Metal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for the oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in-situ-transformed metal (oxy)hydroxides during OER is often overlooked. We reveal the extraordinary role and mechanism of surface-adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy, and density functional theory (DFT) calculations show that the carboxylic groups around metal (oxy)hydroxides can efficiently induce interfacial electron redistribution, facilitate an abundant high-valence state of nickel species with a partially distorted octahedral structure, and optimize the d-band center together with the beneficial Gibbs free energy of the intermediate. Furthermore, the results of in situ Raman and FTIR spectra reveal that the surface-adsorbed carboxylate ligands as Lewis base can promote sluggish OER kinetics by accelerating proton transfer and facilitating adsorption, activation, and dissociation of hydroxyl ions (OH ).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202104148 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Photoinduced Reductive C-O Couplings from Unsymmetrical Bis-Cyclometalated Pt(IV) Dicarboxylato Complexes.
Inorg Chem
December 2024
Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo 19, Murcia 30100, Spain.
Unsymmetrical bis-cyclometalated dicarboxylato complexes (-6-32)-[Pt(tpy)(OCR)] [tpy = cyclometalated 2-(-tolyl)pyridine, R = -Bu (), Me (), Ph (), CF ()], are obtained from the reaction of -[Pt(tpy)] with the appropriate PhI(OCR) reagent. Treatment of complexes of this type with different carboxylates (R'CO) results in the formation of mixed-carboxylato derivatives, namely (-6-43)-[Pt(tpy)(OCMe)(OCR')] [R' = -Bu (), CF (), Ph ()], (-6-34)-[Pt(tpy)(OCCF)(OCR')] [R' = -Bu (), Me (), Ph ()], and (-6-34)-[Pt(tpy)(OC--Bu)(OCMe)] (). Irradiation of - and - with UV light (365 nm) in MeCN gives 5-methyl-2-(2-pyridyl)phenyl pivalate (), 5-methyl-2-(2-pyridyl)phenyl acetate () or 5-methyl-2-(2-pyridyl)phenyl benzoate () as the major photoproduct from most complexes, resulting from a reductive C-O coupling between a tpy ligand and a carboxylato ligand.
View Article and Find Full Text PDFConstructing an Isopolymolybdate-Based Bifunctional Photocatalyst for Promoting Nitroaromatic Reduction and C-H Oxidation.
Inorg Chem
December 2024
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Molecular Sciences, Henan University, Kaifeng, Henan 475004, P. R. China.
Amide compounds are widely present in drug molecules and natural products, which can be synthesized by acid-amine condensation. It is urgent to design new photocatalysts for achieving both nitroaromatic reduction and C-H oxidation to obtain raw materials, carboxylic acids, and aromatic amines. Herein, a novel isopolymolybdate-incorporated photoactive metal-organic framework, -TPT, was constructed by combining the oxidation catalyst [MoO], Ni(II) cation, and photosensitive ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT).
View Article and Find Full Text PDFProbing the Histamine H Receptor Binding Site to Explore Ligand Binding Kinetics.
J Med Chem
December 2024
Amsterdam Institute of Molecular and Life Sciences (AIMMS), Division of Medicinal Chemistry, Faculty of Science, Vrije Universiteit Amsterdam, De Boelelaan 1108, 1081 HZ Amsterdam, The Netherlands.
Analysis of structure-kinetic relationships (SKR) can contribute to an improved understanding of receptor-ligand interactions. Here, fragment (4-(2-benzylphenoxy)-1-methylpiperidine) was used in different fragment growing approaches to mimic the putative binding mode of the long residence time (RT) ligands olopatadine, acrivastine, and levocetirizine at the histamine H receptor (HR). SKR analyses reveal that introduction of a carboxylic acid moiety can increase RT at HR up to 11-fold.
View Article and Find Full Text PDFDelivery of Monomethyl Auristatin F to the Tumor Microenvironment with Noninternalizing Fibroblast Activation Protein-Cleavable Small Molecule-Drug Conjugates Elicits Potent Anticancer Activity.
Bioconjug Chem
December 2024
Philochem AG, R&D Department, CH-8112 Otelfingen, Switzerland.
OncoFAP is an ultrahigh affinity ligand of fibroblast activation protein (FAP), a tumor-associated antigen overexpressed in the stroma of the majority of solid tumors. OncoFAP has been previously implemented as a tumor-homing moiety for the development of small molecule drug conjugates (SMDCs). In the same context, the glycine--proline dipeptide was included with the aim to selectively undergo cleavage only in the presence of the target FAP, triggering the consequent release of the cytotoxic payload in the tumor microenvironment.
View Article and Find Full Text PDFstudies of triazole derivatives as inhibitors for estrogen receptor (ER) mutant L536S and anaplastic lymphoma kinase: DFT/tD-DFT, molecular docking, and MD simulations.
J Biomol Struct Dyn
December 2024
Department of Chemistry, Dyal Singh College, University of Delhi, New Delhi, India.
From the most prevalent cancers, breast and lung cancers have a meager survival rate for both men and women. These two cancers are related to each other. Breast cancer can possibly spread to the lungs or the region between the lung and the chest wall.
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!