首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   208篇
  免费   8篇
  国内免费   74篇
化学   245篇
晶体学   1篇
力学   15篇
综合类   2篇
数学   8篇
物理学   19篇
  2023年   3篇
  2022年   7篇
  2021年   7篇
  2020年   8篇
  2019年   8篇
  2018年   14篇
  2017年   9篇
  2016年   13篇
  2015年   8篇
  2014年   11篇
  2013年   22篇
  2012年   20篇
  2011年   9篇
  2010年   9篇
  2009年   10篇
  2008年   5篇
  2007年   10篇
  2006年   8篇
  2005年   10篇
  2004年   8篇
  2003年   16篇
  2002年   5篇
  2001年   10篇
  2000年   11篇
  1999年   4篇
  1998年   6篇
  1997年   3篇
  1996年   6篇
  1995年   7篇
  1994年   4篇
  1993年   1篇
  1992年   3篇
  1991年   3篇
  1990年   3篇
  1989年   2篇
  1987年   1篇
  1986年   1篇
  1981年   1篇
  1980年   2篇
  1978年   2篇
排序方式: 共有290条查询结果,搜索用时 46 毫秒
281.
聚合氯化铁的制备及其絮凝效果   总被引:1,自引:0,他引:1  
以赤铁矿和工业盐酸为原料,采用盐酸酸浸和加碱聚合等方法制取聚合氯化铁絮凝剂(PFC),将其用来处理造纸废水,并与市售聚合氯化铁和碱式氯化铝絮凝剂进行比较.结果表明,在碱化度为2∶1、聚合温度为40℃、陈化时间为24h时,自制聚合氯化铁絮凝剂对造纸废水具有较好的处理效果;投加量为1.4mL/L时,造纸废水的浊度降低了99%,化学需氧量(COD)降低了69.55%,优于市售絮凝剂对造纸废水的处理效果;且三种絮凝剂用量相同时,自制的聚合氯化铁絮凝剂形成絮体的速率和沉降速率都较快.  相似文献   
282.
Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.  相似文献   
283.
An efficient synthesis of 1,2,3,4-tetrahydro-2-pyrimidinones and -thiones using ferric perchlorate as the catalyst from an aldehyde, ethyl acetoacetate, and urea or thiourea in acetonitrile was described. Compared to the classical Biginelli reaction conditions, this new method consistently has the advantage of full catalysis, good yields and short reaction time.  相似文献   
284.
《Analytical letters》2012,45(1):221-229
Abstract

The use of artificial neural networks (ANN) in optimizing salicylic acid (SA) determination is presented in this paper. A simple and rapid spectrophotometric method for salicylic acid (SA) determination was carried out based on the complexation of salicylic acid–ferric(III) nitrate, SAFe(III). The SA forms a stable purple complex with ferric(III) nitrate at pH 2.45. The useful dynamic linear range is 0.01–0.35 g/L. It has a maximum absorption at 524 nm and the stability is more than 50 hours. The results were used for artificial neural networks (ANNs) training to optimize data. For training and validation purposes, a back‐propagation (BP) artificial neural network (ANN) was used. The results showed that ANN technique was very effective and useful in broadening the limited dynamic linear response range mentioned to an extensive calibration response (0.01–0.70 g/L). It was found that a network with 22 hidden neurons was highly accurate in predicting the determination of SA. This network scores a summation of squared error (SSE) skill and low average predicted error of 0.0078 and 0.00427 g/L, respectively.  相似文献   
285.
Transition-metal-salt-mediated radical reactions of fullerenes have attracted extensive attention as a new and important method for fullerene functionalization. The application of relatively cheap and easily available ferric perchlorate (Fe(ClO 4 ) 3 ) to the synthesis of [60]fullerene (C 60 ) has demonstrated remarkable advantages and afforded a series of novel fullerene derivatives. In this review we present our recent progress in this area and summarize the reactions of C 60 with malonate esters, β-keto esters, nitriles, aldehydes/ketones, and arylboronic acids in the presence of Fe(ClO 4 ) 3 to afford the C 60-fused disubstituted lactones, C 60-fused hemiketal, C 60-fused dihydrofuran, C 60-fused oxazoles, C 60-fused 1,3-dioxolanes, and fullerenyl boronic esters. The possible reaction mechanisms for the above-mentioned reactions are also described in detail.  相似文献   
286.
Fe3+可与电沉积在玻碳电极表面的对氨基苯磺酸发生静电吸附作用并与[Fe(CN)6]4-形成普鲁士蓝(PB),进一步交替重复吸附Fe3+和[Fe(CN)6]4-反应,形成PB晶体.该晶体对还原过氧化氢(H2O2)具有很高的电化学活性.通过循环伏安法、交流阻抗法和计时电流法对传感器进行了电化学表征.研究了该传感器对H2O2的电催化作用,探讨了工作电位,PH值及干扰物质对响应电流的影响.结果表明,在磷酸盐缓冲溶液中(pH =5.4,0.1 mol/L),响应电流与H2O2的浓度在0.97 ~ 32.33 mmol/L范围内具有良好的线性关系,相关系数为0.9993,传感器的响应时间小于5 s,检测限为0.48 mmol/L( S/N为3).  相似文献   
287.
