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181.
Two multi-nuclear titanium complexes [Ti(η5-Cp*)Cl(μ-O)]3 (1) and [(η5-Cp*TiCl)(μ-O)2(η5-Cp*Ti)2(μ-O)(μ-O)2]2Ti (Cp* = C5Me5) (2) have been investigated as the precatalysts for syndiospecific polymerization of styrene. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, complexes 1 and 2 display much higher catalytic activities towards styrene polymerization, and produce the higher molecular weight polystyrenes with higher syndiotacticities and melting temperatures (Tm) than the mother complex Cp*TiCl3 does when the polymerization temperature is above 70℃and the Al/Ti molar ratio is in the low range especially.  相似文献   
182.
Hydrodynamic Cavitation (HC) offers an attractive platform for intensifying oxidative desulphurization of fuels. In the first part of this work, we present new results on oxidising single ring thiophene in a model fuel over the extended range of volume fraction of organic phase from 2.5 to 80 v/v %. We also present influence of type and scale of HC device on performance of oxidative desulphurization. Further experiments revealed that oxidising radicals generated in-situ by HC alone were not able to oxidise dual ring thiophenes. External catalyst (formic acid) and oxidising agents (hydrogen peroxide, H2O2) were therefore used with HC. Based on our prior work with acoustic cavitation (AC), the volumetric ratios for H2O2 and formic acid were identified as 0.95 v/v % and 6.25 v/v % respectively. The data of oxidation of dual ring thiophenes with n-dodecane and n-hexane as model fuels and typical transport fuels (diesel, kerosene, and petrol) using these oxidant and catalyst is presented. The observed performance with HC was compared with results obtained from a stirred tank and AC set-up. The presented data indicates that HC is able to intensify oxidation of sulphur species. The presented results provide a sound basis for further developments on HC based oxidative desulphurization processes.  相似文献   
183.
Multi-metal electrocatalysts provide nearly unlimited catalytic possibilities arising from synergistic element interactions. We propose a polymer/metal precursor spraying technique that can easily be adapted to produce a large variety of compositional different multi-metal catalyst materials. To demonstrate this, 11 catalysts were synthesized, characterized, and investigated for the oxygen evolution reaction (OER). Further investigation of the most active OER catalyst, namely CoNiFeMoCr, revealed a polycrystalline structure, and operando Raman measurements indicate that multiple active sites are participating in the reaction. Moreover, Ni foam-supported CoNiFeMoCr electrodes were developed and applied for water splitting in flow-through electrolysis cells with electrolyte gaps and in zero-gap membrane electrode assembly (MEA) configurations. The proposed alkaline MEA-type electrolyzers reached up to 3 A cm−2, and 24 h measurements demonstrated no loss of current density of 1 A cm−2.  相似文献   
184.
We demonstrate the great feasibility of MBenes as a new class of tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO3RR). As a proof of concept, FeB2 is first employed as a model MBene catalyst for the NO3RR, showing a maximum NH3-Faradaic efficiency of 96.8 % with a corresponding NH3 yield of 25.5 mg h−1 cm−2 at −0.6 V vs. RHE. Mechanistic studies reveal that the exceptional NO3RR activity of FeB2 arises from the tandem catalysis mechanism, that is, B sites activate NO3 to form intermediates, while Fe sites dissociate H2O and increase *H supply on B sites to promote the intermediate hydrogenation and enhance the NO3-to-NH3 conversion.  相似文献   
185.
As a special carbon material, graphdiyne (GDY) features the superiorities of incomplete charge transfer effect on the atomic level, tunable electronic structure and anchoring metal atoms directly with organometallic coordination bonds M (metal)-C (alkynyl carbon in GDY), providing it an ideal platform to construct single-atom catalysts (ACs). The coordination environment of single atoms anchored on GDY plays a key role in their catalytic performance. The mini-review highlights state-of-the-art progress in the rational design of GDY-based ACs and their applications, and mainly reveals the relationship between the coordination engineering of the GDY-based ACs and corresponding catalytic performance. Finally, some prospects concerning the future development of GDY-based ACs in energy conversion are also discussed.  相似文献   
186.
