Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Spin engineering of single-site metal catalysts.

ABSTRACT: Single-site metal atoms (SMAs) on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance. However, rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging. Herein, N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN₄ centers (d-FeN₄). This unique d-FeN₄ demonstrates much higher intrinsic activity toward oxygen reduction reaction (ORR) in HClO₄ than FeN₄ without micropore underneath and commercial Pt/C. Both theoretical calculation and electronic structure characterization imply that d-FeN₄ endows central Fe with medium spin (t_2g ⁴ e_g ¹), which provides a spin channel for electron transition compared with FeN₄ with low spin. This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR, thus showing faster kinetics than FeN₄. This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis.

SUBMITTER: Li Z

PROVIDER: S-EPMC9249949 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

Project description:Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via ?-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

| S-EPMC5013626 | biostudies-literature

Spin-orbit engineering in transition metal dichalcogenide alloy monolayers.

Project description:Binary transition metal dichalcogenide monolayers share common properties such as a direct optical bandgap, spin-orbit splittings of hundreds of meV, light-matter interaction dominated by robust excitons and coupled spin-valley states. Here we demonstrate spin-orbit-engineering in Mo(1-x)WxSe2 alloy monolayers for optoelectronics and applications based on spin- and valley-control. We probe the impact of the tuning of the conduction band spin-orbit spin-splitting on the bright versus dark exciton population. For MoSe2 monolayers, the photoluminescence intensity decreases as a function of temperature by an order of magnitude (4-300?K), whereas for WSe2 we measure surprisingly an order of magnitude increase. The ternary material shows a trend between these two extreme behaviours. We also show a non-linear increase of the valley polarization as a function of tungsten concentration, where 40% tungsten incorporation is sufficient to achieve valley polarization as high as in binary WSe2.

| S-EPMC4682039 | biostudies-literature

A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts.

Project description:Development of single-site catalysts supported by ultrathin two-dimensional (2D) porous matrix with ultrahigh surface area is highly desired but also challenging. Here we report a cocoon silk chemistry strategy to synthesize isolated metal single-site catalysts embedded in ultrathin 2D porous N-doped carbon nanosheets (M-ISA/CNS, M?=?Fe, Co, Ni). X-ray absorption fine structure analysis and spherical aberration correction electron microscopy demonstrate an atomic dispersion of metal atoms on N-doped carbon matrix. In particular, the Co-ISA/CNS exhibit ultrahigh specific surface area (2105?m2?g-1) and high activity for C-H bond activation in the direct catalytic oxidation of benzene to phenol with hydrogen peroxide at room temperature, while the Co species in the form of phthalocyanine and metal nanoparticle show a negligible activity. Density functional theory calculations discover that the generated O?=?Co?=?O center intermediates on the single Co sites are responsible for the high activity of benzene oxidation to phenol.

| S-EPMC6155020 | biostudies-literature

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering.

Project description:Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

| S-EPMC5030650 | biostudies-literature

Single-site metal-organic framework catalysts for the oxidative coupling of arenes <i>via</i> C-H/C-H activation.

Project description:C-H activation reactions are generally associated with relatively low turnover numbers (TONs) and high catalyst concentrations due to a combination of low catalyst stability and activity, highlighting the need for recyclable heterogeneous catalysts with stable single-atom active sites. In this work, several palladium loaded metal-organic frameworks (MOFs) were tested as single-site catalysts for the oxidative coupling of arenes (e.g. o-xylene) via C-H/C-H activation. Isolation of the palladium active sites on the MOF supports reduced Pd(0) aggregate formation and thus catalyst deactivation, resulting in higher turnover numbers (TONs) compared to the homogeneous benchmark reaction. Notably, a threefold higher TON could be achieved for palladium loaded MOF-808 due to increased catalyst stability and the heterogeneous catalyst could efficiently be reused, resulting in a cumulative TON of 1218 after three runs. Additionally, the palladium single-atom active sites on MOF-808 were successfully identified by Fourier transform infrared (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopy.

| S-EPMC6432273 | biostudies-literature

Site-specific electrodeposition enables self-terminating growth of atomically dispersed metal catalysts.

