全文获取类型
收费全文 | 25831篇 |
免费 | 4682篇 |
国内免费 | 3259篇 |
专业分类
化学 | 18179篇 |
晶体学 | 289篇 |
力学 | 1968篇 |
综合类 | 220篇 |
数学 | 2942篇 |
物理学 | 10174篇 |
出版年
2024年 | 50篇 |
2023年 | 524篇 |
2022年 | 782篇 |
2021年 | 871篇 |
2020年 | 1054篇 |
2019年 | 937篇 |
2018年 | 832篇 |
2017年 | 763篇 |
2016年 | 1204篇 |
2015年 | 1171篇 |
2014年 | 1399篇 |
2013年 | 1781篇 |
2012年 | 2296篇 |
2011年 | 2445篇 |
2010年 | 1620篇 |
2009年 | 1533篇 |
2008年 | 1773篇 |
2007年 | 1486篇 |
2006年 | 1553篇 |
2005年 | 1222篇 |
2004年 | 985篇 |
2003年 | 813篇 |
2002年 | 791篇 |
2001年 | 665篇 |
2000年 | 574篇 |
1999年 | 636篇 |
1998年 | 489篇 |
1997年 | 462篇 |
1996年 | 496篇 |
1995年 | 417篇 |
1994年 | 387篇 |
1993年 | 312篇 |
1992年 | 278篇 |
1991年 | 224篇 |
1990年 | 203篇 |
1989年 | 169篇 |
1988年 | 151篇 |
1987年 | 99篇 |
1986年 | 94篇 |
1985年 | 65篇 |
1984年 | 49篇 |
1983年 | 40篇 |
1982年 | 28篇 |
1981年 | 20篇 |
1980年 | 14篇 |
1979年 | 4篇 |
1975年 | 1篇 |
1966年 | 1篇 |
1957年 | 7篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
951.
Yong Guan Huanyao Zhang Anna Zheng Dafu Wei Jian Hu Zhenzhen Wang Xiang Xu 《先进技术聚合物》2019,30(7):1555-1563
Recently, silicone rubber (VMQ) was extensively used in household articles and medical devices. To develop a kind of safe and long‐term antimicrobial VMQ was of great significance. In this work, a kind of vinyl‐contained polyhexamethylene guanidine hydrochloride (VPHMG) was synthesized and used as antimicrobial additive for VMQ. With the increasing of VPHMG addition, the mechanical properties and antimicrobial properties of VMQ‐VPHMG were significantly improved. In particular, the antimicrobial rates against Escherichia coli and Staphylococcus aureus were higher than 99.99% as for 4 wt% of VPHMG addition. Moreover, the surface concentration of VPHMG as well as the antimicrobial rates revealed almost unchanged after being extracted by water and methanol. All the results indicated the vinyl‐contained VPHMG vulcanization and therefore provided the permanent antimicrobial performance for VMQ. 相似文献
952.
Hanghang Wang Haiyan Li Yonggao Zheng Pengcheng Lian Prof. Dr. Xiaobing Wan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(9):2195-2198
In this communication, an unprecedented interception of CnF2n+1(O)SO. radical with a copper-based carbene has been established. Distinguished by wide substrate scopes and mild reaction conditions, this novel radical–carbene coupling reaction (RCC reaction) provides a fundamentally different and mechanistically interesting strategy for the synthesis of perfluoroalkanesulfinate esters. 相似文献
953.
Dr. Yiteng Zheng Ziyu Tang Prof. Simon G. Podkolzin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5174-5179
The development of improved technologies for biomass processing into transportation fuels and industrial chemicals is hindered due to a lack of efficient catalysts for selective oxygen removal. Here we report that platinum nanoparticles decorated with subnanometer molybdenum clusters can efficiently catalyze hydrodeoxygenation of acetic acid, which serves as a model biomass compound. In contrast with monometallic Mo catalysts that are inactive and monometallic Pt catalysts that have low activities and selectivities, bimetallic Pt–Mo catalysts exhibit synergistic effects with high activities and selectivities. The maximum activity occurs at a Pt to Mo molar ratio of three. Although Mo atoms themselves are catalytically inactive, they serve as preferential binding anchors for oxygen atoms while a catalytic transformation proceeds on neighboring surface Pt atoms. Beyond biomass processing, Pt–Mo nanoparticles are promising catalysts for a wide variety of reactions that require a transformation of molecules with an oxygen atom and, more broadly, in other fields of science and technology that require tuning of surface–oxygen interactions. 相似文献
954.
