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141.
共轭二烯烃的聚合是配位阴离子聚合,双金属配合物是聚合的活性中心,控制单体的构象是控制聚合物结构的关键。单体在低值配位场稳定化能(LFSE)过渡金属离子,如Co~(2+)、Ti~(3+)上螯合,螯合单体具有顺式构象,所得聚合物具有顺1,4结构;在中等LFSE的过渡金属离子,如V~(3+)、Cr~(3+)上配位,配位单体具有反式构象,所得聚合物具有反1,4结构或是1,2聚合物;高LFSE值过渡金属离子不易控制活性价态,双金属配合物不够稳定,所得聚合物分子量常较低,结构规整性也常不够理想。 相似文献
142.
Zhengtian Yu James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1085-1094
The syndiospecific propylene polymerizations catalyzed by isopropylidene(cyclopentadienyl)(fluorenyl)- and (2,2-dimethylpropylidene)(cyclopentadienyl)(fluorenyl)-zirconocenium ( 1 + and 2 +) have been investigated theoretically and compared with experimental observations. With the ab initio calculated structures for the transition state (TS) of 1 +(M)P and 2 +(M)P (M = propylene, P = 2-methylpentyl), their steric energies (E°) have been computed using MM2 force-field. The difference between steric energies E°(m) and E°(r) for the meso and racemic enchainment of propylene, respectively, is defined as the stereocontrol energy [δE°(m ? r)] for syndiotactic propagation. The δE°(m ? r) for the TS of 1 + (M)P is about 2.1 kcal/mol, the value is 1 kcal/mol greater for 2 +(M)P. The observed steric pentad distributions of the syndiotactic poly(propylene) obtained by these catalysts are consistent with smaller effective stereocontrol energy, which is about two-third as large as δE°(m ? r) values calculated for the MM2 optimized structure. Syndiotactic enchainment is favored over isotactic enchainment for all combinations of site configurations in the catalyst. α-Agostic interaction seems to enhance syndioselectivity, whereas γ-agostic interaction changes the stereoselectivity to meso enchainment. The mirror plane symmetry of the syndiotactic propagating species renders the stereoselectivity of the polymerization insensitive to reaction conditions. These catalysts are also highly regiospecific. © 1995 John Wiley & Sons, Inc. 相似文献
143.
Cassandra T. Eagle David FarrarGrant N. Holder Michelle L. HatleyShirley L. Humphrey Elizabeth V. OlsonMaria Quintos Joseph SadighiTom Wideman 《Tetrahedron letters》2003,44(12):2593-2595
The catalytic activities of three structural isomers of Rh2[N(C6H5)COCH3]4 in cyclopropanation reactions were surveyed. These studies showed cis cyclopropanation selectivity with bulky alkenes for 2,2-cis- and 2,2-trans-Rh2[N(C6H5)COCH3]4. 相似文献
144.
Fe-Mn, Co-Mn and Ni-Mn composite oxide catalysts based on high specific surface area MnO2 precursor were prepared and applied to catalytic combustion of CH4. Results were compared with that of unmodified MnOx and 1wt.% Pd/-Al2O3. Below 450°C, manganese oxide catalysts show higher activity than Pd/-Al2O3, while the modified manganese oxide catalysts exhibit higher activity than the unmodified one below 420°C. All catalysts were characterized by means of N2-BET, XRD, TG-DTA and H2-TPR. Due to the interaction between Fe, Co or Ni oxides and manganese oxide, the activity of the oxygen species of the modified catalysts is improved, which leads to the increase of their CH4 combustion activity. 相似文献
145.
As supported PtxNi1–x catalysts are used for hydrogenation reactions, it seemed necessary to assess the surface composition of the reduced samples. To approach the usual reduction conditions we applied in situ reduction in a reaction chamber (1 mbar H2 up to 500 °C) placed in ultra high vacuum recipient (UHV: 10–9 to 2.10–10mbar). All ion scattering spectroscopy measurements were performed in UHV. Charging of the samples was avoided by electron bombardment (5 eV). The variation of the surface composition was determined after subsequent sputtering, thermal treatment at 500 °C and during oxygen adsorption. A comparison with previous results of surface compositions of binary alloys (polycrystalline foils [1, 2] and single crystals PtxNi1–x [3]) is given.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
146.
