全文获取类型
收费全文 | 730篇 |
免费 | 242篇 |
国内免费 | 182篇 |
专业分类
化学 | 1131篇 |
晶体学 | 3篇 |
力学 | 1篇 |
综合类 | 3篇 |
物理学 | 16篇 |
出版年
2024年 | 6篇 |
2023年 | 25篇 |
2022年 | 62篇 |
2021年 | 64篇 |
2020年 | 169篇 |
2019年 | 76篇 |
2018年 | 84篇 |
2017年 | 41篇 |
2016年 | 74篇 |
2015年 | 70篇 |
2014年 | 60篇 |
2013年 | 55篇 |
2012年 | 49篇 |
2011年 | 45篇 |
2010年 | 26篇 |
2009年 | 26篇 |
2008年 | 34篇 |
2007年 | 30篇 |
2006年 | 29篇 |
2005年 | 25篇 |
2004年 | 27篇 |
2003年 | 12篇 |
2002年 | 10篇 |
2001年 | 10篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
排序方式: 共有1154条查询结果,搜索用时 31 毫秒
31.
Yuping Liu Hongxing Wang Fengru Liu Jialing Kang Dr. Feng Qiu Prof. Changchun Ke Dr. Yu Huang Prof. Sheng Han Prof. Fan Zhang Prof. Xiaodong Zhuang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2155-2164
Transition metal-based nanoparticle-embedded carbon materials have received increasing attention for constructing next-generation electrochemical catalysts for energy storage and conversion. However, designing hybrid carbon materials with controllable hierarchical micro/mesoporous structures, excellent dispersion of metal nanoparticles, and multiple heteroatom-doping remains challenging. Here, a novel pyridinium-containing ionic hypercrosslinked micellar frameworks (IHMFs) prepared from the core–shell unimicelle of s-poly(tert-butyl acrylate)-b-poly(4-bromomethyl) styrene (s-PtBA-b-PBMS) and linear poly(4-vinylpyridine) were used as self-sacrificial templates for confined growth of molybdenum disulfide (MoS2) inside cationic IHMFs through electrostatic interaction. After pyrolysis, MoS2-anchored nitrogen-doped porous carbons possessing tunable hierarchical micro/mesoporous structures and favorable distributions of MoS2 nanoparticles exhibited excellent electrocatalytic activity for hydrogen evolution reaction as well as small Tafel slope of 66.7 mV dec−1, low onset potential, and excellent cycling stability under acidic condition. Crucially, hierarchical micro/mesoporous structure and high surface area could boost their catalytic hydrogen evolution performance. This approach provides a novel route for preparation of micro/mesoporous hybrid carbon materials with confined transition metal nanoparticles for electrochemical energy conversion. 相似文献
32.
Zhong Ren Li Xiao Gongwei Wang Juntao Lu Lin Zhuang 《天然气化学杂志》2014,(3):265-268
Although most transition metals have been tested as the promoter to Pt for electrocatalysis toward fuel cell reactions,semi-conductor elements,such as Si,have hitherto not been examined.Here we report a simple synthesis of intermetallic Pt2Si electrode using magnetron sputtering and the electrocatalysis toward ethanol oxidation reaction(EOR).In comparison to Pt,the intermetallic Pt2Si surface turns out to be much more active in catalyzing the EOR:the onset potential shifts negatively by 150 mV,and the current density at 0.6 V increases by a magnitude of one order.Such an enormous enhancement in EOR catalysis is ascribed to the promotion effects of Si,which can not only provide active surface oxygenated species to accelerate the removal of COads,but also strongly alter the electronic property of Pt,as clearly indicated by the core-level shift in XPS spectrum. 相似文献
33.
