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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

1.2K
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

30.5K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
30.5K
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

781
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Valence Bond Theory02:42

Valence Bond Theory

11.2K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
11.2K
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

3.2K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
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Structural Effects in Polyoxometalate-Based Supramolecular Assemblies for Enhanced Proton Conduction.

Bo Hu1,2, Bailing Liu1,2, Qingqing Pan2

  • 1Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P.R. China.

Angewandte Chemie (International Ed. in English)
|November 4, 2025
PubMed
Summary

A novel proton conductor, BPN, demonstrates high conductivity for fuel cells. Its unique structure facilitates efficient proton transport, enhancing performance in direct methanol fuel cells.

Keywords:
PolyoxometalatesProton conductorProton dynamicsSupramolecular clusters

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Supramolecular Chemistry

Background:

  • Proton conductors are crucial for proton exchange membrane fuel cells (PEMFCs).
  • Engineered charge-assisted hydrogen-bonding networks are key for advanced proton conductivity.
  • Existing materials often face limitations in efficiency and stability.

Purpose of the Study:

  • To synthesize and characterize a novel proton-conducting supramolecular cluster, BPN.
  • To investigate the mechanisms of proton transport within the BPN material.
  • To evaluate the performance of BPN in fuel cell applications.

Main Methods:

  • Synthesis and characterization of the supramolecular cluster ([Bi6O5(OH)3]2.24[PW12O40]1[NO3]2.4[H3O]5.8, BPN).
  • Molecular dynamics (MD) simulations to study hydrogen bonding and water-facilitated proton transport.
  • Proton conductivity measurements at various temperatures and humidity levels.
  • Nuclear Magnetic Resonance (NMR) spectroscopy (1H MAS NMR) and Density Functional Theory (DFT) calculations to analyze proton mobility and activation barriers.

Main Results:

  • BPN exhibits a maximum proton conductivity of 0.12 S cm-1 at 90 °C and 97% relative humidity, comparable to Nafion.
  • MD simulations revealed charge-assisted dynamic hydrogen bonds and water molecules mediating proton transport.
  • NMR and DFT studies indicated that Bi-O sites enhance proton migration and PW12O40 stabilizes transition states, lowering the activation barrier to 0.14 eV.
  • BPN-Nafion hybrid membranes improved direct methanol fuel cell performance, achieving an open-circuit voltage of 0.82 V and power density of 86 mW cm-2.

Conclusions:

  • The synthesized BPN material shows promising proton conductivity for fuel cell applications.
  • The integrative design strategy combining inorganic clusters and hydrogen-bonding networks is effective for developing advanced proton conductors.
  • This approach offers a scalable platform for creating PEMFC materials with tunable proton transport and enhanced stability.