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Related Concept Videos

Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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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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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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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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Hess's Law03:40

Hess's Law

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There are two ways to determine the amount of heat involved in a chemical change: measure it experimentally, or calculate it from other experimentally determined enthalpy changes. Some reactions are difficult, if not impossible, to investigate and make accurate measurements for experimentally. And even when a reaction is not hard to perform or measure, it is convenient to be able to determine the heat involved in a reaction without having to perform an experiment.
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Updated: Dec 23, 2025

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
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CeTi2O6-A Promising Oxide for Solar Thermochemical Hydrogen Production.

S Shahab Naghavi1, Jiangang He2, C Wolverton2

  • 1Department of Physical and Computational Chemistry, Shahid Beheshti University, G.C., Evin, 1983969411 Tehran, Iran.

ACS Applied Materials & Interfaces
|April 23, 2020
PubMed
Summary

Researchers identified CeTi2O6 as a promising material for solar thermochemical hydrogen (STCH) production. This material offers a large entropy of reduction and lower enthalpy, overcoming limitations of ceria for efficient hydrogen generation.

Keywords:
Ce4+ oxide screeningbrannerite structuredensity functional theorysolar energy storagesolar thermochemical water splittingthermochemical redox cycle

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Area of Science:

  • Materials Science
  • Renewable Energy
  • Chemical Engineering

Background:

  • High entropy of reduction is key for efficient solar thermochemical hydrogen (STCH) production via water splitting.
  • Ceria (CeO2) exhibits high performance but requires impractically high temperatures (>1500 °C) due to its large reduction enthalpy.

Purpose of the Study:

  • To screen for Ce4+-based oxides with superior thermodynamics for STCH compared to ceria.
  • To identify new materials with large entropy of reduction and lower reduction enthalpy for practical STCH applications.

Main Methods:

  • Systematic screening of Ce4+-based oxides from the Inorganic Crystal Structure Database (ICSD) and literature.
  • Density functional theory (DFT) calculations to determine oxygen vacancy formation energies (reduction enthalpies).

Main Results:

  • CeTi2O6 with a brannerite structure identified as the most promising STCH candidate.
  • CeTi2O6 demonstrates a lower reduction enthalpy than ceria, sufficient for water splitting.
  • CeTi2O6 exhibits high thermal stability and a large entropy of reduction for Ce4+ → Ce3+ redox.

Conclusions:

  • CeTi2O6 is a superior alternative to ceria for STCH production due to its favorable thermodynamic properties.
  • The findings support a design strategy for exploring novel Ce4+ oxides for enhanced STCH efficiency.
  • Further research into Ce4+-based oxides is warranted for advancing STCH technology.