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41.
以MCM-41为载体,以镍(Ni)为助剂,制备了Ni含量不同的WP/MCM-41催化剂。采用XRD、BET、SEM和XPS对催化剂进行了表征;以二苯并噻吩(DBT)为模型化合物,通过高压微反装置考察催化剂的加氢脱硫(HDS)活性。结果表明,Ni的加入促进了活性组分WP的生长并使其晶相尺寸略有增加,一定含量的Ni有利于提高催化剂的比表面积。Ni对WP/MCM-41催化剂二苯并噻吩HDS反应具有促进作用。少量Ni的加入有利于WP活性相的生成并增加了活性位的数量;加入过量的Ni,在催化剂中形成了具有一定活性的类似Ni-W-P结构的物种,减少了活性组分WP所占的比例,从而使催化剂DBT的 HDS活性降低。其中,Ni的质量分数为1%的催化剂(cat-Ni-1)具有相对较高活性,其DBT 脱硫率和转化率分别为76.78%和72.16%,比不加Ni的催化剂分别提高了30.04%和21.62%。二苯并噻吩在WP/MCM-41催化剂上以加氢脱硫途径为主,Ni的加入对提高加氢脱硫途径选择性起到了促进作用,且加氢脱硫选择性随Ni含量的增加而提高。 相似文献
42.
43.
Ranjit Bag Sourav Kar Suvam Saha Suman Gomosta Beesam Raghavendra Thierry Roisnel Sundargopal Ghosh 《化学:亚洲杂志》2020,15(6):780-786
Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe2(CO)9] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl4] (Cp*=η5‐C5Me5) and [LiBH4?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ3‐BH)2H2{Cp*W(CO)2}2{Fe(CO)2}] ( 1 ) and bis‐borylene, [(μ3‐BH)2{Cp*W(CO)2}2{Fe(CO)3}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru3(CO)12]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ3‐BH)2{WCp*(CO)2}2{Ru(CO)3}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co2(CO)8] with nido‐[(RhCp*)2(B3H7)], which afforded triply‐bridging bis‐borylene species [(μ3‐BH)2(RhCp*)2Co2(CO)4(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; 1H, 11B, 13C NMR spectroscopy; IR spectroscopy and mass spectrometry. 相似文献
44.
The three-dimensional morphology has sufficient interface contact and can be in favor of the electronic transport process. In this work, the demand for high-performance electrodes such as energy storage devices has been designed. Polypyrrole and tungsten oxide composite materials (PPy-WO3) have been synthesized by cyclic voltammetry (CV) technology at −0.6 to 0.9 V versus saturated calomel electrode (SCE) for 20 cycles. The PPy-WO320 mV/s, PPy-WO360 mV/s, and PPy-WO3120 mV/s electrodes have been prepared by CV technology at sweep rates of 20, 60, and 120 mV/s. The influences of scan rate on morphologies and charge storage properties of the composites are discussed. Among them, a three-dimensional flake structure for PPy-WO320 mV/s with a size of up to several micrometers was synthesized. PPy-WO320 mV/s composites as electrode materials exhibit a wide charge storage potential window of 1.4 V (between −0.9 and 0.5 V vs. SCE) and a specific capacitance of 145.13 F/g at 1 mA/cm2. Moreover, the long-term stability of PPy-WO320 mV/s and PPy has been investigated in 5 M LiCl aqueous electrolyte. The stability of the materials can be improved by inorganic and organic composites. 相似文献
45.
在pH≈6.5及NaAsO_2和Co(NO_3)_3·6H_2O存在下,Na_2WO_4·2H_2O 与Ce (NO_3)_3·6H_2O反应,得到了Na_9[CeW_(10)-O_(36)]·34H_2单晶。用元素分析 及X射线单晶衍射法确定了其组成与结构,晶体学数据为:a = 1.3010(5) nm, b = 1.3072(5) nm, c = 1.9962(8) nm, α= 101.073(7) °, β = 104.411(5) ° γ = 90.473(4) °, V = 3.221(2) nm~3,空间群P1,V=3.211(2)nm~3, Z = 4, 最终R因子[1>2σ(I)]R_1=0.0424, wR_2 = 0.0549, R因子(全部数据)R_1=0. 1357, wR_2 = 0.0808.[CeW_(10)O(36)]~(9-)具有D_(4d)对称性。 相似文献
46.
本文合成了1-(2-吡啶甲基)-1,2,4-三唑(L),并研究了其与有机锡和羰基钼(钨)的配位反应,合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L2SnR2Cl2(R=Me,n-Bu或Ph)和羰基金属配合物LM(CO)5(M=Mo或W),以及N,N螯合双齿配位的四羰基金属配合物LM(CO)4。当用氯化苄处理L时,制得了相应的三唑盐,该盐用氧化银处理后与M(CO)5THF或M(CO)4(NHC5H10)2(NHC5H10为哌啶)反应,得到了基于三唑的氮杂环卡宾衍生物L’M(CO)5和L’M(CO)4(L’=1-(2-吡啶甲基)-4-苄基-1,2,4-三唑-5-碳烯)。X-射线单晶衍射分析表明,在L’M(CO)5中氮杂环卡宾配体L’表现为通过卡宾碳配位的单齿配体;而在L’M(CO)4中,L’表现为通过卡宾碳和吡啶氮原子配位的螯合[C,N]双齿配体。 相似文献
47.