Fe−N−C catalysts with single-atom Fe−N4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, the limited intrinsic activity and dissatisfactory durability have significantly restrained the practical application of proton-exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting the ORR performance and stability of Fe−N4 catalysts. The integration of Fe−N4 configurations with highly uniform Co4 ACs on the N-doped carbon substrate (Co4@/Fe1@NC) is realized through a “pre-constrained” strategy using Co4 molecular clusters and Fe(acac)3 implanted carbon precursors. The as-developed Co4@/Fe1@NC catalyst exhibits excellent ORR activity with a half-wave potential (E1/2) of 0.835 V vs. RHE in acidic media and a high peak power density of 840 mW cm−2 in a H2−O2 fuel cell test. First-principles calculations further clarify the ORR catalytic mechanism on the identified Fe−N4 that modified with Co4 ACs. This work provides a viable strategy for precisely establishing atomically dispersed polymetallic centers catalysts for efficient energy-related catalysis.  相似文献   
187.
Upgrading CO2 into multi-carbon (C2+) compounds through the CO2 reduction reaction (CO2RR) offers a practical approach to mitigate atmospheric CO2 while simultaneously producing high value chemicals. The reaction pathways for C2+ production involve multi-step proton-coupled electron transfer (PCET) and C−C coupling processes. By increasing the surface coverage of adsorbed protons (*Had) and *CO intermediates, the reaction kinetics of PCET and C−C coupling can be accelerated, thereby promoting C2+ production. However, *Had and *CO are competitively adsorbed intermediates on monocomponent catalysts, making it difficult to break the linear scaling relationship between the adsorption energies of the *Had/*CO intermediate. Recently, tandem catalysts consisting of multicomponents have been developed to improve the surface coverage of *Had or *CO by enhancing water dissociation or CO2-to-CO production on auxiliary sites. In this context, we provide a comprehensive overview of the design principles of tandem catalysts based on reaction pathways for C2+ products. Moreover, the development of cascade CO2RR catalytic systems that integrate CO2RR with downstream catalysis has expanded the range of potential CO2 upgrading products. Therefore, we also discuss recent advancements in cascade CO2RR catalytic systems, highlighting the challenges and perspectives in these systems.  相似文献   
188.
Dual-atom catalysts (DACs) have been a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising to enhance performance and even catalyze more complex reactions. However, precisely regulating active site structure and uncovering dual-atom metal interaction remain grand challenges. In this review, we clarify the significance of the inter-metal interaction of DACs based on the understanding of active center structures. Three diatomic configurations are elaborated, including isolated dual single-atom, N/O-bridged dual-atom, and direct dual-metal bonding interaction. Subsequently, the up-to-date progress in heterogeneous oxidation reactions, hydrogenation/dehydrogenation reactions, electrocatalytic reactions, and photocatalytic reactions are summarized. The structure-activity relationship between DACs and catalytic performance is then discussed at an atomic level. Finally, the challenges and future directions to engineer the structure of DACs are discussed. This review will offer new prospects for the rational design of efficient DACs toward heterogeneous catalysis.  相似文献   
189.
Efficient and inexpensive catalysts for the O2 reduction reaction (ORR) are needed for the advancement of renewable energy technologies. In this study, we designed a computational catalyst-screening method to identify single and di-atom metal dopants from first-row transition elements supported on defect-containing nitrogenated graphene surfaces for the ORR. Based on formation-energy calculations and micro-kinetic modelling of reaction pathways using intermediate binding free energies, we have identified four potentially interesting single-atom catalysts (SACs) and fifteen di-atom catalysts (DACs) with relatively high estimated catalytic activity at 0.8 V vs RHE. Among the best SACs, MnNC shows high stability in both acidic and alkaline media according to our model. For the DACs, we found four possible candidates, MnMn, FeFe, CoCo, and MnNi doped on quad-atom vacancy sites having considerable stability over a wide pH range. The remaining SACs and DACs with high activity are either less stable or show a stability region at an alkaline pH.  相似文献   
190.
This work reported that a silicon-centered alkyl borane/ammonium salt binary (two-component) catalyst exhibits much higher activity than its bifunctional analogue (one-component) for the ring-opening polymerization of propylene oxide, showing 7.3 times the activity of its bifunctional analogue at a low catalyst loading of 0.01 mol %, and even 15.3 times the activity at an extremely low loading of 0.002 mol %. By using 19F NMR spectroscopy, control experiments, and theoretical calculation we discovered that the central silicon atom displays appropriate electron density and a larger intramolecular cavity, which is useful to co-activate the monomer and to deliver propagating chains, thus leading to a better intramolecular synergic effect than its bifunctional analogue. A unique two-pathway initiation mode was proposed to explain the unusual high activity of the binary catalytic system. This study breaks the traditional impression of the binary Lewis acid/nucleophilic catalyst with poor activity because of the increase in entropy.  相似文献   
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