Xin Dong Juan Yang Xiao-Ting Zheng Yan Chen Li-Hong Ye Bin Wang Hui Zheng Jun Cao Qiu-Yan Wang Yu-Han Hu 《Electrophoresis》2020,41(1-2):123-130
A novel micro matrix solid phase dispersion method was successfully used for the extraction of quaternary alkaloids in Phellodendri chinensis cortex. The elution of target compounds was accomplished with sodium hexanesulfonate as the eluent solvent. A neutral ion pair was formed between ion-pairing reagent and positively charged alkaloids in this process, which was beneficial for selectively extraction of polar alkaloids. Several parameters were optimized and the optimal conditions were listed as follows: silica gel as the sorbent, silica to sample mass ratio of 1:1, the grinding time of 1 min. The exhaustive elution of targets was achieved by 200 µL methanol/water (9:1) containing 150 mM sodium hexane sulfonate at pH 4.5. The method validation covered linearity, recovery, precision of intraday and interday, limits of detection, limits of quantitation, and repeatability. This established method was rapid, simple, environmentally friendly, and highly sensitive. 相似文献
955.
Xin Cheng Dr. Zi-Yu Li Li-Hui Mou Yi Ren Dr. Qing-Yu Liu Prof. Dr. Xun-Lei Ding Prof. Dr. Sheng-Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16523-16527
The side-on-end-on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V5N5]−) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV). 相似文献
956.
Meng-Meng Zhao Lin Zhou Ping-Ping Shi Xuan Zheng Xiao-Gang Chen Ji-Xing Gao Lei He Prof. Dr. Qiong Ye Prof. Dr. Cai-Ming Liu Prof. Dr. Da-Wei Fu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(25):6447-6454
Organic–inorganic hybrid perovskite-type multiferroics have attracted considerable research interest owing to their fundamental scientific significance and promising technological applications in sensors and multiple-state memories. The recent achievements with divalent metal dicyanamide compounds revealed such malleable frameworks as a unique platform for developing novel functional materials. Herein, two 3D organic–inorganic hybrid perovskites [Et3P(CH2)2F][Mn(dca)3] ( 1 ) and [Et3P(CH2)2Cl][Mn(dca)3] ( 2 ) (dca=dicyanamide, N(CN)2−) are presented. Accompanying the sequential phase transitions, they display a broad range of intriguing physical properties, including above room temperature ferroelastic behavior, switchable dielectricity, and low-temperature antiferromagnetic ordering (Tc=2.4 K for both 1 and 2 ). It is also worth noting that the spontaneous strain value of 1 is far beyond that of 2 in the first ferroelastic phase, as a result of the precise halogen substitution. From the point view of molecular design, this work should inspire further exploration of multifunctional molecular materials with desirable properties. 相似文献
957.
Dr. Lingxing Zeng Biyu Kang Fenqiang Luo Yixing Fang Cheng Zheng Junbin Liu Renpin Liu Xinye Li Prof. Dr. Qinghua Chen Prof. Dr. Mingdeng Wei Prof. Dr. Qingrong Qian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(58):13411-13421
Sodium/potassium-ion batteries (SIBs/PIBs) arouse intensive interest on account of the natural abundance of sodium/potassium resources, the competitive cost and appropriate redox potential. Nevertheless, the huge challenge for SIBs/PIBs lies in the scarcity of an anode material with high capacity and stable structure, which are capable of accommodating large-size ions during cycling. Furthermore, using sustainable natural biomass to fabricate electrodes for energy storage applications is a hot topic. Herein, an ultra-small few-layer nanostructured MoSe2 embedded on N, P co-doped bio-carbon is reported, which is synthesized by using chlorella as the adsorbent and precursor. As a consequence, the MoSe2/NP-C-2 composite represents exceedingly impressive electrochemical performance for both sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). It displays a promising reversible capacity (523 mAh g−1 at 100 mA g−1 after 100 cycles) and impressive long-term cycling performance (192 mAh g−1 at 5 A g−1 even after 1000 cycles) in SIBs, which are some of the best properties of MoSe2-based anode materials for SIBs to date. To further probe the great potential applications, full SIBs pairing the MoSe2/NP-C-2 composite anode with a Na3V2(PO4)3 cathode also exhibits a satisfactory capacity of 215 mAh g−1 at 500 mA g−1 after 100 cycles. Moreover, it also delivers a decent reversible capacity of 131 mAh g−1 at 1 A g−1 even after 250 cycles for PIBs. 相似文献
958.
