全文获取类型
收费全文 | 6335篇 |
免费 | 584篇 |
国内免费 | 3396篇 |
专业分类
化学 | 9849篇 |
晶体学 | 38篇 |
力学 | 21篇 |
综合类 | 85篇 |
数学 | 8篇 |
物理学 | 314篇 |
出版年
2024年 | 8篇 |
2023年 | 110篇 |
2022年 | 193篇 |
2021年 | 246篇 |
2020年 | 339篇 |
2019年 | 363篇 |
2018年 | 319篇 |
2017年 | 306篇 |
2016年 | 308篇 |
2015年 | 299篇 |
2014年 | 425篇 |
2013年 | 594篇 |
2012年 | 397篇 |
2011年 | 477篇 |
2010年 | 393篇 |
2009年 | 365篇 |
2008年 | 451篇 |
2007年 | 451篇 |
2006年 | 413篇 |
2005年 | 415篇 |
2004年 | 444篇 |
2003年 | 387篇 |
2002年 | 298篇 |
2001年 | 300篇 |
2000年 | 305篇 |
1999年 | 217篇 |
1998年 | 210篇 |
1997年 | 224篇 |
1996年 | 166篇 |
1995年 | 190篇 |
1994年 | 152篇 |
1993年 | 193篇 |
1992年 | 114篇 |
1991年 | 62篇 |
1990年 | 64篇 |
1989年 | 42篇 |
1988年 | 28篇 |
1987年 | 16篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co3Mn2@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―Nx (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN− ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.![]()
相似文献
62.
Formation of active phases of Fe/C,Cr/C and Fe–Cr/C catalysts in oxidative dehydrogenation of ethane
《Mendeleev Communications》2023,33(3):422-424
The oxidative dehydrogenation of ethane into ethylene using CO2 as an oxidant at temperatures of 650–750 °C was carried out over Fe/C, Cr/C and Fe–Cr/C catalysts deposited on a carbon support. Before and after the reaction the catalysts were investigated by X-ray powder diffraction (XRD), in situ magnetometry and transmission electron microscopy methods. The correlation between activity of Fe/C, Cr/C and Fe–Cr/C catalytic systems and their phase composition was established. 相似文献
63.
采用浸渍法制备了经过不同聚合物分散剂处理的Pt/SAPO-11催化剂,并通过X射线衍射(XRD)、透射电子显微镜(TEM)、N2吸附-脱附和NH3程序升温脱附(TPD)等对催化剂的组织结构进行了表征。结果表明,分散剂不会破坏催化剂的结构,反而提高了其孔体积、孔径和比表面积,同时改变了沸石的酸强度和酸量,其中以聚乙烯吡咯烷酮处理的Pt/SAPO-11催化剂孔体积、孔径和酸性分布最佳。在固定床反应器上对不同分散剂处理的Pt/SAPO-11催化剂催化性能进行评价,结果表明聚乙烯吡咯烷酮处理的Pt/SAPO-11催化剂也表现出最佳的催化性能,麻风树油的加氢脱氧率高达99.45%,生物航空煤油组分收率和异构烷烃组分(C8~C16)的选择性分别达到了44.67%和56.37%。 相似文献
64.
65.
为了提高Cu/USY催化剂在乙炔氢氯化反应中的催化活性,设计并成功制备了一系列离子液体修饰的分子筛负载的铜基催化剂(Cu@TPPB/USY).当铜和TPPB的百分含量均为15时,在反应温度为160℃,乙炔气体空速为120 h-1,氯化氢与乙炔的摩尔比为1.25:1的条件下,催化剂的乙炔转化率提升了1.17倍,氯乙烯选择性一直保持在98%以上.结合催化剂的傅里叶红外(FT-IR)、 N2物理吸脱附(BET)、热重分析(TG)、 X射线光电子能谱(XPS)、透射电镜(TEM)、 X射线衍射(XRD)、氢气程序升温还原(H2-TPR)和等离子体发射光谱(ICP-OES)的表征,认为TPPB的修饰不仅可以促进催化剂中Cu物种的分散,抑制其还原和流失,还能减少催化剂表面积碳、增强Cu活性物种与载体间的相互作用力,有效地提高Cu/USY催化剂的催化活性. 相似文献
66.
利用ALD制备了TiO2限域的Pd催化剂, 研究了限域空间内Pd纳米颗粒与TiO2的界面作用对1,4-丁炔二醇(BYD)加氢性能的影响. 相比于管外负载型催化剂, 限域催化剂在催化1,4-丁炔二醇选择性加氢反应中体现出非常高的催化活性和1,4-丁烯二醇的选择性. HR-TEM、 EDX-Mapping、 XRD、 XPS和H2-TPR表征说明, 限域体系中Pd-TiO2的界面相互作用强于传统TiO2表面负载型Pd催化剂, 这种强界面作用不仅能够提高BYD的加氢活性, 也可抑制半加氢产物1,4-丁烯二醇的异构化和深度加氢, 提高1,4-丁烯二醇的选择性, 而且限域结构也可阻止管内壁Pd纳米颗粒的脱落, 提高催化剂的稳定性. 相似文献
67.
