The electrochemical oxygen evolution reaction is a bottleneck reaction in hydrolysis and electrolysis because the four-step electron transfer leads to slow reaction kinetics and large overpotentials. This situation can be improved by fast charge transfer by optimizing the interfacial electronic structure and enhancing polarization. Herein, a unique metal (Ni) organic (diphenylalanine, DPA) framework Ni(DPA) (Ni-MOF) with tunable polarization is designed to bond with FeNi-LDH (layered double hydroxides) nanoflakes. The Ni-MOF@FeNi-LDH heterostructure delivers excellent oxygen evolution performance exemplified by an ultralow overpotential of 198 mV at 100 mA cm compared to other (FeNi-LDH)-based catalysts. Experiments and theoretical calculations show that FeNi-LDH exists in an electron-rich state in Ni-MOF@FeNi-LDH due to polarization enhancement caused by interfacial bonding with Ni-MOF. This effectively changes the local electronic structure of the metal Fe/Ni active sites and optimizes adsorption of the oxygen-containing intermediates. Polarization and electron transfer of Ni-MOF are further enhanced by magnetoelectric coupling consequently giving rise to better electrocatalytic properties as a result of high-density electron transfer to active sites. These findings reveal a promising interface and polarization modulation strategy to improve electrocatalysis.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1016/j.jcis.2023.03.153 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Electron transfer in polysaccharide monooxygenase catalysis.
Proc Natl Acad Sci U S A
January 2025
California Institute for Quantitative Biosciences, University of California, Berkeley, CA 94720.
Polysaccharide monooxygenase (PMO) catalysis involves the chemically difficult hydroxylation of unactivated C-H bonds in carbohydrates. The reaction requires reducing equivalents and will utilize either oxygen or hydrogen peroxide as a cosubstrate. Two key mechanistic questions are addressed here: 1) How does the enzyme regulate the timely and tightly controlled electron delivery to the mononuclear copper active site, especially when bound substrate occludes the active site? and 2) How does this electron delivery differ when utilizing oxygen or hydrogen peroxide as a cosubstrate? Using a computational approach, potential paths of electron transfer (ET) to the active site copper ion were identified in a representative AA9 family PMO from (PMO9E).
View Article and Find Full Text PDFCovalent Grafting of Graphene Quantum Dots onto Stepped TiO-Mediated Electronic Modulation for Electrocatalytic Hydrogen Evolution.
Inorg Chem
January 2025
School of Chemistry and Chemical Engineering, and Institute for Innovative Materials and Energy, Yangzhou University, 180 Si-Wang-Ting Road, Yangzhou 225002, China.
The interaction between electrocatalytic active centers and their support is essential to the electrocatalytic performance, which could regulate the electronic structure of the metal centers but requires precise design. Herein, we report on covalent grafting of graphene quantum dots (GQDs) on stepped TiO as a support to anchoring cobalt phosphide nanoparticles (CoP/GQD/S-TiO) for electrocatalytic hydrogen evolution reaction (HER). The covalent ester bonds between GQDs and TiO endow enlarged anchoring sites to achieve highly dispersed electroactive CoP nanoparticles but, more importantly, provide an efficient electron-transfer pathway from TiO to GQDs which could regulate the electronic structure of CoP.
View Article and Find Full Text PDFHigh-Resolution Mapping of Photocatalytic Activity by Diffusion-Based and Tunneling Modes of Photo-Scanning Electrochemical Microscopy.
ACS Nano
January 2025
Department of Chemistry and Biochemistry, Queens College, Flushing, New York 11367, United States.
Semiconductor nanomaterials and nanostructured interfaces have important technological applications, ranging from fuel production to electrosynthesis. Their photocatalytic activity is known to be highly heterogeneous, both in an ensemble of nanomaterials and within a single entity. Photoelectrochemical imaging techniques are potentially useful for high-resolution mapping of photo(electro)catalytic active sites; however, the nanoscale spatial resolution required for such experiments has not yet been attained.
View Article and Find Full Text PDFRational design of redox active metal organic frameworks for mediated electron transfer of enzymes.
Mater Horiz
January 2025
Department of Material Sciences, Institute of Pure and Applied Sciences, University of Tsukuba, 1-1-1, Tennodai, Ibaraki 305-5358, Japan.
The efficient immobilization of redox mediators remains a major challenge in the design of mediated enzyme electrode platforms. In addition to stability, the ability of the redox-active material to mediate electron transfer from the active-site buried enzymes, such as flavin adenine dinucleotide-dependent glucose dehydrogenase (FADGDH) and lactate oxidase (LOx), is also crucial. Conventional immobilization techniques can be synthetically challenging, and immobilized mediators often exhibit limited durability, particularly in continuous operation.
View Article and Find Full Text PDFMultifunctional CuBiS-BP@PEI Radiosensitizer with Enhanced Reactive Oxygen Species Activity for Multimodal Synergistic Therapy.
ACS Biomater Sci Eng
January 2025
Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fujian-Taiwan Science and Technology Cooperation Base of Biomedical Materials and Tissue Engineering, Engineering Research Center of Industrial Biocatalysis, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China.
Development of radiosensitizers with high-energy deposition efficiency, electron transfer, and oxidative stress amplification will help to improve the efficiency of radiotherapy. To overcome the drawbacks of radiotherapy alone, it is also crucial to design a multifunctional radiosensitizer that simultaneously realizes multimodal treatment and tumor microenvironment modulation. Herein, a multifunctional radiosensitizer based on the CuBiS-BP@PEI nanoheterostructure (NHS) for multimodal cancer treatment is designed.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!