Prof. Caihong Fang Guili Zhao Zijun Zhang Qian Ding Nan Yu Zhiqing Cui Ting Bi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7351-7358
Multifunctional metal nanostructures with a hollow feature, especially for nanoframes, are highly attractive owing to their high surface-to-volume ratios. However, pre-grown metal nanocrystals are always involved during the preparation procedure, and a synthetic strategy without the use of a pre-grown template is still a challenge. In this article, a template-free strategy is reported for the preparation of novel AuPt alloy nanoframes through simply mixing HAuCl4 and H2PtCl6 under mild conditions. The alloy nanostructures show a bipyramid-frame hollow architecture with the existence of only the ten ridges and absence of their side faces. This is the first report of bipyramid-like nanoframes and a template-free method under mild conditions. This configuration merges the plasmonic features of Au and highly active catalytic sites of Pt in a single nanostructure, making it an ideal multifunctional platform for catalyzing and monitoring the catalytic reaction in real time. The superior catalytic activity is demonstrated by using the reduction of nitrobenzene to the corresponding aminobenzene as a model reaction. More importantly, the AuPt nanoframes can track the reduction process on the basis of the SERS signals of the reactants, intermediates, and products, which helps to reveal the reaction mechanism. In addition, the AuPt nanoframes show much higher electrocatalytic properties toward the methanol oxidation reaction than commercial Pt/C electrocatalysts. 相似文献
959.
Given a planar continuum Gaussian free field h𝒰 in a domain 𝒰 with Dirichlet boundary condition and any δ > 0, we let be a real-valued smooth Gaussian process where is the average of h𝒰 along a circle of radius δ with center v. For γ > 0, we study the Liouville first-passage percolation (in scale δ), i.e., the shortest path distance in 𝒰 where the weight of each path P is given by . We show that the distance between two typical points is for all sufficiently small but fixed γ > 0 and some constant c* > 0. In addition, we obtain similar upper bounds on the Liouville first-passage percolation for discrete Gaussian free fields, as well as the Liouville graph distance, which roughly speaking is the minimal number of euclidean balls with comparable Liouville quantum gravity measure whose union contains a continuous path between two endpoints. Our results contradict some reasonable interpretations of Watabiki's prediction (1993) on the random distance of Liouville quantum gravity at high temperatures.© 2019 Wiley Periodicals, Inc. 相似文献
960.
工业催化:选择性提升策略 总被引:1,自引:0,他引:1
工业催化直接或间接贡献了世界GDP的20%-30%,推动了产业变革和社会进步.对于工业催化,开发高活性、高选择性和高稳定性的多相催化剂至关重要,而选择性是最主要的挑战.因为实现催化选择性的精确控制是绿色化学的重要概念之一,更是工业催化可持续发展的重要驱动力;而且,选择性不仅决定了催化过程的原子经济性,也影响到后续分离过程的能耗.针对多数工业催化反应存在'活性越高、选择性越低'的相互制约与矛盾问题,本文以若干能源化工催化反应为例,试图总结催化选择性提升的一般策略,以期为有关工业应用的催化新过程提供科学参考.多相催化一般经历与反应物有关的步骤(反应物的外扩散、内扩散和化学吸附)、与反应有关的步骤(活化和表面反应)、以及与产物相关的步骤(产物脱附、内扩散和外扩散).本文依此归纳并举例说明提高选择性的一般策略.在汽油催化吸附脱硫中,主要利用了催化剂中零价镍-氧化锌耦合活性中心的选择吸附策略,使零价镍优先吸附含硫化合物,从而实现选择性脱硫而不饱和烯烃.在甲苯和甲醇侧链烷基化反应中,主要利用了特定空间分布的酸碱吸附位,实现吸附甲苯和稳定甲醛中间体的协同匹配.在乙苯脱乙基型二甲苯异构化反应中,主要利用了双床层对催化剂功能的分离策略,在不同的择形催化剂床层中分别进行乙苯脱乙基反应和二甲苯异构化反应,从而提高对二甲苯的产量.在苯选择加氢制环己烯反应中,主要利用强化产品脱附的策略,促进环己烯产品从亲水改性的催化剂表面脱附,实现环己烯选择性的提升.这些炼油与化工研究案例中同时存在多个连串-平行反应,主要是利用吸附中心、反应中心在时间或空间上的耦合、解耦或限域策略,调控不同途径的扩散能垒、反应能垒,实现了催化剂选择性的提升.多相催化多是复杂过程,基于提高选择性的初步认识,还要结合具体复杂催化过程,系统研究单策略以及多策略组合作用下的选择催化过程,实现在合理时间尺度、空间尺度上设计高选择性的催化剂,而这本质上是一种介尺度催化. 相似文献