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Related Concept Videos

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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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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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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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
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Polyoxometalate-Based Compounds for Photo- and Electrocatalytic Applications.

Ning Li1, Jiang Liu2, Bao-Xia Dong1

  • 1School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, P. R. China.

Angewandte Chemie (International Ed. in English)
|July 8, 2020
PubMed
Summary

Polyoxometalate (POM)-based compounds are effective catalysts for water splitting and CO2 reduction. This review highlights their advantages and challenges in photo/electrocatalysis for a sustainable energy future.

Keywords:
CO2 reduction reactionhydrogen evolution reactionoxygen evolution reactionphoto/electrocatalysispolyoxometalate-based compounds

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Photo/electrocatalysis of water splitting and CO2 reduction are crucial for addressing the energy crisis and CO2 emissions.
  • Developing efficient catalysts is essential to overcome activation energy barriers and accelerate reaction dynamics for hydrogen evolution (HER), oxygen evolution (OER), and CO2 reduction (CO2RR).
  • Polyoxometalate (POM)-based compounds offer unique advantages, including tunable compositions, diverse structures, and excellent stability, making them promising candidates for these catalytic processes.

Purpose of the Study:

  • To provide an introduction to photo/electrocatalytic HER, OER, and CO2RR.
  • To classify pristine POM-based compounds for different catalytic reactions.
  • To highlight recent advancements in engineering POM-based compounds as efficient photo/electrocatalysts and discuss their future prospects.

Main Methods:

  • Review of existing literature on POM-based compounds in photo/electrocatalysis.
  • Classification of POM structures and compositions based on their catalytic applications.
  • Analysis of recent breakthroughs and strategies for enhancing POM catalytic performance.

Main Results:

  • POM-based compounds exhibit significant potential as photo/electrocatalysts due to their inherent properties like redox stability and quasi-semiconductor behavior.
  • Engineered POMs demonstrate improved efficiency in HER, OER, and CO2RR.
  • The review categorizes POMs and discusses their specific roles in various catalytic reactions.

Conclusions:

  • POM-based compounds are versatile and highly effective materials for photo/electrocatalytic water splitting and CO2 reduction.
  • Further research into the design and application of POMs can accelerate the development of sustainable energy technologies.
  • Addressing current challenges and exploring novel strategies will unlock the full potential of POMs in catalysis.