NH_3-TPD技术表征固体催化剂的酸性似乎已很成熟,其实不然。如该技术表征HZSM-5沸石时,有作者观察到773K左右的高温脱氨峰,而有些作者则检测不到。诚然,各作者间所用试样及预处理条件等存在差异,但实验装置和实验操作条件不同带来的影响也不可忽视。此外,该技术在用于表征一些新的较复杂的催化剂时,其程脱谱也会呈现出新现象,这些现象有时是不能通过酸性来解释的,这是因为NH_3作为探针分子不仅具有碱性,同时还有还原性和配位性。本文对载镍沸石上NH_3-TPD谱图中出现的某些新峰进行了剖析和归属。 相似文献
147.
The dehydrogenation reaction of ethane over Cr/CeO2 catalysts in presence of CO2 was studied with fixed-bed micro-reactor. The Cr/CeO2 catalysts of different Cr loading have been synthesized using impregnation techniques. The Cr/CeO2 system has already been found to be active and selective in the reaction at around 740 ℃. The function of carbon dioxide is to remove coke and hydrogen to accelerate dehydrogenation of ethane. The results of catalysts characterizations indicated that Cr3+ and Cr6+ occurred on the surface of the catalysts. The 1.2 mmol Cr/100m2 CeO2 catalyst sample with a monolayer dispersion of Cr on CeO2 support showed a stronger surface acidity and a maximum yield of ethylene of about 35.5% at 36.6% conversion of ethane. 相似文献
148.
Catalytic wet air oxidation of oleic acid on ceria-supported platinum catalyst.effect of pH 总被引:1,自引:0,他引:1
Beno?t Levasseur Benoist Renard Jacques Barbier Jr. Daniel Duprez 《Reaction Kinetics and Catalysis Letters》2006,87(2):269-279
Summary Catalytic wet air oxidation (CWAO) of oleic acid was carried out in a batch reactor on platinum supported ceria catalyst (Pt/CeO2). Oleic acid is a water insoluble linear unsaturated fatty acid of 18 carbon atoms. To increase the homogeneity of the solution
by saponification, the influence of NaOH additions in oleic acid CWAO mechanism and catalyst performances have been investigated.
The oxidation of such molecule occurs by two types of mechanisms: successive carboxy-decarboxylation which leads essentially
to CO2and/or C-C bonds splitting in the alkyl chain inducing a high formation of acetic acid. With or without NaOH, the 5%Pt/CeO2catalyst is active in the conversion of oleic acid and selective to carbon dioxide. In alkaline medium, oleic acid is initially
saponified which increases the solubility of the reactant before it to be oxidized. Finally the oxidation is slightly delayed
by the presence of NaOH. The catalyst characterizations show no significant difference before and after reaction.</o:p> 相似文献
149.
铁,钴,铜酞菁/Y型分子筛的制备,表征及催化苯酚羟化的研究 总被引:4,自引:0,他引:4
制备了铁,钴,铜酞菁/Y型发子筛,利用元素分析,IR、UV-Vis,TG、BET及XRD确定了分子筛笼中铁,钴,铜酞菁化合物的生成及其晶体结构,考察了实验参数对苯酚的转化率及产物选择性的影响。 相似文献
150.
A series of polymer-supported tetranuclear rhodium carbonyl cluster catalysts were prepared b the reaction of Rh_4(CO)_(12) with several kinds of polymer supports such as crosslinked poly (N-vinylpyrrolidone) (PNVP) and crosslinked poly ( styrene-co-maleic anhydride) (PMAn), and subsequently were used to catalyze the hydroformylation of olefins. The catalysts were characterized by IR, SEM and XPS. The influence of the supports structure and crosslinking, metal's content and particle size of the supports on the catalysts hydroformylation properties was studied. The factors which affect the catalytic conversion were also examined. The experimental results show that the polymer-supported Rh cluster catalysts possess very high catalytic activity and aldehyde selectivity as well as good reproducibility. 相似文献