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1.
The coupling of reaction and diffusion between neighboring active sites in the catalyst pore leads to the spatiotemporal fluctuation in component concentration, which is very important to catalyst performance and hence its optimal design. Molecular dynamics simulation with hard-sphere and pseudo-particle modeling has previously revealed the non-stochastic concentration fluctuation of the reactant/product near isolated active site due to such coupling, using a simple model reaction of A → B in 2D pores. The topic is further developed in this work by studying the concentration fluctuation due to such coupling between neighboring active sites in 3D pores. Two 3D pore models containing an isolated active site and two adjacent active sites were constructed, respectively. For the isolated site, the concentration fluctuation intensifies for larger pores, but the product yield decreases, and for a given pore size, the product yield reaches a peak at a certain reactant concentration. For two neighboring sites, their distance (d) is found to have little effect on the reaction, but significant to the diffusion. For the same reaction competing at both sites, larger d leads to more efficient diffusion and better overall performance. However, for sequential reactions at the two sites, higher overall performance presents at a smaller d. The results should be helpful to the catalyst design and reaction control in the relevant processes.  相似文献   
2.
Catalyst slurries (inks) were prepared with and without thermal treatment to determine the support/ionomer structures and interactions in the catalyst layer (CL) which impact on membrane electrode performance and durability. The thermal treatment of the ink has a nominal effect on the ionomer/support structure in which the carbon support is non-graphitised. The agglomerate/aggregate structures have a high degree of support/ionomer interface and sufficient macroporosity for water movement in the CL. This improves the membrane electrode assembly (MEA) performance, but also accelerates electrochemical carbon degradation. Thermal treatment of graphitised support-containing inks resulted in increased performance facilitated by a larger support/ionomer interface. Without thermal treatment, the more hydrophobic support would form aggregate structures in which water contact was restricted, limiting proton transfer, isolating catalyst, decreasing performance. The water limited access, would however, prolong stability during accelerates carbon degradation. The electrochemical properties were studied using full and half MEA cells.  相似文献   
3.
Large amounts of water containing-ammonium nitrogen(NH4+-N)have attracted increasing attention.Catalytic ozonation technology,involving the generation of hydroxyl radical(OH)with strong oxidation ability,was originally utilized to degrade organic-containing wastewater.In this paper,Ce/MnOx composite metal oxide catalysts prepared with different preparation conditions were used to degrade wastewater containing inorganic pollutant(NH4+-N).The as-prepared catalyst features were characterized using X-ray diffraction(XRD),Brunauer-Emmett-Teller method(BET),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and H2-temperature programmed reduction(H2-TPR)techniques.The results show that the catalyst,prepared by conditions with precipitant Na2CO3 and Ce/Mn molar ratio 1:2 calcined at 400℃for 3 h in pH 11.0,displays the optimal performance,with the removal rate of NH4+-N and selectivity to gaseous nitrogen,88.14 wt%and 53.67 wt%,respectively.The effects of several operating factors including solution pH,initial NH4+-N concentrations and scavengers were evaluated.In addition,XRD patterns of catalyst with the best performance and the comparative study on decontamination of NH4+-N by various processes(O3,catalyst and catalyst/O3)show that the primary metal oxides are CeO2 and MnO2 in Ce/MnOx composite metal oxide catalysts,which have a synergistic effect on the catalytic ozonation of NH4+-N,and the new phase MnO2 plays a great role.After 5 consecutive use cycles,the degradation efficiency is declined slightly,and can still achieve better than 70 wt%over 1 h reaction.Additionally,the application of catalytic ozonation for actual wastewater on the removal rate of NH4+-N was investigated.Possible mechanism and degradation pathway of NH4+-N were also proposed.In a word,the application of CeO2-MnO2 composite metal oxide catalysts in catalytic ozonation can be regarded as an effective,feasible and promising method for the treatment of NH4+-N.  相似文献   
4.
5-Hydroxymethylfurfural (5-HMF), as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels, has been attracted extensive attention. In this research, using Pickering high internal phase emulsions (Pickering HIPEs) as template and functional metal-organic frameworks (MOFs, UiO-66-SO3H and UiO-66-NH2)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process, which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF. The effects of the emulsion parameters including the amount of surfactant (ranging from 0.5% to 2.0% (mass)), the internal phase volume fraction (ranging from 75% to 90%) and the acid/base Pickering particles mass ratio (ranging from 0:6 to 6:0) on the morphology and catalytic performance of solid catalyst were systematically researched. The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion, and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield. The highest 5-HMF yield, about 40.5%, can be obtained by using polymer/MOFs composite as catalyst (Poly-P12, the pore size of (53.3 ±11.3) μm, the acid density of 1.99 mmol·g-1 and the base density of 1.13 mol·g-1) under the optimal reaction conditions (130 ℃, 3 h). Herein, the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method, which provided a favorable experimental basis and theoretical reference for achieving efficient production of high added-value product from abundant biomass.  相似文献   
5.
