共查询到20条相似文献，搜索用时 15 毫秒
1.
DC Clary 《Science (New York, N.Y.)》1998,279(5358):1879-1882
It is now possible to use rigorous quantum scattering theory to perform accurate calculations on the detailed state-to-state dynamics of chemical reactions in the gas phase. Calculations on simple reactions, such as H + D2 --> HD + D and F + H2 --> HF + H, compete with experiment in their accuracy. Recent advances in theory promise to extend such accurate predictions to more complicated reactions, such as OH + H2 --> H2O + H, and even to reactions of molecules on solid surfaces. New experimental techniques for probing reaction transition states, such as negative-ion photodetachment spectroscopy and pump-probe femtosecond spectroscopy, are stimulating the development of new theories. 相似文献
2.
采用弱碱 NH4 HCO3作为沉淀剂,CoCl·6H2 O和 FeCl3·6H2 O作为反应物,在一定摩尔比条件下,通过化学共沉淀法制备了铁酸钴纳米粒子,并采用 FT-IR、XRD、TEM和振动样品磁强计对其进行了表征。结果表明,制得的铁酸钴纳米粒子为尖晶石型结构,其粒径为20 nm左右,并且由于反应过程中弱碱 NH4 HCO3分解产生的CO2和 H2 O 气体对产物的阻隔作用,制得的铁酸钴纳米粒子的分散性较好,饱和磁化强度为55.5 Am2·kg-1。 相似文献
3.
Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces. 相似文献
4.
Swaddle TW Rosenqvist J Yu P Bylaska E Phillips BL Casey WH 《Science (New York, N.Y.)》2005,308(5727):1450-1453
Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products. 相似文献
5.
Even in small molecules, the influence of electronic state on rotational and vibrational product energies is not well understood. Here, we use experiments and theory to address this issue in photodissociation of formaldehyde, H2CO, to the radical products H + HCO. These products result from dissociation from the singlet ground electronic state or the first excited triplet state (T1) of H2CO. Fluorescence spectra reveal a sudden decrease in the HCO rotational energy with increasing photolysis energy accompanied by substantial HCO vibrational excitation. Calculations of the rotational distribution using an ab initio potential energy surface for the T1 state are in very good agreement with experiment and strongly support dominance of the T1 state in the dynamics at the higher photolysis energies. 相似文献
6.
Because of its high resistivity and subsequent low electroactivity, sulfur is not normally considered a room-temperature battery cathode. An elemental sulfur cathode has been made with a measured capacity of over 900 ampere.hours per kilogram, more than 90 percent of the theoretical storage capacity of solid sulfur at room temperature, accessed by means of a lightweight, highly conductive, aqueous polysulfide interface through the electrocatalyzed reaction S + H(2)O + 2e(-) --> HS(-) + OH(-). This solid sulfur cathode was first used in a battery with an aluminum anode for an overall discharge reaction 2Al + 3S + 3OH(-) + 3H(2)O --> 2Al(OH)(3) + 3HS(-), giving a cell potential of 1.3 volts. The theoretical specific energy of the aluminum-sulfur battery (based on potassium salts) is 910 watt.hours per kilogram with an experimental specific energy of up to 220 watt.hours per kilogram. 相似文献
7.
Experimental and theoretical differential cross sections for a four-atom reaction: HD + OH → H₂O + D 总被引：1，自引：0，他引：1
Xiao C Xu X Liu S Wang T Dong W Yang T Sun Z Dai D Xu X Zhang DH Yang X 《Science (New York, N.Y.)》2011,333(6041):440-442
Quantum dynamical theories have progressed to the stage in which state-to-state differential cross sections can now be routinely computed with high accuracy for three-atom systems since the first such calculation was carried out more than 30 years ago for the H + H(2) system. For reactions beyond three atoms, however, highly accurate quantum dynamical calculations of differential cross sections have not been feasible. We have recently developed a quantum wave packet method to compute full-dimensional differential cross sections for four-atom reactions. Here, we report benchmark calculations carried out for the prototypical HD + OH → H(2)O + D reaction on an accurate potential energy surface that yield differential cross sections in excellent agreement with those from a high-resolution, crossed-molecular beam experiment. 相似文献
8.
Boddien A Mellmann D Gärtner F Jackstell R Junge H Dyson PJ Laurenczy G Ludwig R Beller M 《Science (New York, N.Y.)》2011,333(6050):1733-1736
Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO(2)H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H(2) from FA. Applying 0.005 mole percent of Fe(BF(4))(2)·6H(2)O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH(2)CH(2)PPh(2))(3), PP(3)] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms. 相似文献
9.