Small‐Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro‐oxidation 下载免费PDF全文
Yuan Liu Dr. Haijing Yan Dr. Xiaoguang Zhou Dr. Mingxia Li Prof. Honggang Fu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18345-18353
The anchoring of small‐sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H4[SiO4(W3O9)4] (SiW12) and CNTs modified with polyethylenimine (PEI‐CNTs) was ground to dryness. Small‐sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH3. Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small‐sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro‐oxidation reaction. The mass activity of Pt‐WN/CNTs‐G‐70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg?1Pt, better that those of commercial Pt/C (340 mA mg?1Pt) and Pt/CNTs (162 mA mg?1Pt). The Pt‐WN/CNTs‐G also displayed good CO tolerance. In contrast, Pt‐WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg?1Pt, verifying the key role of grinding treatment in the preparation of WN/CNTs with good co‐catalytic effect. 相似文献
48.
Hussain F Bassil BS Kortz U Kholdeeva OA Timofeeva MN de Oliveira P Keita B Nadjo L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(17):4733-4742
The dititanium-containing 19-tungstodiarsenate(III) [Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)](8-) (1) has been synthesized and characterized by IR, TGA, elemental analysis, electrochemistry, and catalytic studies. Single-crystal X-ray analysis was carried out on Cs(8)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)].2CsCl.12H(2)O (Cs-1), which crystallizes in the monoclinic system, space group P2(1)/m, with a=12.7764(19), b=19.425(3), c=18.149(3) A, beta=110.234(3) degrees, and Z=2. Polyanion 1 comprises two (B-alpha-As(III)W(9)O(33)) Keggin moieties linked through an octahedral {WO(5)(H(2)O)} fragment and two unprecedented square-pyramidal {TiO(4)(OH)} groups, leading to a sandwich-type structure with nominal C(2v) symmetry. Synthesis of 1 was accomplished by reaction of TiOSO(4) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous, acidic medium (pH 2). Polyanion 1 could also be isolated as a tetra-n-butyl ammonium (TBA) salt, {(n-C(4)H(9))(4)N}(5)H(3)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)] (TBA-1). TBA-1 was studied by cyclic voltammetry in acetonitrile (MeCN) solutions containing 0.1 M LiClO(4) and compared with the results obtained with Cs-1 in aqueous media. In MeCN, the Ti(IV) and W(VI) waves could not be separated distinctly. An important adsorption phenomenon on the glassy carbon working electrode was encountered both in cyclic voltammetry and in controlled potential electrolysis and was confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) studies on a carbon film. TBA-1, dissolved in MeCN, reacts with H(2)O(2) to give peroxo complexes stable enough for characterization by UV-visible spectroscopy, cyclic voltammetry, and EQCM. TBA-1 shows high catalytic activity (TOF=11.3 h(-1)) in cyclohexene oxidation with aqueous H(2)O(2) producing products typical of a heterolytic oxidation mechanism. The stability of TBA-1 under turnover conditions was confirmed by using IR, UV-visible spectroscopy as well as cyclic voltammetry. 相似文献
49.
A. Z. Voskoboinikov E. B. Chuklanova A. I. Gusev A. V. Kisin I. P. Beletskaya 《Russian Chemical Bulletin》1993,42(3):547-551
The cluster [Na(DME)3]2[W3(CO)14] (1) was prepared by treating CpLuCl2 with an equimolar mixture of Na2W(CO)5 and Na2W2(CO)10 in DME and characterized by X-ray analysis (MoK
radiation, 653 reflections,R = 0.125). The crystals are rhombic,a=18.749(4) Å,b=15.074(3) Å,c=9.505(3) Å,Z = 2, space groupC
mmm. The W-W distance in the W-W-W chain is 2.79 Å. The carbonyl ligands at the tungsten atoms are eclipsed. Compound 1 is the first example of a homometallic carbonyl cluster of an early transition metal. It is suggested that CpLuCl2 interacts with Na2W(CO)5 to afford the highly reactive species CpLu
(CO)5 which further reacts with Na2W2(CO)10 to form1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 582–585, March, 1993. 相似文献
50.
Lei Sun Jiahui Geng Dr. Mengyou Gao Dr. Dehua Zheng Zhongxin Jing Qingyun Zhao Prof. Jianjian Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10998-11004
Fe0.95S1.05 with high reactivity and stability was incorporated into WS2 nanosheets via a one-step solvothermal method for the first time. The resulted hybrid catalyst has much higher catalytic activity than WS2 and Fe0.95S1.05 alone, and the optimal WS2/Fe0.95S1.05 hybrid catalyst was found by adjusting the feed ratio. The addition of Fe0.95S1.05 was proven to be able to enhance the hydrogen evolution reaction (HER) activity of WS2, and vice versa. At the same time, it was found that the catalytic effect of the hybrid catalyst was the best when the feed ratio was W : Fe=2 : 1. In other words, we confirmed that there is a synergistic effect between W- and Fe-based sulfide hybrid catalysts, and validated that the reason for the improved HER performance is the strong interaction between the two in the middle sulfur. WS2/Fe0.95S1.05-2 hybrid catalyst leads to enhanced HER activity, which shows a low overpotential of ∼0.172 V at 10 mA cm−2, low Tafel slope of ∼53.47 mV/decade. This study supplies innovative synthesis of a highly active WS2/Fe0.95S1.05 hybrid catalyst for HER. 相似文献