Single‐Atom‐Layer Catalysis in a MoS2 Monolayer Activated by Long‐Range Ferromagnetism for the Hydrogen Evolution Reaction: Beyond Single‐Atom Catalysis
Abstract:Single-atom-layer catalysts with fully activated basal-atoms will provide asolution to the low loading-density bottlenecko fs ingle-atom catalysts.H erein, we activate the majority of the basal sites of monolayer MoS 2 ,b yd oping Co ions to induce long-range ferromagnetic order.This strategy,as revealed by in situ synchrotron radiation microscopic infrared spectroscopya nd electrochemical measurements,c ould activate more than 50 %ofthe originally inert basal-plane Satoms in the ferromagnetic monolayer for th… Show more
“…The thickness of FD-MoS 2 -3 was measured to be 0.76 nm via atomic force microscopy (AFM) in Supplementary Fig. 1 , in accordance with the characteristic of monolayer MoS 2 structures 16 . Fig.…”
Section: Resultssupporting
confidence: 68%
“…The synergistic effect between the point defects were also revealed to improve the HER performance of MoS 2 13 – 15 . However, current defect engineering strategies on MoS 2 are mostly based on heterogeneous atom doping 7 , 12 , 14 – 16 , as mentioned above, particularly noble metal doping, which may add the cost and complexity for synthesis approaches. Seeking a facile and economical defect engineering strategy on 2D electrochemical catalysts is of great importance.…”
Defect engineering is an effective strategy to improve the activity of two-dimensional molybdenum disulfide base planes toward electrocatalytic hydrogen evolution reaction. Here, we report a Frenkel-defected monolayer MoS2 catalyst, in which a fraction of Mo atoms in MoS2 spontaneously leave their places in the lattice, creating vacancies and becoming interstitials by lodging in nearby locations. Unique charge distributions are introduced in the MoS2 surface planes, and those interstitial Mo atoms are more conducive to H adsorption, thus greatly promoting the HER activity of monolayer MoS2 base planes. At the current density of 10 mA cm−2, the optimal Frenkel-defected monolayer MoS2 exhibits a lower overpotential (164 mV) than either pristine monolayer MoS2 surface plane (358 mV) or Pt-single-atom doped MoS2 (211 mV). This work provides insights into the structure-property relationship of point-defected MoS2 and highlights the advantages of Frenkel defects in tuning the catalytic performance of MoS2 materials.
“…The thickness of FD-MoS 2 -3 was measured to be 0.76 nm via atomic force microscopy (AFM) in Supplementary Fig. 1 , in accordance with the characteristic of monolayer MoS 2 structures 16 . Fig.…”
Section: Resultssupporting
confidence: 68%
“…The synergistic effect between the point defects were also revealed to improve the HER performance of MoS 2 13 – 15 . However, current defect engineering strategies on MoS 2 are mostly based on heterogeneous atom doping 7 , 12 , 14 – 16 , as mentioned above, particularly noble metal doping, which may add the cost and complexity for synthesis approaches. Seeking a facile and economical defect engineering strategy on 2D electrochemical catalysts is of great importance.…”
Defect engineering is an effective strategy to improve the activity of two-dimensional molybdenum disulfide base planes toward electrocatalytic hydrogen evolution reaction. Here, we report a Frenkel-defected monolayer MoS2 catalyst, in which a fraction of Mo atoms in MoS2 spontaneously leave their places in the lattice, creating vacancies and becoming interstitials by lodging in nearby locations. Unique charge distributions are introduced in the MoS2 surface planes, and those interstitial Mo atoms are more conducive to H adsorption, thus greatly promoting the HER activity of monolayer MoS2 base planes. At the current density of 10 mA cm−2, the optimal Frenkel-defected monolayer MoS2 exhibits a lower overpotential (164 mV) than either pristine monolayer MoS2 surface plane (358 mV) or Pt-single-atom doped MoS2 (211 mV). This work provides insights into the structure-property relationship of point-defected MoS2 and highlights the advantages of Frenkel defects in tuning the catalytic performance of MoS2 materials.
“…[ 29–35 ] Compared with other supports, the electronic structure of isolated metal atoms can be finely tuned by the anchoring atom and the neighboring transition metal atoms. [ 21,29,36–38 ] This results in a programmable coordination environment to control the catalytic behavior by the metal–support interaction and thus influences the catalytic activity. [ 39–41 ]…”
The facile creation of high‐performance single‐atom catalysts (SACs) is intriguing in heterogeneous catalysis, especially on 2D transition‐metal dichalcogenides. An efficient spontaneous reduction approach to access atomically dispersed iron atoms supported over defect‐containing MoS2 nanosheets is herein reported. Advanced characterization methods demonstrate that the isolated iron atoms situate atop of molybdenum atoms and coordinate with three neighboring sulfur atoms. This Fe SAC delivers exceptional catalytic efficiency (1 atm O2 @ 120 °C) in the selective oxidation of benzyl alcohol to benzaldehyde, with 99% selectivity under almost 100% conversion. The turnover frequency is calculated to be as high as 2105 h−1. Moreover, it shows admirable recyclability, storage stability, and substrate tolerance. Density functional theory calculations reveal that the high catalytic activity stems from the optimized electronic structure of single iron atoms over the MoS2 support.
“…One of the effective strategies to solve the problem is to sufficiently activate the inert basal plane of TMDs materials as active regions to anchor the metal species 9,10 . Some physical or chemical methods have been reported to fully utilize the inert basal atoms, such as constructing vacancies 11,12 , manipulating strain 13,14 , creating distortion 15 , inducting doped atoms [16][17][18][19] and so on. Among these, injecting lattice strain into the TMDs planes can create the active surface and induce the strain-assisted single metal sites, which may be benificial to improve the catalytic activity.…”
Engineering the local three-dimensional structure of metal sites has important effect to maximize the activity and selectivity of single-atom site catalysts. Here, we engineer a strain-assisted single Pt sites structure on highly curved MoS 2 surface to enhance the H 2 S sensor property. Through introducing N-methyl-2-pyrrolidone (NMP) as guiding molecules, a multilayer MoS 2 structure with bending base planes is achieved. This bending behavior can not only inject uniform in-plane strain into the original inert MoS 2 basal plane but also introduce sufficient accessible sites to anchor Pt monomers. Further experimental and theoretical results show that the high-curvature MoS 2 surface endows 0.8% stretch strain onto the low-coordinated single Pt sites with a unique "tip" effect, which will lead to more accumulation of electrons around the Pt species, thus accelerating the electric transfer process between H 2 S and supports. The final catalyst delivers the pronouncedly enhanced H 2 S
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