The significance of identifying the fundamental mechanism of interactions between adjacent catalytic active centers has long been underestimated. Utilizing density functional theory calculations, we demonstrate controllable cooperative interaction between two nearby Fe centers embedded on nitrogenated graphene aided by CO adsorption. The interconnected adjacent Fe atoms respond cooperatively to CO molecules with communicative structural self-adaption and electronic transformation. The adsorbed CO changes not only the spin of the active site it is attached to but also that of its adjacent site. Consequently, the two adjacent Fe atoms feature unique oscillatory long-range spin coupling. Our theoretical investigation suggests cooperative communication between adjacent active sites on a single-atom catalyst is nontrivial.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.8b07816 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Mechanistic insights and atmospheric implications of the degradation reaction of 3-methoxy-1-propanol by reaction with hydroxyl radicals and identification of the end products in the presence of O/NO.
Sci Rep
January 2025
Department of Physical Chemistry, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk, 80-233, Poland.
The study investigated the degradation of 3-methoxy-1-propanol (3M1P) by OH using the M06-2X/6-311++G(d, p) level, with CCSD(T) single-point corrections. We focused on hydrogen atom abstraction from various alkyl groups within the molecule. The rate coefficient for 3M1P degradation was calculated from the sum of the rate coefficients corresponding to the removal of H-atoms from primary (-CH), secondary (-CH-), tertiary (-CH< ), and alcohol (-ΟH) groups.
View Article and Find Full Text PDFDiatomic Palladium Catalyst for Enhanced Photocatalytic Water-Donating Transfer Hydrogenation.
J Am Chem Soc
January 2025
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Jiangsu Province Key Laboratory of Green Biomass-Based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, People's Republic of China.
Diatomic catalysts (DACs) present unique opportunities for harnessing ensemble effects between adjacent metal atoms, thus, expanding the properties of single-atom catalysts (SACs). However, the precise preparation and characterization of this type of catalyst remains challenging. Following a precursor-preselected strategy, here, we report the synthesis of a carbon nitride-supported Pd-DAC, which achieves an excellent yield of 92% for photocatalytic water-donating transfer hydrogenation of 4-vinylphenol to 4-ethylphenol, far exceeding that of other metal species, including Pd single atoms (47%) and nanoparticles (1%).
View Article and Find Full Text PDFRealizing C-C Coupling via Accumulation of C1 Intermediates within Dual-Vacancy-Induced Dipole-Limited Domain Field to Propel Photoreduction of CO-to-C2 Fuel.
Adv Mater
January 2025
Faculty of Chemistry and Chemical Engineering, Shantou University, Shantou, 515063, P. R. China.
Photocatalytic conversion of CO and HO into high-value-added C2 fuels remains a tough challenge, mainly due to the insufficient concentration of photogenerated electrons for the instability of C1 intermediates, which often tend to desorb easily and disable to form C─C bonds. In this work, photoreduction of CO-to-CH is successfully achieved by introducing adjacent C, N dual-vacancy sites within the heptazine rings of ultrathin g-CN, which results in the opening of two neighboring heptazine rings and forms a distinctive dipole-limited domain field (DLDF) structure. In situ X-ray photoelectron spectra and in situ fourier transform infrared spectra provide direct evidence of the rapid accumulation and transformation of C1 intermediates, especially CO and CHO, within the DLDF.
View Article and Find Full Text PDFFe─N and FeCo Nanoalloy Dual-Site Modulation by Skeleton Defect in N-Doped Graphene Aerogel for Enhanced Bifunctional Oxygen Electrocatalyst in Zinc-air Battery.
Small
January 2025
Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education of the P. R. China, Shandong University, Jinan, 250100, P. R. China.
The dual-site electrocatalysts formed by metal single atoms combines with metal nanoparticles represent a promising strategy to enhance both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance. Herein, defect engineering is applied to dual-site ORR and OER electrocatalysts. Its design, synthesis, structural properties, and catalytic performance experimentally and theoretically are insightfully studied for the single-atomic Fe─N and the adjacent FeCo nanoalloy (FeCo) as dual-site loading on nitrogen-doped graphene aerogel (Fe─N/FeCo@NGA).
View Article and Find Full Text PDFElectronic Structure Modulation Induced by the Synergy of Cobalt Low-Nuclearity Clusters and Mononuclear Sites for Efficient Oxygen Electrocatalysis.
ACS Nano
December 2024
School of Chemistry and Materials Science, Nanjing University of Information Science & Technology, Nanjing 210044, PR China.
The development of high-performance bifunctional single-atom catalysts for use in applications, such as zinc-air batteries, is greatly impeded by mild oxygen reduction and evolution reactions (ORR and OER). Herein, we report a bifunctional oxygen electrocatalyst designed to overcome these limitations. The catalyst consists of well-dispersed low-nuclearity Co clusters and adjacent Co single atoms over a nitrogen-doped carbon matrix (Co/NC).
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!