The controllable synthesis of stable single-metal site catalysts with an expected coordination environment for high catalytic activity and selectivity is still challenging. Here, we propose a cation-exchange strategy for precise production of an edge-rich sulfur (S) and nitrogen (N) dual-decorated single-metal (M) site catalysts (M = Cu, Pt, Pd, etc.) library. Our strategy relies on the anionic frameworks of sulfides and N-rich polymer shell to generate abundant S and N defects during high-temperature annealing, further facilitating the stabilization of exchanged metal species with atomic dispersion and excellent accessibility. This process was traced by in situ transmission electron microscopy, during which no metal aggregates were observed. Both experiments and theoretical results reveal the precisely obtained S, N dual-decorated Cu sites exhibit a high activity and low reaction energy barrier in catalytic hydroxylation of benzene at room temperature. These findings provide a route to controllably produce stable single-metal site catalysts and an engineering approach for regulating the central metal to improve catalytic performance.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.0c03415 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Photocatalytic Oxidative Coupling of Methane to Ethane Using CO2 as a Soft Oxidant Over the Au/TiO2-Vo Nanosheets.
Angew Chem Int Ed Engl
December 2024
University of Science and Technology of China, Hefei National Research Center for Physical Sciences at Microscale, jinzhai road, hefei, CHINA.
Herein, we first report a photocatalytic OCM using CO2 as a soft oxidant for C2H6 production under mild conditions, where an efficient photocatalyst with unique interface sites is constructed to facilitate CO2 adsorption and activation, while concurrently boosting CH4 dissociation. As a prototype, the Au quantum dots anchored on oxygen-deficient TiO2 nanosheets are fabricated, where the Au-Vo-Ti interface sites for CO2 adsorption and activation are collectively disclosed by in situ Kelvin probe force microscopy, quasi in situ X-ray photoelectron spectroscopy and theoretical calculations. Compared with single metal site, the Au-Vo-Ti interface sites exhibit the lower CO2 adsorption energy and decrease the energy barrier of the *CO2 hydrogenation step from 1.
View Article and Find Full Text PDFSingle-Atom Mo Supported by TiO for Photocatalytic Nitrogen Fixation.
Langmuir
December 2024
State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021, PR China.
The challenge of achieving efficient photocatalysts for the fixation of ambient nitrogen to ammonia persists. The utilization efficiency of single-metal-atom catalysts leads to an increased number of active sites, while their distinctive geometrical and electronic characteristics contribute to enhancing the intrinsic activity of each individual site. In this study, we present a method using an organic molecule to assist in loading TiO with Mo single atoms for the purpose of photocatalytic nitrogen fixation.
View Article and Find Full Text PDFHow Can One Metal Power Nucleic Acid Phosphodiester Bond Cleavage by a Nuclease? Multiscale Computational Studies Highlight a Diverse Mechanistic Landscape.
J Phys Chem B
December 2024
Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, Alberta, Canada T1K 3M4.
Despite the remarkable resistance of the nucleic acid phosphodiester backbone to degradation affording genetic stability, the P-O bond must be broken during DNA repair and RNA metabolism, among many other critical cellular processes. Nucleases are powerful enzymes that can enhance the uncatalyzed rate of phosphodiester bond cleavage by up to ∼10-fold. Despite the most well accepted hydrolysis mechanism involving two metals (M to activate a water nucleophile and M to stabilize the leaving group), experimental evidence suggests that some nucleases can use a single metal to facilitate the chemical step, a controversial concept in the literature.
View Article and Find Full Text PDFWhat Is the "Other" Site in M-N-C?
J Am Chem Soc
December 2024
Texas Materials Institute and Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78731, United States.
Single metal atoms embedded in nitrogen-doped graphene (M-N-C) have emerged as a promising catalyst for a wide variety of reactions. In addition to the pyridinic site, there is another site responsible for the catalytic activity, but its structure is under debate. Here, we resolve its structure using first-principles calculations.
View Article and Find Full Text PDFMechanism of Catalysis and Substrate Binding of Epoxyqueuosine Reductase in the Biosynthetic Pathway to Queuosine-Modified tRNA.
Biochemistry
December 2024
Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
Post-transcriptional modifications at the anticodon stem-loop of tRNAs are key to the translation function. Metabolic pathways to these modifications often incorporate complex enzymology. A notable example is the hypermodified nucleoside, queuosine, found at the wobble position of Asn, Asp, His, and Tyr encoding tRNAs.
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!