By doping with 5 wt % TiF4 and activated carbon (AC), onset and main dehydrogenation temperatures of MgH2 significantly reduce (ΔT = 138 and 109 °C, respectively) with hydrogen capacity of 4.4 wt % H2. Up-scaling to storage tank begins with packing volume and sample weight of 28.8 mL and ~14.5 g, respectively, and continues to 92.6 mL and ~60.5–67 g, respectively. Detailed hydrogen sorption mechanisms and kinetics of the tank tightly packed with four beds of MgH2TiF4-AC (~60.5 g) are investigated. De/rehydrogenation mechanisms are detected by three temperature sensors located at different positions along the tank radius, while hydrogen permeability is benefited by stainless steel mesh sheets and tube inserted in the hydride beds. Fast desorption kinetics of MgH2TiF4-AC tank at ~275–283 °C, approaching to onset dehydrogenation temperature of the powder sample (272 °C) suggests comparable performances of laboratory and tank scales. Hydrogen desorption (T = 300 °C and P(H2) = 1 bar) and absorption (T = 250 °C and P(H2) = 10–15 bar) of MgH2TiF4-AC tank provide gravimetric and volumetric capacities during the 1st-2nd cycles of 4.46 wt % H2 and 28 gH2/L, respectively, while those during the 3rd-15th cycles are up to 3.62 wt % H2 and 23 gH2/L, respectively. Due to homogeneous heat transfer along the tank radius, de/rehydrogenation kinetics superior at the tank center and degrading forward the tank wall can be due to poor hydrogen permeability. Particle sintering and/or agglomeration upon cycling yield deficient hydrogen content reproduced.  相似文献   
6.
In this paper,CeO_2 with a pore size of 2-4 nm was synthesized by hydrothermal method.The CeO_2 modified graphene-supported Pt catalyst was prepared by the microwave-assisted ethylene glycol reduction chloroplatinic acid method,and the effect of the addition of CeO_2 prepared by different hydrothermal reaction time on the catalytic performance of Pt-based catalysts was investigated.The microstructures of CeO_2 and catalysts were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),specific surface area and pore size analyzer(BET),scanning electron microscopy(SEM) and electron spectroscopy(EDAX),transmission electron microscopy(TEM),and the catalysts electrochemical performance was tested by electrochemical workstation.The results show that the catalytic performance of the four catalysts with CeO_2 is better than that of the catalyst without CeO_2.Adding CeO_2 with a specific surface area of 120.15 m~2/g prepared by hydrothermal reaction time of 39 h to Pt/C synthesis catalyst,its electrocatalytic performance,stability and resistance to poisoning are the best.The electrochemical active surface area is 102.83 m~2/g,the peak current density of ethanol oxidation is 757.17 A/g and steady-state current density of 1100 s is 108.17 A/g which shows the lowest activation energy for ethanol oxidation reaction.When the cyclic voltammogram is scanned for 500 cycles,the oxidation peak current density retention rate is 87.74%.  相似文献   
7.
The metal-supported solid oxide fuel cell (MS-SOFC) is of current research interest in the clean energy field due to its high performance, quick start-up, thermal cycle stability, and lower raw material cost compared to the conventional cermet-based SOFC. To efficiently operate a MS-SOFC using complex hydrocarbon and logistic fuels, it is required to introduce an internal reforming catalyst within the anode metal scaffold. This review article discusses some examples of the performance of MS-SOFCs under hydrocarbon and logistic fuels with and without an additional reforming catalyst. We also discuss the performance improvement of conventional cermet-based SOFCs by adding reforming catalysts via the infiltration method. This information can be directly applied to future MS-SOFC applications. Furthermore, this review article proposes possible novel methods such as direct precursor infiltration, catalyst-anode premixing, and atomic layer deposition methods to introduce the reforming catalyst into a MS-SOFC for improving its initial electrochemical performance and long-term stability under hydrocarbon and logistics fuel.  相似文献   
8.
In this study, the high activity NiLiB catalysts were fabricated through wet chemical reduction method. Their morphological structures, crystallinity, surface area and composition were examined by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), BrunauerEmmettTeller (BET) method and energy-dispersive X-ray spectroscopy (EDS). The aluminum-water reaction tests were explored in the range of temperatures from 3575 °C. It was found that water could react with aluminum to generate hydrogen gas. The yield and hydrogen generation rate were significantly increased when all prepared catalysts were added into the reaction. The NiLiB (XLiCl = 0.1 g) catalyst exhibited the highest cumulative hydrogen volume of 201.3 ml with an average hydrogen production rate of 0.50 ml min1 at 55 °C. This phenomenon could be pointed to the emergence of the micro galvanic cell formed by the NiLiB, Li/NiLiB, Li and Al, which accelerated aluminum to rapidly react with water.  相似文献   
9.
An on-site laboratory with direct access to cleaned and conditioned steel mill gases was recently put into operation. The long-term performance and stability of Clariant's MegaMax®800 methanol synthesis catalyst utilizing steel mill gases is currently being investigated. First test results revealed that in order to investigate deactivation mechanisms arising from particular properties of the cleaned steel mill gases, the overlaying effect of thermal deactivation of the catalyst has to be minimized.  相似文献   
10.
Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles, which can be polymerize form the monomer of dimethoxymethane (DMM). The industrial synthesis of DMM is mainly involved two-step process: methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor. Due to huge energy consumption, this typical synthesis route of DMM needs to be upgraded and more green routes should be determined. In this review, four state-of-the-art one-step direct synthetic routes, including two upgrading routes (methanol direct oxidation and direct dehydrogenation) and two green routes (methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation), have been summarized and compared. Combination with the reaction mechanism and catalytic performance on the different catalysts, the challenges and opportunities for every synthetic route are proposed. The relationships between catalyst structure and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.  相似文献   
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