Abstract

A new multifunctional colorimetric and fluorescent chemosensor 1 for Fe3+/2+ and Al3+ has been synthesized in the one-step procedure. The sensor 1 detected both Fe2+ and Fe3+ through the color change from yellow to brown and Al3+ via turn-on fluorescence. The binding stoichiometries of sensor 1 with Fe3+/2+ and Al3+ were proposed to be 1:1 with the analyses of ESI-mass and Job plot. Importantly, the detection limits of 1 for Fe3+/2+ (2.11 and 2.70 μM) and Al3+ (3.44 μM) were lower than the EPA guideline (5.37 μM) for Fe3+/2+ and WHO guideline (7.41 μM) for Al3+. Compound 1 was used to quantify ferric species (Fe3+) in real samples. Moreover, the sensing processes for Fe3+/2+ and Al3+ were proposed with the spectroscopic studies and theoretical calculations.  相似文献   
288.
Formation of free radical intermediates in a NaOH/H(2)O(2)/Fe(III) system has been studied by ESR spectroscopy in the presence of the spin trap 5,5-dimethy-1-pyrroline N-oxide (DMPO). DMPO/O(2(*) ) (-) and DMPO/(*)OH signals were simultaneously detected in this system, but only the DMPO/(*)OH signal could be observed in the absence of Fe(III). Effects of pH values and Fe(III) concentrations on the ESR signal intensities were investigated in detail. Formation of DMPO/O(2(*) ) (-) adduct was inhibited by the addition of superoxide dismutase (SOD), catalase or nitro blue tetrazolium (NBT), and by chelating the Fe(III) with some chelators, including ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and desferrioxamine (DFO). Deoxygenation from the NaOH/H(2)O(2)/Fe(III) mixture had a slight effect on the formation of DMPO/O(2(*) ) (-). DMPO/O(2(*) ) (-) signal was also detected from the NaOH/H(2)O(2)/Fe(II) mixture, but it can be totally suppressed under anaerobic conditions. Considering the hydrolysis of Fe(III) into polymerization iron species with oxide phases in the alkaline medium, Fe(2)O(3) was directly suspended into a mixture of NaOH/H(2)O(2) for comparison. Fortunately, the presence of Fe(2)O(3) suspension was found to be of benefit to the production of DMPO/O(2(*) ) (-). Influence of aging time of hydrolytic iron species on the superoxide anion radical generation was also studied. These results suggest that the generation of O(2(*) ) (-) from the NaOH/H(2)O(2)/Fe(III) system was probably caused by the heterogeneous surface catalysis initiated by hydrolytic iron species.  相似文献   
289.
A graph G is called T-unique if any other graph having the same Tutte polynomial as G is isomorphic to G. Recently, there has been much interest in determining T-unique graphs and matroids. For example, de Mier and Noy [A. de Mier, M. Noy, On graphs determined by their Tutte polynomials, Graphs Combin. 20 (2004) 105-119; A. de Mier, M. Noy, Tutte uniqueness of line graphs, Discrete Math. 301 (2005) 57-65] showed that wheels, ladders, Möbius ladders, square of cycles, hypercubes, and certain class of line graphs are all T-unique. In this paper, we prove that the twisted wheels are also T-unique.  相似文献   
290.
Huge plastic consumption and depletion of fossil fuels are at the top of the world's environmental and energy challenges. The scientific community has tackled these issues through different approaches. Catalytic pyrolysis of plastic wastes to valuable products has been proved as a sustainable route which fits with the circular economy aspects. The design of catalytic materials is the central factor for performing the catalytic conversion of plastic wastes. This review aims to conduct a Bibliometric analysis of the pyrolysis of plastic wastes and non-precious-based catalysts by mapping research studies over the last fifty years. The analysis was developed via VOSviewer and RStudio tools. It showed the historical progress regarding plastic waste pyrolysis to produce valuable products and chemicals worldwide. The research shows that the top five countries with the highest citations and publications in this field were Spain, China, England, the USA and India. The Journal of Analytical and Applied Pyrolysis had the most comprehensive coverage of plastic waste. The relationship between the catalyst and the mechanism of plastic waste can influence the production yield and selectivity. The research gap and underrepresented research topics were identified, and previous research studies on developing non-precious-based catalysts that were most relevant to the current topic were reviewed and discussed. The challenges and perspectives on catalyst preparation and development for material complexity were critically discussed. Challenges of previous studies and directions for future research were provided. This report might guide the reader to take a general look at plastic waste valorization by pyrolysis and easily understand the main challenges.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号