Eugster HP 《Science (New York, N.Y.)》1967,157(3793):1177-1180
Two new hydrous sodium silicates, NaSi(7)O(13)(OH)(3).3H(2)O (magadiite) and NaSi(11)O(20.5)(OH)(4).3H(2)O (kenyaite), were found in lake beds at Lake Magadi, Kenya. Both are well-crystallized layered silicates with large basal spacings. Concretions within the magadiite bed consist of kenyaite or quartz (chert) in the center, surrounded by kenyaite. In dilute acids magadiite and kenyaite are converted to 6SiO(2).H(2)O (SH), the first known crystalline hydrate of silica. The magadiite bed probably represents a chemical precipitate from alkaline brines. Percolating waters convert magadiite to kenyaite and eventually to chert. Thus a mechanism has been outlined for the formation of bedded chert deposits through inorganic precipitation. Alternations between silica-rich and iron-rich bands of iron formations may be due to concentration cycles in alkaline lakes. 相似文献
10.
以5年生盆栽南方红豆杉幼苗为试验材料,研究UV-B辐射增强条件下,喷施外源一氧化氮供体硝普钠对南方红豆杉幼苗针叶光合色素质量分数、自由基质量分数、次生代谢物质质量分数等生理指标和生理机制的影响。结果表明:喷施0.1 mmol·L-1SNP显著增加针叶叶绿素a、叶绿素b、类胡萝卜素及总叶绿素质量分数,提高次生代谢产物质量分数,降低针叶内H2O2质量分数(p0.05);UV-B处理显著降低针叶光合色素质量分数及叶绿素a/b,提高紫杉醇质量分数,增加针叶内H2O2质量分数(11.1%,p0.05)和羟基自由基(·OH)水平(100%,p0.05);与UV-B相比,UV-B+SNP显著降低了针叶H2O2质量分数和·OH水平(p0.05)。UV-B+SNP处理下南方红豆杉针叶类黄酮的质量分数((35.40±0.05)mg·g-1)及单宁的质量分数((30.90±0.31)mg·g-1)明显高于其他处理(p0.05)。研究证实NO作为信号分子可以诱导南方红豆杉提高光合色素质量分数、降低自由基水平、促进次生代谢产物合成积累。 相似文献
11.
Zhai Y Pierre D Si R Deng W Ferrin P Nilekar AU Peng G Herron JA Bell DC Saltsburg H Mavrikakis M Flytzani-Stephanopoulos M 《Science (New York, N.Y.)》2010,329(5999):1633-1636
We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H(2)O + CO → H(2) + CO(2)) used for producing H(2). The alkali ion-associated surface OH groups are activated by CO at low temperatures (~100°C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O(x)(OH)(y) species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria. 相似文献
12.
Majewski J Margulis L Jacquemain D Leveiller F Bohm C Arad T Talmon Y Lahav M Leiserowitz L 《Science (New York, N.Y.)》1993,261(5123):899-902
A new approach is described for probing domains of ordered self-assemblies of amphiphilic monolayers at the aqueous solution interface. The method has potential importance for the study of membrane structure, Langmuir-Blodgett films, and nucleation processes of two-and three-dimensional crystals. Electron diffraction (ED) patterns indicative of two-dimensional crystalline self-assembly were obtained from samples, which were examined by cryo-electron microscopy, of monolayers of water-insoluble amphiphiles on vitrified aqueour substrates. The apparent hexagonal symmetry of an ED pattern from a C(16)H(33)OH monolayer was interpreted in terms of multiple twinning. Monolayers of the CL(31)H(63)OH and cadmium salt of C(19)H(39)CO(2)H that were studied by dark-field techniques displayed faceted two-dimensional crystallites with a maximal size of 1 to 2 micrometers. Epitaxial nucleation of hexagonal ice by the C(31)H(63)OH monolayer has also been demonstrated by ED. 相似文献
13.
Clark JR 《Science (New York, N.Y.)》1963,141(3586):1178-1179
The crystal structure of tunellite, SrO.3B(2)O(3).4H(2)O, with infinite sheets of composition n[B(6)O(9)(OH)(2)](2-), has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons. 相似文献
14.
