全文获取类型
收费全文 | 12141篇 |
免费 | 1337篇 |
国内免费 | 1931篇 |
专业分类
化学 | 4188篇 |
晶体学 | 153篇 |
力学 | 404篇 |
综合类 | 129篇 |
数学 | 621篇 |
物理学 | 2295篇 |
综合类 | 7619篇 |
出版年
2024年 | 65篇 |
2023年 | 149篇 |
2022年 | 398篇 |
2021年 | 409篇 |
2020年 | 378篇 |
2019年 | 343篇 |
2018年 | 294篇 |
2017年 | 386篇 |
2016年 | 426篇 |
2015年 | 581篇 |
2014年 | 800篇 |
2013年 | 913篇 |
2012年 | 944篇 |
2011年 | 923篇 |
2010年 | 925篇 |
2009年 | 962篇 |
2008年 | 1026篇 |
2007年 | 1025篇 |
2006年 | 814篇 |
2005年 | 678篇 |
2004年 | 528篇 |
2003年 | 359篇 |
2002年 | 404篇 |
2001年 | 355篇 |
2000年 | 362篇 |
1999年 | 197篇 |
1998年 | 104篇 |
1997年 | 86篇 |
1996年 | 76篇 |
1995年 | 63篇 |
1994年 | 62篇 |
1993年 | 73篇 |
1992年 | 58篇 |
1991年 | 38篇 |
1990年 | 46篇 |
1989年 | 40篇 |
1988年 | 14篇 |
1987年 | 15篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 10篇 |
1983年 | 13篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 11篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1971年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
41.
Juan Hong Liang-Fu Tang Zhi Yang Yu-Ping Zhai Mujia Nan 《Transition Metal Chemistry》2005,30(4):439-444
A series of [M(CO)5I]− and [M2(CO)10I]− anion complexes have been synthesized by the photochemical reaction of PhCH2N(CH3)3I or FcCH2N(CH3)3I (Fc=ferrocenyl) with M(CO)6 (M = Cr, Mo or W), and characterized by elemental analyses, i.r., 1H-n.m.r. and 13C-n.m.r. spectra in the case of the molybdenum and tungsten complexes. These complexes exhibit considerably different electrochemical behavior, when investigated by cyclic voltammetry. The crystal structures of [PhCH2N(CH3)3][Cr(CO)5I] and [FcCH2N(CH3)3][W2(CO)10I] have been determined by X-ray diffraction, indicating that only weak contacts maybe exist between anions and cations by the I...H bond in the former, and there are no direct interactions between anions and cations in the latter. 相似文献
42.
建立了散射背景下测定人体血清中Zn^2+含量的激光热透镜光谱分析方法。比较了蛋白质微粒散射对于分光光度法和激光热透镜光谱分析法测定的影响。结果表明,激光热透镜光谱分析方法能够避免溶液中存留蛋白质微粒散射的影响。Zn^2+量在0~1.6μg/mL范围内呈线性关系(r=0.9986),检出限为1ng/mL。应用于人体血清中Zn^2+含量的测定,与原子吸收法测定结果基本一致。 相似文献
43.
A new titrimetric method for determination of tin (4%) in aluminium alloys, tin- and lead-base alloys, solders, white bearing alloys, special bronzes and silver brazing alloys is proposed. HEDTA, Semi-Xylenol Orange and bismuth perchlorate are used as titrant, indicator and back-titrant respectively. Measures are taken to overcome the hydrolysis of Sn(IV). Monochloroacetic acid and ethylene glycol are added as auxiliary agents. The standard deviation of this method was found to be 0.2 mg and its coefficient of variation to vary from 0.25 to 2%, according to amount of tin. A novel method of sample decomposition and a modified method for separating Sn(IV) are also suggested. 相似文献
44.
45.
46.
通过IR方法,观测并讨论了在不同条件下制备的超高分子量PE(WHMPE)凝胶膜中旁式(G构象)构象与超拉伸性的关系,提出了G构象浓度及分布对UHMPE凝胶膜超拉伸性影响的新概念,同时也讨论了它与链缠结之间的联系,发现:反映G构象的相对浓度的比值σ=I1303I1352随制膜浓度的增大而增加,在临界浓度C0(0.4~0.5g@100ml)附近所形成的膜,具有超高拉伸性(λ=200),其G构象的变化与Matsuo由比浓粘度提出的缠结链改变相对应;热处理温度比热处理时间对σ值的影响更显著,在一定温度下约4分钟后σ值基本不变;在σ值最低的温度范围拉伸,凝胶膜具有良好的超高拉伸性. 相似文献
47.
The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l–1 NH3-NH4Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH3-NH4Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml–1 to 50.0 g ml–1. The detection limit (three times the signal-to-noise) was 1.0 g ml–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results. 相似文献
48.
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
49.
50.
以正硅酸乙酯(TEOS)为硅源,十六烷基三甲基溴化铵(CTAB)为表面活性剂,仲钨酸铵为钨源,采用水热晶化法一步合成了不同钨含量(以Si、W物质的量比nSi/nW表示)的WO3-MCM-48,然后经甲烷/氢气(V/V=1/4)混和气体程序升温还原碳化(TPC),制备出了WxC-MCM-48(x=1、2)催化剂,采用XRD、N2吸附-脱附和NH3-TPD对样品的结构进行了表征,用噻吩作为模型化合物,对WxC-MCM-48催化剂的加氢脱硫催化活性进行了评价。结果表明,在一定钨含量的条件下,WO3-MCM-48和WxC-MCM-48样品仍然保持MCM-48的三维立方有序介孔结构,nSi/nW=30~15时,碳化钨的物相为W2C;nSi/nW=7.5时,碳化钨为W2C和WC物相,WxC-MCM-48催化剂表现出了良好的加氢脱硫催化性能。 相似文献