全文获取类型
收费全文 | 3368篇 |
免费 | 667篇 |
国内免费 | 1340篇 |
专业分类
化学 | 2623篇 |
晶体学 | 199篇 |
力学 | 265篇 |
综合类 | 119篇 |
数学 | 505篇 |
物理学 | 1664篇 |
出版年
2024年 | 2篇 |
2023年 | 37篇 |
2022年 | 117篇 |
2021年 | 99篇 |
2020年 | 113篇 |
2019年 | 125篇 |
2018年 | 123篇 |
2017年 | 160篇 |
2016年 | 112篇 |
2015年 | 182篇 |
2014年 | 192篇 |
2013年 | 270篇 |
2012年 | 282篇 |
2011年 | 296篇 |
2010年 | 300篇 |
2009年 | 317篇 |
2008年 | 332篇 |
2007年 | 339篇 |
2006年 | 307篇 |
2005年 | 289篇 |
2004年 | 230篇 |
2003年 | 186篇 |
2002年 | 168篇 |
2001年 | 146篇 |
2000年 | 170篇 |
1999年 | 102篇 |
1998年 | 45篇 |
1997年 | 31篇 |
1996年 | 20篇 |
1995年 | 34篇 |
1994年 | 30篇 |
1993年 | 27篇 |
1992年 | 16篇 |
1991年 | 16篇 |
1990年 | 18篇 |
1989年 | 15篇 |
1988年 | 16篇 |
1987年 | 15篇 |
1986年 | 11篇 |
1985年 | 16篇 |
1984年 | 4篇 |
1983年 | 15篇 |
1982年 | 7篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1973年 | 2篇 |
1965年 | 7篇 |
1959年 | 2篇 |
排序方式: 共有5375条查询结果,搜索用时 15 毫秒
101.
102.
二甲醚电氧化及其阳极催化剂研究 总被引:6,自引:0,他引:6
Anode electro-catalysts for direct dimethyl-ether fuel cell (DDFC), Pt/C, PtRu/C (1∶1) and PtSn/C (3∶2), were prepared by chemical impregnation-reduction method with formaldehyde as the reductant. DME electro-oxidation and adsorption at Pt electrode and Pt electro-catalysts were investigated by Cyclic Voltammetry(CV), Quasi-steady state polarization and Gas Chromatography(GC). CV showed that there were two current peaks of DME electro-oxidation at Pt electrode around 0.8V (vs RHE); DME was adsorbed at Pt electrode more weakly and slowly than oxygen, methanol, even hydrogen; the onset potential of DME oxidation was 50mV less than that of methanol, and DME peak potential 110 mV lower, thus more advantageous for using in fuel cells than methanol. GC showed that small amount of HCHO was generated during DME electro-oxidation. The mechanism of DME electro-oxidation was proposed. Among the three electro-catalysts (Pt/C, PtRu/C and PtSn/C), Pt alloy catalysts, especially PtRu/C, showed a higher performance toward DME electro-oxidation, as in the case of methanol. Temperature experiments showed that both DME electro-oxidation and adsorption on Pt and Pt alloy catalysts were favored with increased temperature. 相似文献
103.
含羧酸配体的鼓形有机锡氧簇合物:六聚苯基锡氧3-吲哚丁酸酯的合成及晶体结构 总被引:7,自引:0,他引:7
利用Ph3SnOH和3-吲哚丁酸以1:1摩尔比反应,合成了新型含羧酸配体的鼓形 有机锡氧簇合物:六聚苯基锡氧3-吲哚西酸酯。通过元素分析、红外光谱和X射线 单晶衍射对其结构进行了表征。测试结果表明:该化合物为三斜晶系,空间群P1, a=1.1722(6),b=1.5694(8)nm,c=1.7227(9)nm,α=116.251(8)°,β=100. 854(10)°,γ=95.606(9)°,Z=1,V=2.732(3)nm^3,Dc=1.554g·cm^-3,μ =1.420mm^-1,F(000)=1276,R=0.0630,ωR=0.0762。晶体结构中,六配位的锡原 子呈畸变的八面体构型。 相似文献
104.
Study on Tonghaosu and Its Analogs: Isolation, Structure Identification and Synthesis of Antifeedant B-ring-homo-tonghaosu 总被引:1,自引:0,他引:1
The methanolic extract from a Chinese endemic Chrysanthemum plant, Dendranthema indicum var. aromaticum, was found to show high antifeeding activity against Pieris brassicae L., and by bioassay-guided separation, the active component, B-ring-homo-tonghaosu, 2-(2‘,4‘-hexadiynylidene)-1,6-dioxaspiro-[4,5]-dec-3-ene (2) was isolated. Its structure was elucidated by comparing its spectroscopic data with those of 2 reported in the literatures. Furthermore new convenient total synthesis methods of B-ring-homo-tonghaosu were also developed to confirm its structure and make its further application in crop protection available. In addition, extensive comparison of spectroscopic data showed that the structure of compound 21 reported in literature should be revised to 2. 相似文献
105.
协调政府与社会资本合作的利益分歧,进而实现个体理性向集体理性的趋同,这是纾解PPP项目合作困境的切入点之一。基于合作博弈理论,本文构建PPP项目非完全利益群体的合作形成机制,分析政府与社会资本间“合作共赢”的必要因素。研究表明,由政府与社会资本组成的PPP项目非完全利益群体,可在“理性-效用转移-有效协商”机制的协同作用下主动采取最优合作策略。其中,理性机制验证了政府与社会资本达成合作意向的前提,效用转移机制可实现二者之间的风险-收益对等,有效协商机制将达成政府与社会资本合作的帕累托均衡。 相似文献
106.
The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) (A),β = 109.187(2)o, V = 1482.6(2) (A)3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with Ⅰ > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel. 相似文献
107.
1INTRoDUCTIoNIntenseinterestintransition-metalclusterscontinuesbecausetheyrepresentpos-sibleconceptualbridgesbetweenhomogeneousandheterogeneouscatalystsmoreoveralsobecausetheyrepresentsyntheticchallenges.TheuseofelementsofGroup16ofthePeriodicTableassingleatomligandsforclustergrowthandstabilizationofthemetalcorearenowwellestablished[1i.ThereisanincreasinginterestintheuseofSe-bridgrdclusters,manyofthereactionsofSe2Fe2(CO),andSe2Fe,(CO),havebeenreported"';however,therehasbeenverylittlewor… 相似文献
108.
109.
110.
由[Cu(MeCN)2 (PPh3)2 ](BF4 )和 4′ 苯基 2,2′:6′,2″ 三联吡啶(4′ Phtpy)在室温下反应,合成了一个新颖的具有光致发光性能的五配位配合物[Cu(4′ Phtpy)(PPh3)2 ](BF4 ).对配合物进行了X射线衍射结构表征,并进行了红外光谱、紫外可见光谱、荧光光谱等光谱学分析.晶体属单斜晶系,空间群Pn,晶胞参数:a =1 0 80 7(6)nm,b =1 0 943 (6)nm,c=2 1610(12 )nm,α =90°,β =10 2 785(10 )°,γ =90°,V =2 492(2 )nm3,Z =2,Dc=1 3 5 4g·cm-3.配合物中,Cu(Ⅰ)与 4′ Phtpy的 3个N,2个PPh3的P配位呈变形三角双锥型结构,其轴向由Cu键合联吡啶的末端 2个N所组成,赤道平面由联吡啶的中心N原子和 2个PPh3的P原子所组成 相似文献