of enzymes for the food and feed processing industries. 相似文献
87.
Qun He Daobin Liu Ji Hoon Lee Yumeng Liu Zhenhua Xie Sooyeon Hwang Shyam Kattel Li Song Jingguang G. Chen 《Angewandte Chemie (International ed. in English)》2020,59(8):3033-3037
The electrochemical CO2 reduction reaction (CO2RR) to yield synthesis gas (syngas, CO and H2) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2RR activity and the CO/H2 ratio. To address this issue, nitrogen‐doped carbon supported single‐atom catalysts are designed as electrocatalysts to produce syngas from CO2RR. While Co and Ni single‐atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm?2) with CO/H2 ratios (0.23–2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single‐atom configurations for the H2 and CO evolution. The results present a useful case on how non‐precious transition metal species can maintain high CO2RR activity with tunable CO/H2 ratios. 相似文献
88.
Michael G. Pfeffer Tanja Kowacs Dr. Maria Wächtler Dr. Julien Guthmuller Prof. Dr. Benjamin Dietzek Prof. Dr. Johannes G. Vos Prof. Dr. Sven Rau 《Angewandte Chemie (International ed. in English)》2015,54(22):6627-6631
A molecular photocatalyst consisting of a RuII photocenter, a tetrapyridophenazine bridging ligand, and a PtX2 (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies. 相似文献
89.
Michael E. Cates tienne Fodor Tomer Markovich Cesare Nardini Elsen Tjhung 《Entropy (Basel, Switzerland)》2022,24(2)
Many complex fluids can be described by continuum hydrodynamic field equations, to which noise must be added in order to capture thermal fluctuations. In almost all cases, the resulting coarse-grained stochastic partial differential equations carry a short-scale cutoff, which is also reflected in numerical discretisation schemes. We draw together our recent findings concerning the construction of such schemes and the interpretation of their continuum limits, focusing, for simplicity, on models with a purely diffusive scalar field, such as ‘Model B’ which describes phase separation in binary fluid mixtures. We address the requirement that the steady-state entropy production rate (EPR) must vanish for any stochastic hydrodynamic model in a thermal equilibrium. Only if this is achieved can the given discretisation scheme be relied upon to correctly calculate the nonvanishing EPR for ‘active field theories’ in which new terms are deliberately added to the fluctuating hydrodynamic equations that break detailed balance. To compute the correct probabilities of forward and time-reversed paths (whose ratio determines the EPR), we must make a careful treatment of so-called ‘spurious drift’ and other closely related terms that depend on the discretisation scheme. We show that such subtleties can arise not only in the temporal discretisation (as is well documented for stochastic ODEs with multiplicative noise) but also from spatial discretisation, even when noise is additive, as most active field theories assume. We then review how such noise can become multiplicative via off-diagonal couplings to additional fields that thermodynamically encode the underlying chemical processes responsible for activity. In this case, the spurious drift terms need careful accounting, not just to evaluate correctly the EPR but also to numerically implement the Langevin dynamics itself. 相似文献
90.
The standard textbooks contain good explanations of how and why equilibrium thermodynamics emerges in a reservoir with particles that are subjected to Gaussian noise. However, in systems that convert or transport energy, the noise is often not Gaussian. Instead, displacements exhibit an -stable distribution. Such noise is commonly called Lévy noise. With such noise, we see a thermodynamics that deviates from what traditional equilibrium theory stipulates. In addition, with particles that can propel themselves, so-called active particles, we find that the rules of equilibrium thermodynamics no longer apply. No general nonequilibrium thermodynamic theory is available and understanding is often ad hoc. We study a system with overdamped particles that are subjected to Lévy noise. We pick a system with a geometry that leads to concise formulae to describe the accumulation of particles in a cavity. The nonhomogeneous distribution of particles can be seen as a dissipative structure, i.e., a lower-entropy steady state that allows for throughput of energy and concurrent production of entropy. After the mechanism that maintains nonequilibrium is switched off, the relaxation back to homogeneity represents an increase in entropy and a decrease of free energy. For our setup we can analytically connect the nonequilibrium noise and active particle behavior to entropy decrease and energy buildup with simple and intuitive formulae. 相似文献