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排序方式: 共有1038条查询结果,搜索用时 15 毫秒
31.
J. M. Hammond J. F. Hooper W. G. P. Robertson 《Journal of polymer science. Part A, Polymer chemistry》1971,9(2):295-298
Polymerization of various cyclic ethers by BF3·O(C2H5)2 in the presence of polymeric glycol leads to the formation of hydroxyl terminated block copolymers. Where poly(oxyethylene glycol) is used as the polymeric glycol, fission of the poly(oxyethylene glycol) chain occurs, and block copolymers, containing shorter ethylene oxide unit sequences are obtained. With poly(oxypropylene glycol), on the other hand, the polymer chain remains intact. This may be due to the steric influence of the pendant methyl groups. The cyclic oligomers formed as by-products in the polymerizations are easily removed. 相似文献
32.
Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO2, the primary greenhouse gas. Notably, the concentration of CO2 in the atmosphere is increasing annually at an astounding rate. Electrochemical CO2 reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO2 emissions. Despite the steady progress in the selective generation of C1 products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C2H4) has a higher energy density than do C1 species and is an important industrial feedstock in high demand. However, the conversion of CO2 to C2H4 is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C2H4 by taking advantage of the prominent interaction of Cu with shape-controlled CeO2 nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO2. The overall ECR Faradaic efficiency (FE) over Cu/CeO2(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO2(100) (FE ≈ 51.5%) and Cu/CeO2(111) (FE ≈ 48.4%) in 0.1 mol·L-1 KHCO3 solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO2(100), CeO2(110), and CeO2(111). In particular, the FE toward C2H4 formation and the partial current density increased in the sequence Cu/CeO2(111) < Cu/CeO2(100) < Cu/CeO2(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO2(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO2(100) and Cu/CeO2(111) were FEC2H4 ≈ 31.8% and FEC2H4 ≈ 29.6%, respectively. The C2H4 selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C2H4 remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO2(110) to yield C2H4 was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO2 but also remarkably stabilized Cu+, thereby boosting the ECR to produce C2H4. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering. 相似文献
33.
Cronin L McGregor PA Parsons S Teat S Gould RO White VA Long NJ Robertson N 《Inorganic chemistry》2004,43(25):8023-8029
The "one-pot" synthesis and characterization of a large 28-mer macrocycle (H(4)L(2)) with oxamido units capable of complexing guest ions through oxygen or nitrogen donor atoms is reported. Single-crystal structure determination of H(8)L(2)(NO(3))(4) and (Cu(2)[H(2)L(2)](H(2)O)(2))(NO(3))(2) demonstrated that the macrocycle contains two sites capable of complexing two nitrate anions or two copper(II) ions, involving a large structural reorganization in the conformation of the macrocyclic framework on coordination of the copper(II) ions when compared to the nitrate. Electrochemical and magnetic susceptibility measurements on the dinuclear Cu(II) complex and the related mononuclear and trinuclear Cu(II) complexes derived from the related 14-mer macrocycle were carried out and illustrate the role of the oxamido groups in mediating metal-metal interaction and delocalization. 相似文献
34.
The molecular structures of the title compounds have been determined by gas phase electron diffraction methods. The SiMn and GeMn bond lengths are 240.7 ? 0.5 and 248.7 ? 0.2 pm respectively and the CMnC angles in the silyl and germyl cases are 94.5 ± 2° and 97 ± 2° respectively. Comparisons are made with the reported structure of CH3Mn(CO)5 and HeI photoelectron spectra of these compounds in an attempt to determine the extent of d → d π-bonding in the SiMn or GeMn bonds. 相似文献
35.
Susan Robertson David Ellis Georgina M. Rosair Alan J. Welch 《Journal of organometallic chemistry》2003,680(1-2):286-293
The reaction of the labelled carborane ligand [3-Et-7,8-Ph2-7,8-nido-C2B9H8]2− with a source of {Pt(PMe2Ph)2}2+ affords non-isomerised 1,2-Ph2-3,3-(PMe2Ph)2-6-Et-3,1,2-closo-PtC2B9H8 (1). The analogous reaction between [3-F-7,8-Ph2-7,8-nido-C2B9H8]2− and {Pt(PMe2Ph)2}2+ yields 1,8-Ph2-2,2-(PMe2Ph)2-4-F-2,1,8-closo-PtC2B9H8 (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph2-2,2-(PMe2Ph)2-4-Et-2,1,8-closo-PtC2B9H8 (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB2 face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques. 相似文献
36.
考虑立体活性孤对电子附近次级键配位原子的贡献, 对文献报道的三十个氨基多羧酸锑(III)螯合物的晶体结构中配位多面体描述进行了全面的修正. 配位多面体的几何构型指定采用了单位球内截多面体的两面角判据及其相关的ANVPDA程序. 所有配位多面体几何构型的修正均得到了键价计算的有力支持. 相似文献
37.
