全文获取类型
收费全文 | 1610篇 |
免费 | 289篇 |
国内免费 | 161篇 |
专业分类
化学 | 1263篇 |
晶体学 | 15篇 |
力学 | 87篇 |
综合类 | 3篇 |
数学 | 113篇 |
物理学 | 579篇 |
出版年
2024年 | 9篇 |
2023年 | 31篇 |
2022年 | 42篇 |
2021年 | 73篇 |
2020年 | 60篇 |
2019年 | 63篇 |
2018年 | 59篇 |
2017年 | 46篇 |
2016年 | 77篇 |
2015年 | 84篇 |
2014年 | 87篇 |
2013年 | 107篇 |
2012年 | 155篇 |
2011年 | 158篇 |
2010年 | 99篇 |
2009年 | 83篇 |
2008年 | 123篇 |
2007年 | 106篇 |
2006年 | 103篇 |
2005年 | 96篇 |
2004年 | 62篇 |
2003年 | 40篇 |
2002年 | 44篇 |
2001年 | 26篇 |
2000年 | 28篇 |
1999年 | 25篇 |
1998年 | 17篇 |
1997年 | 20篇 |
1996年 | 17篇 |
1995年 | 18篇 |
1994年 | 13篇 |
1993年 | 8篇 |
1992年 | 13篇 |
1991年 | 19篇 |
1990年 | 13篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 5篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1947年 | 1篇 |
1946年 | 1篇 |
排序方式: 共有2060条查询结果,搜索用时 0 毫秒
111.
112.
Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction
Haibo He Gang Wang Shengchao Chai Xiang Li Liang Zhai Lixin Wu Haolong Li 《中国化学快报》2021,32(6):2013-2016
The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_3 PW_(12)O_(4 O)(PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3 × 10~(-4) S/cm and a storage modulus of 1.1 × 10~7 Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials. 相似文献
113.
大量乙烯中少量乙炔的去除是化工生产中的重要过程之一,理想途径是将其选择加氢生成乙烯.负载型Pd催化剂因具有很高的乙炔转化率而被广泛用于该过程,但乙烯选择性很低,同时会使原料气中的乙烯被加氢,造成原料气的浪费.采用其它元素对Pd纳米粒子表面修饰,覆盖部分活性位,可以在一定程度上提高乙烯选择性,但是会大大降低Pd的利用率.因此,制备兼具高活性和高选择性且经济实用的催化剂,仍是这一过程亟待解决的主要问题之一.我们的前期工作中,将Pd与IB族金属(Au,Ag,Cu)分别结合制备得到了一系列含Pd的合金单原子催化剂(SAC),发现它们在大量乙烯存在条件下的乙炔选择加氢反应中表现出优异的催化性能.其中,Pd的用量仅为ppm级别,大大提高了Pd的利用率.作为IB族最为廉价的金属,Pd与Cu形成的合金SAC在提高Pd原子利用率的同时,能够进一步降低催化剂的经济成本.然而,当形成合金SAC时,Cu/Pd原子比例的极限值仍然不确定.本文通过固定Pd的担载量,采用简单的等体积共浸渍的方法,制备了一系列不同Cu/Pd原子比例的氧化硅负载的双金属催化剂.首先,我们采用程序升温还原(TPR)和X射线衍射(XRD)对催化剂的还原能力和双金属纳米粒子的尺寸进行了考察.进一步,采用X射线吸收光谱(XAS,包括EXAFS和XANES)对双金属催化剂中Pd的配位环境进行了分析.最后,结合它们在大量乙烯存在条件下的乙炔选择加氢反应中的催化性能,对形成合金SAC时Cu/Pd原子比例进行了讨论.TPR结果显示,Cu与Pd结合时会促进双金属纳米粒子的还原.XRD结果表明,随着Cu含量的降低,双金属纳米粒子的尺寸明显减小.XANES结果证实,当Pd与Cu结合时,Pd会带有部分负电荷,这也与Pd的电负性大于Cu相一致.通过对EXAFS拟合结果进行分析,我们发现当Cu/Pd的原子比例≥40/1时,Pd原子可以被Cu原子完全分隔开,形成含Pd的合金SAC,使其在大量乙烯存在条件下的乙炔选择加氢反应中表现出优异的催化性能.通过对还原温度的考察,我们发现还原温度由250 oC升高到400 oC时,对同一催化剂的催化性能影响不大;EXAFS拟合结果显示,对比分别经过250和400 oC还原后的催化剂,Pd的配位环境变化不明显,这可能是导致催化性能相似的主要原因. 相似文献
114.
Guanzhe Xu Yan Xiao Liang Cheng Runhua Zhou Heng Xu Yimin Chai Meidong Lang 《Journal of Polymer Science.Polymer Physics》2017,55(11):856-865
Deferoxamine grafted alginate (SA‐DFA) was successfully synthesized via amidation of sodium alginate with deferoxamine mesylate as determined by H‐NMR and elemental analysis. SA‐DFA with different graft yield was obtained by adjusting the ratio of sodium alginate and deferoxamine mesylate. It was found that aqueous solution of SA‐DFA could form hydrogel spontaneously due to hydrogen bonding interactions, which also endowed the SA‐DFA hydrogel with self‐healing capability. The healing efficiency of SA‐DFA hydrogels ranged from 53.64 to 90.16%. In addition, surface morphologies of SA‐DFA hydrogels before/after self‐healing process were demonstrated by SEM images. We anticipated that such self‐healable alginate hydrogel would be applied in the field of wound healing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 856–865 相似文献
115.