Project description:The growth of atomically dispersed metal catalysts (ADMCs) remains a great challenge owing to the thermodynamically driven atom aggregation. Here we report a surface-limited electrodeposition technique that uses site-specific substrates for the rapid and room-temperature synthesis of ADMCs. We obtained ADMCs by the underpotential deposition of a non-noble single-atom metal onto the chalcogen atoms of transition metal dichalcogenides and subsequent galvanic displacement with a more-noble single-atom metal. The site-specific electrodeposition enables the formation of energetically favorable metal-support bonds, and then automatically terminates the sequential formation of metallic bonding. The self-terminating effect restricts the metal deposition to the atomic scale. The modulated ADMCs exhibit remarkable activity and stability in the hydrogen evolution reaction compared to state-of-the-art single-atom electrocatalysts. We demonstrate that this methodology could be extended to the synthesis of a variety of ADMCs (Pt, Pd, Rh, Cu, Pb, Bi, and Sn), showing its general scope for functional ADMCs manufacturing in heterogeneous catalysis.

| S-EPMC7486907 | biostudies-literature

In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation.

Project description:Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O2 is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T20 values up to 130 °C below the previously reported Rh1/NPTA.

| S-EPMC6430772 | biostudies-literature

Strong metal-support interaction promoted scalable production of thermally stable single-atom catalysts.

Project description:Single-atom catalysts (SACs) have demonstrated superior catalytic performance in numerous heterogeneous reactions. However, producing thermally stable SACs, especially in a simple and scalable way, remains a formidable challenge. Here, we report the synthesis of Ru SACs from commercial RuO2 powders by physical mixing of sub-micron RuO2 aggregates with a MgAl1.2Fe0.8O4 spinel. Atomically dispersed Ru is confirmed by aberration-corrected scanning transmission electron microscopy and X-ray absorption spectroscopy. Detailed studies reveal that the dispersion process does not arise from a gas atom trapping mechanism, but rather from anti-Ostwald ripening promoted by a strong covalent metal-support interaction. This synthetic strategy is simple and amenable to the large-scale manufacture of thermally stable SACs for industrial applications.

| S-EPMC7062790 | biostudies-literature

Coulomb-driven single defect engineering for scalable qubits and spin sensors in diamond.

Project description:Qubits based on colour centres in diamond became a prominent system for solid-state quantum information processing and sensing. But the deterministic creation of qubits and the control of their environment are still critical issues, preventing the development of a room-temperature quantum computer. We report on the high creation yield of NV centres of 75% (a tenfold enhancement) by charge-assisted defect engineering, together with an improvement of their spin coherence. The method strongly favours the formation and negative charge state of the NV centres with respect to intrinsic diamond, while it hinders the formation of competing and perturbing defects such as di-vacancies or NVH complexes. We evidence spectrally the charge state tuning of the implantation-induced vacancies from V0 to V-, key element of this Coulomb-driven engineering. The generality of the method is demonstrated using several donors (phosphorous, oxygen and sulphur) and applying it to other centres (SnV and MgV) in diamond.

| S-EPMC6823384 | biostudies-literature

Modulating the strong metal-support interaction of single-atom catalysts via vicinal structure decoration.

Project description:Metal-support interaction predominately determines the electronic structure of metal atoms in single-atom catalysts (SACs), largely affecting their catalytic performance. However, directly tuning the metal-support interaction in oxide supported SACs remains challenging. Here, we report a new strategy to subtly regulate the strong covalent metal-support interaction (CMSI) of Pt/CoFe2O4 SACs by a simple water soaking treatment. Detailed studies reveal that the CMSI is weakened by the bonding of H+, generated from water dissociation, onto the interface of Pt-O-Fe, resulting in reduced charge transfer from metal to support and leading to an increase of C-H bond activation in CH4 combustion by more than 50 folds. This strategy is general and can be extended to other CMSI-existed metal-supported catalysts, providing a powerful tool to modulating the catalytic performance of SACs.

| S-EPMC9307766 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data