全文获取类型
收费全文 | 3809篇 |
免费 | 616篇 |
国内免费 | 738篇 |
专业分类
化学 | 2807篇 |
晶体学 | 88篇 |
力学 | 90篇 |
综合类 | 94篇 |
数学 | 439篇 |
物理学 | 1645篇 |
出版年
2024年 | 4篇 |
2023年 | 55篇 |
2022年 | 96篇 |
2021年 | 107篇 |
2020年 | 193篇 |
2019年 | 176篇 |
2018年 | 164篇 |
2017年 | 152篇 |
2016年 | 150篇 |
2015年 | 105篇 |
2014年 | 417篇 |
2013年 | 468篇 |
2012年 | 323篇 |
2011年 | 411篇 |
2010年 | 313篇 |
2009年 | 376篇 |
2008年 | 260篇 |
2007年 | 222篇 |
2006年 | 146篇 |
2005年 | 104篇 |
2004年 | 118篇 |
2003年 | 97篇 |
2002年 | 115篇 |
2001年 | 92篇 |
2000年 | 85篇 |
1999年 | 57篇 |
1998年 | 65篇 |
1997年 | 52篇 |
1996年 | 49篇 |
1995年 | 53篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 20篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 6篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1959年 | 1篇 |
排序方式: 共有5163条查询结果,搜索用时 15 毫秒
41.
Yuanhong Kang Guanhong Chen Haiming Hua Minghao Zhang Jin Yang Pengxiang Lin Huiya Yang Zeheng Lv Qilong Wu Prof. Jinbao Zhao Dr. Yang Yang 《Angewandte Chemie (International ed. in English)》2023,62(22):e202300418
Zn−I2 batteries stand out in the family of aqueous Zn-metal batteries (AZMBs) due to their low-cost and immanent safety. However, Zn dendrite growth, polyiodide shuttle effect and sluggish I2 redox kinetics result in dramatically capacity decay of Zn−I2 batteries. Herein, a Janus separator composed of functional layers on anode/cathode sides is designed to resolve these issues simultaneously. The cathode layer of Fe nanoparticles-decorated single-wall carbon nanotubes can effectively anchor polyiodide and catalyze the redox kinetics of iodine species, while the anode layer of cation exchange resin rich in −SO3− groups is beneficial to attract Zn2+ ions and repel detrimental SO42−/polyiodide, improving the stability of cathode/anode interfaces synergistically. Consequently, the Janus separator endows outstanding cycling stability of symmetrical cells and high-areal-capacity Zn−I2 batteries with a lifespan over 2500 h and a high-areal capacity of 3.6 mAh cm−2. 相似文献
42.
Hui Xu Dr. Shengbo Zhang Xinyuan Zhang Min Xu Dr. Miaomiao Han Prof. Li Rong Zheng Prof. Yunxia Zhang Prof. Guozhong Wang Prof. Haimin Zhang Prof. Huijun Zhao 《Angewandte Chemie (International ed. in English)》2023,62(52):e202314414
The integration of highly active single atoms (SAs) and atom clusters (ACs) into an electrocatalyst is critically important for high-efficiency two-electron oxygen reduction reaction (2e− ORR) to hydrogen peroxide (H2O2). Here we report a tandem impregnation-pyrolysis-etching strategy to fabricate the oxygen-coordinated Fe SAs and ACs anchored on bacterial cellulose-derived carbon (BCC) (FeSAs/ACs-BCC). As the electrocatalyst, FeSAs/ACs-BCC exhibits superior electrocatalytic activity and selectivity toward 2e− ORR, affording an onset potential of 0.78 V (vs. RHE) and a high H2O2 selectivity of 96.5 % in 0.1 M KOH. In a flow cell reactor, the FeSAs/ACs-BCC also achieves high-efficiency H2O2 production with a yield rate of 12.51±0.18 mol gcat−1 h−1 and a faradaic efficiency of 89.4 %±1.3 % at 150 mA cm−2. Additionally, the feasibility of coupling the produced H2O2 and electro-Fenton process for the valorization of ethylene glycol was explored in detail. The theoretical calculations uncover that the oxygen-coordinated Fe SAs effectively regulate the electronic structure of Fe ACs which are the 2e− ORR active sites, resulting in the optimal binding strength of *OOH intermediate for high-efficiency H2O2 production. 相似文献
43.