Surin Saipanya Li Fang Suwaphid Themsirimongkon Suphitsara Maturost Natthapong Pongpichayakul Napapha Promsawan Paralee Waenkaew 《先进技术聚合物》2023,34(1):120-133
The aim of this research was to study the efficiency of polyvinyl alcohol (PVA)-modified graphene oxide (GO) as a supporting material for catalysts that oxidize formic acid. The active metal catalysts (e.g., Pt and Pd) were electrodeposited on PVA/GO surfaces. The morphologies of the prepared catalysts were characterized by scanning electron microscopy and transmission electron microscopy, while their chemical compositions were identified by X-ray diffraction and X-ray photoelectron spectroscopy. The results show that compared with the other catalysts on GO, the prepared active PtPd alloy catalyst nanoparticles with 11.49–20.73 nm sizes were well dispersed on the PVA/GO surfaces. Electrochemical results indicate that the activities of the catalysts with PVA provided a higher current density than that of the catalysts without PVA. The bimetallic 3Pt3Pd/PVA/GO catalyst showed the greatest catalytic activity, stability, and CO oxidation when compared to those of other catalysts. The electronic, morphological, and structural properties promote the mass-charge transfer through the interaction. These results indicate that the PVA-modified GO provides a suitable site for active bimetallic catalyst surfaces, resulting in excellent formic acid oxidation and high CO elimination. The 3Pt3Pd/PVA/GO electrocatalyst is promising for enhancing formic acid oxidation. 相似文献
68.
A straightforward manufacture strategy is proposed to obtain an efficient and robust palladium-alumina (Pd0/Al2O3) cermet monolithic catalyst, specifically designed to perform safe microwave assisted organic synthesis (MAOS). In this approach, a cermet catalyst with high surface area, controlled composition and adapted shape and dimensions to a microwave reactor vessel is generated via 3D printing technology and sintering. The resulting catalyst has been explored in heterogeneous Suzuki, Sonogashira, Stille and Heck cross-coupling reactions, in MAOS. The Pd0 catalyst is permanently active, stable, without leaching and can be recycled and reused at least 200 reaction cycles. The generation of hot spots, sparking or hazardous discharges is controlled by the effective immobilization of the palladium in the monolithic structure during the reaction. The palladium content is forming part of both the internal and external structure, providing greater mechanical resistance and catalytic activity with respect to the basic ceramic material (alumina). 相似文献
69.
Bize Gao Dr. Quanren Zhu Prof. Dr. Yanhui Yi Yue Li Guoxing Wu Yitong Guo Prof. Dr. Zhaochi Feng Prof. Dr. Hongchen Guo 《欧洲无机化学杂志》2023,26(22):e202200661
The epoxidation of propylene with dilute H2O2 aqueous solution over titanium silicalite-1 (TS-1) zeolite catalyst is a green chemical reaction for propylene oxide (PO) production. Carrying out the reaction in gas-phase can get rid of problems caused by using methanol solvent. This paper reports an attempt of using non-zeolite catalyst for the gas-phase epoxidation. Amorphous Ti/SiO2, obtained by grafting amorphous SiO2 with TCl4 in ethanol solvent in a chemical liquid-phase deposition (CLD) process, has been used as the catalyst. Results show that the CLD Ti/SiO2 with appropriate Si/Ti molar ratio is an active catalyst for gas-phase epoxidation, achieving 9.8 % propylene conversion and 66.9 % PO selectivity with 40.3 % H2O2 utilization, which indicates that this amorphous Ti/SiO2 catalyst deserves extensive studies in the future. 相似文献
70.
Dr. Yukun Shi Jie Li Xuejiao Shen Peiling Xie Jiahui Gong Hongchun Sun Xiaojing Hu Baolin Zhu Prof. Dr. Weiping Huang 《Chemphyschem》2023,24(12):e202200910
The objective of the tandem hydroformylation-hydrogenation of alkenes to corresponding alcohols was to design an efficient and stable heterogeneous catalyst. To this end, a series of novel heterogeneous graphitic carbon nitride (g-CN) supported bimetallic Rh−Co nanoparticle catalysts (Rh−Co/g-CN) were prepared and subsequently studied for this one-pot two-step reaction. The lamellar structure makes Rh and Co nanoparticles with diameters of <1 nm and 20 nm, respectively, homogeneously deposited on the surface of g-CN layers, exhibit remarkable conversion of styrene (99.9 %) and chemoselectivity for alcohol (87.8 %). More importantly, Co nanoparticles are found to play an important role in the improvement of the chemoselectivity for alcohol due to the formation of catalytic active species [HCo(CO)y]. Besides the detailed investigation of the catalytic properties of Rh−Co/g-CN under different reaction conditions, the reuse of Rh−Co/g-CN was conducted for five times and no evident decrease in the activity and chemoselectivity was observed. Therefore, we expect that this work could offer an initial insight into g-CN-based heterogeneous catalyst on the tandem hydroformylation-hydrogenation reaction. 相似文献