Aucott SM Kilian P Milton HL Robertson SD Slawin AM Woollins JD 《Inorganic chemistry》2005,44(8):2710-2718
Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The pro-ligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp(2)TiS(2)Ar complexes (Ar = naphthalene) have been shown by temperature-dependent (1)H NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS(2)C(3) rings undergoing inversion on the NMR time scale while the similar Cp(2)TiS(2)Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO(2) groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported. 相似文献
38.
A series of related organo-alkaline earth metal compounds of formula (Ph3C)MX(THF)η, (M = Ca, Sr, Ba; X = Cl: M = Ca, Sr; X = Br: M = Ba; X = CPh3), has been isolated and characterized using analytical and spectroscopic techniques. The polymerization of methylmethacrylate (MMA) has been studied using these organometallic compounds as initiators. Investigations of the tacticity variations of polymethylmethacrylate (PMMA) produced in 1,2-dimethoxyethane or tetrahydrofuran (THF) at 210 K have shown that the syndiotacticity is higher in the former solvent, decreases with the following changes in initiator composition: Ca > Sr ? Ba; Cl > Br; in THF, it is dependent on the monomer concentration. The molecular weight distributions of the PMMA samples are broad and have distinct bi- or poly-modal features. The polymerization process appears to be anionic in nature but the evidence suggests that more than one type of propagation occurs and mechanistic aspects are discussed. Polymerization of bulk MMA by these same initiators is also reported. The initiators RMX(THF)n (M = Sr, R = Me, n = 3 or R = Et, n = 2) and (C3H5)SrBr(THF)2 are shown to be inefficient for polymerization of MMA. The glass transition temperatures of a range of PMMA samples of differing tacticity are presented and discussed. 相似文献
39.
D. S. Robertson 《Speculations in Science and Technology》1998,21(3):187-197
It has been established from geological studies that change in the atmospheric content of carbon dioxide gas commenced about one hundred million years ago. The likely origin of this change is advanced as being the onset of the Brewer circulation caused by the rise in terrain induced by tectonic plate movement. It is demonstrated that tectonic plate movement can be affected by impacts from external bodies which penetrate the crust of the Earth. The consequences of the change in atmospheric concentration of carbon dioxide are proposed as first, extinctions and reductions in animal numbers, including primates, as a result of changes in body chemistry of these animals and second, a change in the rate of weathering of rocks giving rise to changes in the availability of chemicals such as calcium and potassium which are essential for plant and animal life. This latter change contributing to the extinctions and reductions in animal numbers. It is shown that the change in weathering can account for the rise to dominance of angiosperm plants. It is concluded that there were several simultaneous evolutionary environments on Earth which were a function of altitude which gave rise to a vertical variation in atmospheric content of carbon dioxide. This variation disappeared with rise of terrain and the onset of the Brewer circulation. Such changes are advanced and being much more important than any changes in temperature caused by greenhouse effects since the disappearance of atmospheric variations in carbon dioxide allowed animal migration. It is demonstrated that the conditions of extinction could be reintroduced by human activities. 相似文献
40.
Haggag Awad Abd El Mageed K. F. El Sahhar Kenneth R. Robertson Ramin Parham Constantin A. Rebeiz 《Photochemistry and photobiology》1997,66(1):89-96
Abstract— On the basis of the steady-state accumulation of divinyl (DV) or monovinyl (MV) protochlorophyllide (Pchlide) a in darkness (D) or in the light (L), green plants have been classified into three different greening groups namely dark divinyl-light divinyl (DDV-LDV), dark monovinyl-light divinyl (DMV-LDV) and dark monovinyl-light monovinyl (DMV-LMV) (Ionannides et al., Biochem. Syst. Ecol. 22, 211-220,1994). Interruption of the L phase of the photoperiod by a brief period of darkness (LD condition) revealed a predominance of different chlorophyll (Chl) a biosynthetic routes, depending upon the greening group affiliation of the plant species. For example, in DMV-LDV and DMV-LMV plants, the predominant Chl a biosynthetic routes under the LD condition appear to be the MV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Pchlide a. On the basis of DV and MV Pchlide a accumulation rates after re-darkening, this greening group is designated as a light-dark MV (LDMV) subgroup. In DDV-LDV plants, the predominant LD Chi a biosynthetic routes appear to be the DV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Chlide a. This greening group is designated as a light-dark DV (LDDV) subgroup. It is proposed that upon inhibiting the conversion of Pchlide a to Chi a by interruption of the L phase of the photoperiod by a brief period of D, the rates of DV and MV Pchlide a regeneration may reflect the carryover rates of DV and MV Pchlide a biosynthesis in L instead of reflecting a differential use of DV and MV carboxylic biosynthetic rates in D. It is also shown that in LDMV plants, MV Chlide a and MV Chi a are formed without the participation of [4-vinyl] Chlide a reductase. On the basis of recently published evidence, it is also argued that Pchlide oxidoreductase-A (POR-A) may be active in LDDV plants, while POR-B may predominate in LDMV plant species. The evolutionary significance of the LDDV and LDMV greening subgroups is discussed. 相似文献