The O((1)D) + H(2) --> OH + H reaction, which proceeds mainly as an insertion reaction at a collisional energy of 1.3 kilocalories per mole, has been investigated with the high-resolution H atom Rydberg "tagging" time-of-flight technique and the quasiclassical trajectory (QCT) method. Quantum state-resolved differential cross sections were measured for this prototype reaction. Different rotationally-vibrationally excited OH products have markedly different angular distributions, whereas the total reaction products are roughly forward and backward symmetric. Theoretical results obtained from QCT calculations indicate that this reaction is dominated by the insertion mechanism, with a small contribution from the collinear abstraction mechanism through quantum tunneling. 相似文献
15.
Wentworth P 《Science (New York, N.Y.)》2002,296(5576):2247-2249
Catalytic antibodies have emerged as being without peer as rationally designed biocatalysts. They have been shown to catalyze an ever-increasing array of chemical reactions with both high substrate specificity and selectivity. Probing the immune repertoire, via an expanding number of techniques, has lead to the production of proteins that can catalyze chemistry that is both difficult to perform using existing chemical methods and that is not catalyzed by endogenous enzymes. Remarkably, recent evidence has pointed to a hitherto unknown catalytic function of all antibodies that seems to be intrinsic to their immunoglobulin structure, the conversion of 1O2* into H2O2. This new catalytic potential of antibodies points to a new 'chemical arm' of the immune system and reveals that the evolution of catalytic antibodies significantly predates their rational design. 相似文献
16.
Results show that PuO(2+x), a high-composition (x 相似文献
17.
不同营养液水培对卡特兰生长发育的影响 总被引：1，自引：0，他引：1
[目的]研究不同营养液配方对卡特兰（Cattleya hybrida）生长发育的影响。[方法]采用水培方法,以清水培养为对照。[结果]配方C[0.614 0 mg/L Ca（NO3）.24H2O＋0.283 0 mg/L KNO3＋0.240 0 mg/LNH4NO3＋0.136 0 mg/L KH2PO4＋0.154 0 mg/LMgSO4.7H2O＋0.022 0 mg/L K2SO4＋0.017 0 mg/L K2HPO4＋0.012 0 mg/L NaC l＋31.194 0 mg/L Na2Fe-EDTA＋2.863 0 mg/LH3BO3＋2.1190 mg/LMnSO4.4H2O＋0.230 0 mg/L ZnSO4.7H2O＋0.074 9 mg/L CuSO4.5H2O＋0.024 7 mg/L（NH4）6MO7O2.4H2O]所处理植株的各项形态指标均明显优于其他配方,叶绿素含量也高于其他配方,但丙二醛（MDA）的含量与其他配方相比差异不显著。[结论]该研究可为卡特兰的无土栽培提供科学依据。 相似文献
18.
Côté AP Benin AI Ockwig NW O'Keeffe M Matzger AJ Yaghi OM 《Science (New York, N.Y.)》2005,310(5751):1166-1170
Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively). 相似文献
19.
Giese RF 《Science (New York, N.Y.)》1971,172(3980):263-264
The electrostatic energy of the 2M(1) muscovite structure, KAl(2)(Si(3)Al)- O(10)(OH)(2), has been calculated as a function of the orientation of the hydroxyl group (O-H distance = 0.97 angstrom). The minimum in the electrostatic energy occurs when the OH bond makes an angle of 18 degrees with the cleavage plane and an angle of 31 degrees with the b-axis (in the a-b plane), which is 2.5 degrees away from the orientation of the transition moment as determined from infrared measurements on single crystals. If the K+ ion is excluded from the calculation, the O-H bond makes an angle of 53 degrees with the cleavage plane. This indicates the strong influence that the interlayer cation exerts on the hydroxyl hydrogen in mica structures. 相似文献
20.
红黄壤茶园不同培肥模式的土壤理化效应 总被引：4，自引：0，他引：4
通过长期定位试验,研究闽东地区红黄壤茶园不施肥(CK)、全量化肥(C)、(半量化肥+半量有机肥)(C1/2O1/2)、全量有机肥(O)、(全量化肥+豆科绿肥)(CL)及(半量化肥+半量有机肥+豆科绿肥)(C1/2O1/2L)等6种不同培肥模式下土壤理化性质的动态变化。结果表明:与CK模式相比,其他模式均能一定程度上改良土壤理化性状。其中,处理O和C1/2O1/2L的改良效益相对较佳,砂粒(0.05 mm相似文献