采用简单易行的浸渍法将Pt纳米粒子负载到MIL-101(Cr)上,制备了Pt/MIL-101(Cr)催化剂,并对其在肉桂醛选择性加氢反应的催化性能进行了研究。XRD、N2吸附、TEM和催化性能的研究结果表明,Pt的负载量对负载于MIL-101(Cr)上Pt纳米粒子的尺寸及所制备催化剂对肉桂醇的选择性有很大影响。低Pt负载量(1.0%)的Pt/MIL-101(Cr)较其他MOFs和无机材料在肉桂醛选择性加氢反应中表现出了高的催化性能,在优化的反应条件下肉桂醛转化率和对肉桂醇的选择性可分别达96.5%和86.2%。Pt/MIL-101(Cr)催化剂具有良好的稳定性。Pt/MIL-101(Cr)所表现出的优良的催化性能同MIL-101(Cr)载体的孔道结构及其表面性质密切相关。 相似文献
44.
45.
建立了用邻菲啰啉-Fe(Ⅱ)分光光度法测定头孢唑啉钠的方法 .头孢唑啉钠在0.10mol·L-1 NaOH溶液中,100℃水浴加热降解为含巯基的化合物.巯基化合物把Fe3+还原为Fe2+.加入邻菲啰啉显色,通过测定生成的橘红色配位化合物的吸光度间接测定头孢唑啉钠的含量.头孢唑啉钠浓度在0.02~40mg·L-1范围内呈现良好线性关系,线性回归方程A=0.043c(mg·L-1)-0.001,相关系数R=0.998 8,表观摩尔吸光系数ε=2.05×104 L·(mol·cm)-1,相对标准偏差RSD=1.27%,检测限(3σ/k)0.065mg·L-1.在此基础上,测定了市售头孢唑啉钠粉针剂的含量,回收率在99.17%~101.2%之间,结果令人满意. 相似文献
46.
将PEG/PAA凝胶浸入铁/柠檬酸(Fe3+/CA)溶液中,自然光照一定时间可实现凝胶-溶胶的相互转化,而且转化行为受溶液的组成及其p H影响。只有当溶液中[Fe3+]0∶[CA]0≤1∶2,且溶液的p H在1~6之间,该转化才会发生,通过改变溶液中[Fe3+]0∶[CA]0的值或溶液的p H可以有效地控制其转化速率。此外,结果还表明,当凝胶转化为溶胶后,向其中加入高价金属阳离子,例如Fe3+、Al3+、Ce4+、Cu2+等,溶胶又会再次转化为凝胶。由于这种新颖的特性,该凝胶有望应用于药物释放、细胞培养等领域。 相似文献
47.
Dr. Caroline T. Saouma Wesley D. Morris Julia W. Darcy Prof. James M. Mayer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9256-9260
Biological [Fe‐S] clusters are increasingly recognized to undergo proton‐coupled electron transfer (PCET), but the site of protonation, mechanism, and role for PCET remains largely unknown. Here we explore this reactivity with synthetic model clusters. Protonation of the arylthiolate‐ligated [4Fe‐4S] cluster [Fe4S4(SAr)4]2? ( 1 , SAr=S‐2,4‐6‐(iPr)3C6H2) leads to thiol dissociation, reversibly forming [Fe4S4(SAr)3L]1? ( 2 ) and ArSH (L=solvent, and/or conjugate base). Solutions of 2 +ArSH react with the nitroxyl radical TEMPO to give [Fe4S4(SAr)4]1? ( 1ox ) and TEMPOH. This reaction involves PCET coupled to thiolate association and may proceed via the unobserved protonated cluster [Fe4S4(SAr)3(HSAr)]1? ( 1‐H ). Similar reactions with this and related clusters proceed comparably. An understanding of the PCET thermochemistry of this cluster system has been developed, encompassing three different redox levels and two protonation states. 相似文献
48.
Magnetically separable CuO nanoparticles supported on graphene oxide (Fe3O4 NPs/GO-CuO NPs) is synthesized and characterized for the preparation of propargylamines in EtOH, at 90℃. Fe3O4 NPs/GO-CuO NPs is found to be an efficient catalyst for the A3-coupling of aldehydes, amines, and alkynes through C-H activation. Both aromatic and aliphatic aldehydes and alkynes are combined with secondary amines to provide a wide range of propargylamines in moderate to excellent yields. 相似文献
49.
Selective oxidation of sulfides to sulfoxides was successfully performed by employing readily available Fe(NO3)3·9H2O as the active catalyst with oxygen as the oxidant in 2,2,2-trifluoroethanol (TFE) without the formation of sulfones. Nitrate anion could play a crucial role in promoting the reaction due to the oxidation capacity under acidic media. High yields of sulfoxides were exclusively obtained from the corresponding sulfides. Furthermore, both aromatic and aliphatic sulfides gave moderate to high yields of sulfoxides with this protocol. 相似文献
50.
Electrode Modification Using Alkynyl Substituted Fe(II) Phthalocyanine via Electrografting and Click Chemistry for Electrocatalysis 下载免费PDF全文
In this work, tetrakis(5‐hexyn‐oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4‐azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne‐azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM?1 and a limit of detection of 1.09 µM. 相似文献