A new simple pyrene-substituted acylhydrazone derivative, 4-(3,4-dioctyloxy) phenyl-1-pyrene acylhydrazone (PAH-8), was designed and synthesized. The PAH-8 can form thermo-reversible organogel in DMSO, and shows gelation-induced enhanced fluorescence emission. Xerogel exhibits ribbon-like fibrous aggregates with widths of 0.5-1 μm. The PAH-8 organogel indicates photo-responsive behaviors due to the trans-cis isomerizations of -C=N- bond upon exposure to visible or UV light. Upon visible light irradiation, the partial trans-cis isomerization of the -C=N- bond causes the fiber morphology to disappear, resulting in gel-sol transition, whereas the PAH-8 organogel exhibits few photoisomerizations from trans to cis transition without breakage of the gel state upon UV light irradiation. 相似文献
116.
Dr. You Xu Xingjie Chai Tianlun Ren Hongjie Yu Shuli Yin Dr. Ziqiang Wang Prof. Dr. Xiaonian Li Prof. Dr. Liang Wang Dr. Hongjing Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16074-16080
The realization of water electrolysis on the basis of highly active, cost-effective electrocatalysts is significant yet challenging for achieving sustainable hydrogen production from water. Herein, N-doped Ni3S2/N-doped MoS2 1D hetero-nanowires supported by Ni foam (N-Ni3S2/N-MoS2/NF) are readily synthesized through a chemical transformation strategy by using NiMoO4 nanowire array growth on Ni foam (NiMoO4/NF) as the starting material. With the in situ generation of Ni3S2/MoS2 heterointerfaces within nanowires and the incorporation of N− anions, an extraordinary hydrophilic nature with abundant, well-exposed active sites and optimal reaction dynamics for both oxidation and reduction of water are obtained. Attributed to these properties, as-converted N-Ni3S2/N-MoS2/NF exhibits highly efficient electrocatalytic activities for both hydrogen and oxygen evolution reactions under alkaline conditions. The superior bifunctional properties of N-Ni3S2/N-MoS2/NF enable it to effectively catalyze the overall water-splitting reaction. 相似文献
117.
高效液相色谱-电感耦合等离子体质谱联用测定生物样品中无机汞和甲基汞 总被引:7,自引:5,他引:7
建立了高效液相色谱(HPLC)和电感耦合等离子体质谱(ICP-MS)联用测定多种生物样品中的无机汞和甲基汞的方法,并对比了提取生物样品中无机汞和甲基汞的不同前处理方法。实验使用5 mol/L的盐酸超声波提取样品中的无机汞和甲基汞。高效液相色谱流动相为含有0.06 mol/L醋酸氨,20μg/L B i,0.1%(V/V)2-巯基乙醇的5%(V/V)甲醇-水溶液,色谱柱为C18反相柱(5μm,3.9 mm×150 mm)。提取液在液相色谱中分离后,进入电感耦合等离子体质谱检测其中无机汞和甲基汞的浓度。测定了人发(GBW 07601),对虾(GBW 08572),鱼肉组织(IAEA MA-B-3/TM)和牛肝(GBW 080193)4种生物标准参考物,结果与标准参考物的标准值相符。无机汞和甲基汞检出限分别为0.3和0.2μg/L。 相似文献
118.
C. Li Chifang Chai Xueying Mao Hong Ouyang 《Analytical and bioanalytical chemistry》1999,363(5-6):602-605
Chemical speciation of platinum metals and some other siderophile elements in Precambrian/Cambrian black shale, south China, were studied using stepwise dissolution, fire assay preconcentration, inductively coupled plasma mass spectrometry and instrumental neutron activation analysis. The results indicate that platinum metals in Precambrian/Cambrian black shale, south China, are enriched through a syngenetical mineralizing process. 相似文献
119.
120.
A Metal–Organic Framework with Cooperative Phosphines That Permit Post‐Synthetic Installation of Open Metal Sites 下载免费PDF全文
Samuel G. Dunning Gianne Nandra Adam D. Conn Wenrui Chai R. Eric Sikma Ji Sun Lee Pranaw Kunal Joseph E. Reynolds III Jong‐San Chang Alexander Steiner Graeme Henkelman Simon M. Humphrey 《Angewandte Chemie (International ed. in English)》2018,57(30):9295-9299
PCM‐101 is a phosphine coordination material comprised of tris(p‐carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M3(OH)]5+ nodes (M=Co, Ni). PCM‐101 has a unique topology in which R3P: sites are arranged directly trans to one another, with a P???P separation distance dictated by the pillars. Post‐synthetic coordination of soft metals to the P: sites proceeds at room temperature to provide X‐ray quality crystals that permit full structural resolution. Addition of AuCl groups forces a large distortion of the parent framework. In contrast, CuBr undergoes insertion directly between the trans‐P sites to form dimers that mimic solution‐phase complexes, but that are geometrically strained due to steric pressure exerted by the MOF scaffold. The metalated materials are active in heterogeneous hydroaddition catalysis under mild conditions, yielding different major products compared to their molecular counterparts. 相似文献