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Updated: Dec 17, 2025

Morphology Control for Fully Printable Organic–Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer
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Morphology Control for Fully Printable Organic–Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer

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调节光化学选择性与温度:异醇对TiO2

Carla Courtois1, Constantin A Walenta2, Martin Tschurl1

  • 1Chair of Physical Chemistry & Catalysis Research Center, Technical University of Munich, Lichtenbergstr. 4, 85748 Garching, Germany.

Journal of the American Chemical Society
|June 30, 2020
PubMed
概括

控制生物质的化学生产需要了解反应途径. 这项研究揭示了依赖温度的异醇光氧化选择性,这对于设计高效的光催化过程至关重要.

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The Effect of Interfacial Chemical Bonding in TiO2-SiO2 Composites on Their Photocatalytic NOx Abatement Performance11:47

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相关概念视频

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Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control

The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.
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Hydroboration-Oxidation of Alkenes

In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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