Dr. Christian Kulp Konrad Gillmeister Prof. Dr. Wolf Widdra Prof. Michael Bron 《Chemphyschem》2013,14(6):1205-1210
The synthesis of Cu(core)Pt(shell) model catalysts by the direct electrochemical deposition of Pt on Cu particles is presented. Cu particles with an average diameter of 200 nm have been deposited on glassy‐carbon electrodes by double pulse electrodeposition from a copper sulfate solution. Subsequent deposition from a platinum nitrate solution under potential control allows for a high selectivity of the Pt deposition towards Cu. Using a combination of cyclic voltammetry, XPS and sputtering, the structure of the generated particles has been analyzed and their core–shell configuration proven. It is shown that the electrocatalytic activity for the oxygen reduction is similar to that of other PtCu catalyst systems. The synthesized structures could allow for the analysis of structure–activity relations of core–shell catalysts on the way to the simple and controlled synthesis of supported Cu(core)Pt(shell) nanoparticles as oxygen reduction catalysts. 相似文献
34.
采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料(WN-W/NOMC),作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%(w/w)时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m2·g-1,透射电子显微镜(TEM)测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O2饱和的0.1 mol·L-1 KOH溶液中测试了材料的氧还原催化性能(ORR),显示其起始电位为0.87 V(vs RHE),极限电流密度为4.49 mA·cm-2,氧还原反应的转移电子数为3.4,接近于20%(w/w)商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳(0.99 V,5.1 mA·cm-2),但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。 相似文献
35.
燃料电池阴极氧还原(ORR)催化剂目前主要以商业Pt/C为主, 其高成本和稀缺性极大地限制了燃料电池的广泛应用. 为了替代Pt/C催化剂, 廉价高效的非贵金属催化剂目前受到了广泛的研究和关注. 利用氧化石墨烯(GO)为诱导模板, 借助表面丰富的含氧官能团, 实现了Co基金属有机框架材料(MOF) (ZIF-67)在GO表面的原位生长, 构筑了ZIF-67/GO层状复合材料. 热解过程中, 石墨烯的存在有效抑制了Co纳米颗粒的团聚, 并且很好地维持了原始的层状结构. 最终获得的Co@N-C/rGO复合催化剂材料实现了活性位的高度分散, 并且具有丰富的孔结构和优异的导电性能. 在电化学性能测试中Co@N-C/rGO表现出优异的ORR性能, 其起始电位为0.96 V, 半波电位0.83 V, 远优于ZIF-67直接热解得到的Co@N-C材料, 且性能与商业Pt/C催化剂相当. 此外, Co@N-C/rGO复合催化剂还表现出良好的催化稳定性和甲醇耐受性, 显示出该材料作为燃料电池氧还原催化剂的重要潜力. 相似文献
36.
Dr. Antonio Del Vecchio Arianna Sinibaldi Valeria Nori Giuliana Giorgianni Dr. Graziano Di Carmine Dr. Fabio Pesciaioli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202200818
Synergistic catalysis offers the unique possibility of simultaneous activation of both the nucleophile and the electrophile in a reaction. A requirement for this strategy is the stability of the active species towards the reaction conditions and the two concerted catalytic cycles. Since the beginning of the century, aminocatalysis has been established as a platform for the stereoselective activation of carbonyl compounds through HOMO-raising or LUMO-lowering. The burgeoning era of aminocatalysis has been driven by a deep understanding of these activation and stereoinduction modes, thanks to the introduction of versatile and privileged chiral amines. The aim of this review is to cover recent developments in synergistic strategies involving aminocatalysis in combination with organo-, metal-, photo-, and electro-catalysis, focusing on the evolution of privileged aminocatalysts architectures. 相似文献
37.
狄尔斯-阿尔德(Diels-Alder)可以构建结构丰富的有机化合物,被认为是现代有机化学中的基石反应之一。自1928年被发现以来,Diels-Alder (D-A)反应得到了深入发展,这主要是由于该反应能够产生六元环结构,可以一步反应得到具有四个立体中心的产物,从而大大增加分子的复杂性。这种特殊的转化已广泛应用于复杂天然产物的合成、药物化学以及材料科学等领域。近十年,大量天然生物酶(如SpnF、MaDA等)被发现可用于体外单独催化D-A反应,同时,大量的非酶催化剂(如路易斯酸、过渡金属与配体复合物等)也被应用于催化D-A反应。本文主要从D-A反应催化剂的类型分类,对近年来天然酶、酸、过渡金属、电催化等参与的D-A反应进行简要概述,同时对催化剂所存在的问题和局限性进行总结,并对今后发展做了展望。 相似文献
38.
研究影响电催化氧还原反应活性的因素对于合理设计高效的氧还原反应催化剂至关重要。调节催化剂电子结构通常被用于精确调控电催化氧还原反应活性。然而, 该反应发生在液/气/固界面, 很少有报道调控分子催化剂的亲疏水性来提高其催化活性。在此, 我们报道了两种钴卟啉NO2-CoP(5,10,15,20-四(4-硝基苯基)钴卟啉)和5F-CoP(5,10,15,20-四(五氟苯基)钴卟啉)并研究了其电催化氧还原反应性能。通过同时调控meso-位取代基的电子结构和亲水性能, NO2-CoP显示出比5F-CoP更高的电催化氧还原反应活性, 其半波电位向阳极方向移动近60 mV。NO2-CoP比5F-CoP具有更好的亲水性。理论计算表明, NO2-CoP比5F-CoP更容易有效地与O2分子结合形成CoIII-O2·-。这项工作提供了一个简单而有效的策略, 通过使用吸电子和亲水取代基来提高钴卟啉的氧还原反应活性。该策略对于设计和开发其他用于电催化的分子催化剂体系也具有重要的启发意义。 相似文献
39.
Alejandra Medrano-Banda Dr. Alfonso Crespo-Yapur Dr. Miguel Ángel Velasco-Soto Dr. Marcelo Videa 《ChemistryOpen》2022,11(2):e202100241
The synthesis of hybrid platinum materials is fundamental to enable alkaline water electrolysis for cost-effective H2 generation. In this work, we have used a galvanostatic method to co-deposit PtNi films onto polycrystalline gold. The surface concentrations of Ni (ΓNi) and Pt (ΓPt) were calculated from electrochemical measurements; the ΓPt/ΓNi ratio and electrocatalytic activity of these materials towards hydrogen evolution reaction (HER) in 1 M KOH show a strong dependence on the current density pulse applied during the electrodeposition. Analysis of the Tafel parameters hints that, on these deposits, HER proceeds through a Volmer-Heyrovsky mechanism. The galvanostatically deposited PtNi layers present a high current output per Pt gram, 3199 A gPt−1, which is significantly larger compared to other PtNi-based materials obtained by more extended and more complex synthesis methods. 相似文献
40.
Sebastian Wöllner Timothy Nowak Dr. Gui-Rong Zhang Dr. Nils Rockstroh Dr. Hanadi Ghanem Prof. Dr. Stefan Rosiwal Prof. Dr. Angelika Brückner Prof. Dr. Bastian J. M. Etzold 《ChemistryOpen》2021,10(5):600-606
Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) offers a renewable approach to produce the value-added platform chemical 2,5-furandicarboxylic acid (FDCA). The key for the economic viability of this approach is to develop active and selective electrocatalysts. Nevertheless, a reliable catalyst evaluation protocol is still missing, leading to elusive conclusions on criteria for a high-performing catalyst. Herein, we demonstrate that besides the catalyst identity, secondary parameters such as materials of conductive substrates for the working electrode, concentration of the supporting electrolyte, and electrolyzer configurations have profound impact on the catalyst performance and thus need to be optimized before assessing the true activity of a catalyst. Moreover, we highlight the importance of those secondary parameters in suppressing side reactions, which has long been overlooked. The protocol is validated by evaluating the performance of free-standing Cu-foam, and CuCoO modified with NaPO2H2 and Ni, which were immobilized on boron-doped diamond (BDD) electrodes. Recommended practices and figure of merits in carefully evaluating the catalyst performance are proposed. 相似文献