Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable 'fingerprint' for such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3-15 nanometres, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.
Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 .
Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel–vanadium-layered double hydroxide that shows a current density of 27 mA cm−2 (57 mA cm−2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel–iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel–vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting.
The effect of defects on electron-hole separation is not always clear and is sometimes contradictory. Herein, we initially built clear models of two-dimensional atomic layers with tunable defect concentrations, and hence directly disclose the defect type and distribution at atomic level. As a prototype, defective one-unit-cell ZnInS atomic layers are successfully synthesized for the first time. Aberration-corrected scanning transmission electron microscopy directly manifests their distinct zinc vacancy concentrations, confirmed by positron annihilation spectrometry and electron spin resonance analysis. Density-functional calculations reveal that the presence of zinc vacancies ensures higher charge density and efficient carrier transport, verified by ultrafast photogenerated electron transfer time of ∼15 ps from the conduction band of ZnInS to the trap states. Ultrafast transient absorption spectroscopy manifests the higher zinc vacancy concentration that allows for ∼1.7-fold increase in average recovery lifetime, confirmed by surface photovoltage spectroscopy and PL spectroscopy analysis, which ensures promoted carrier separation rates. As a result, the one-unit-cell ZnInS layers with rich zinc vacancies exhibit a carbon monoxide formation rate of 33.2 μmol g h, roughly 3.6 times higher than that of the one-unit-cell ZnInS layers with poor zinc vacancies, while the former's photocatalytic activity shows negligible loss after 24 h photocatalysis. This present work uncovers the role of defects in affecting electron-hole separation at atomic level, opening new opportunities for achieving highly efficient solar CO reduction performances.
Nitrogen fixation is one of the most important issues but a long-standing challenge in chemistry. Here, we propose FeN3-embedded graphene as the catalyst for nitrogen fixation from first-principles calculations. Results show that in view of the chemical coordination, the FeN3 center is highly spin-polarized with a localized magnetic moment substantially to promote N2 adsorption and activate its inert N-N triple bond. The synergy between the graphene and FeN3 equips the system with novel features for the catalytic conversion of the activated N2 into NH3 via a six-proton and six-electron process, following three possible reaction pathways at room temperature. Our findings provide a rational paradigm for catalytic nitrogen fixation that would be conducive to ammonia production.
It is highly desirable yet remains challenging to improve the dispersion and usage of noble metal cocatalysts, beneficial to charge transfer in photocatalysis. Herein, for the first time, single Pt atoms are successfully confined into a metal-organic framework (MOF), in which electrons transfer from the MOF photosensitizer to the Pt acceptor for hydrogen production by water splitting under visible-light irradiation. Remarkably, the single Pt atoms exhibit a superb activity, giving a turnover frequency of 35 h , ≈30 times that of Pt nanoparticles stabilized by the same MOF. Ultrafast transient absorption spectroscopy further unveils that the single Pt atoms confined into the MOF provide highly efficient electron transfer channels and density functional theory calculations indicate that the introduction of single Pt atoms into the MOF improves the hydrogen binding energy, thus greatly boosting the photocatalytic H production activity.
We use x-ray emission spectroscopy to elucidate the molecular structure of liquid methanol, water, and methanol-water solutions. We find that molecules in the pure liquid methanol predominantly persist as hydrogen-bonded chains and rings with six and/or eight molecules of equal abundance. For water-methanol solutions we find evidence of incomplete mixing at the microscopic level. Our results provide a new explanation for a smaller entropy increase in the solution due to water molecules bridging methanol chains to form rings.
Our first principles calculations reveal that oxidative cut of graphene is realized by forming epoxy and then carbonyl pairs. Direct forming carbonyl pair to tear graphene up from an edge position is not favorable in energy. This atomic picture is valuable for developing effective graphene manipulation means. The proposed epoxy pairs may be related to some long puzzling experimental observations on graphene oxide.Due to its novel physical properties and great potential in various applications, graphene has attracted an intense research interest recently. i A big challenge in graphene research is the massive production of high quality samples. The existing physical approaches ii prohibit producing and processing graphene on large scales. In this context, the versatile chemistry of carbon may offer a promising alternative for cost-effective mass production of graphene, as demonstrated by its graphene-oxide (GO) synthesis route. Upon oxidation, graphite readily exfoliates as single sheets in water, forming GO. The π conjugation in graphene can then be largely restored by reducing GO. iii,iv Oxidation now becomes an important chemical means to manipulate graphitic materials.It has been observed that, during oxidation process, graphitic structures automatically break down into smaller parts. iv,v For electronics applications, it is very desirable to cut graphene with designed shape and size. Therefore, an atomistic understanding of the mechanism for such oxidative breakup of graphene sheets is especially valuable. Based on first-principles calculations, an unzipping mechanism has been proposed, vi where the epoxy groups formed during oxidation were suggested to have a preference of aligning in a line. The aligned epoxy groups then induce a rupture of the underlying C-C bonds (Figure 1a). However, it is still not clear how the graphene sheets can eventually break up, since even after the rupture of the C-C bonds the graphene sheet remains bridged by O atoms. Actually, a recent study shows that the mechanical strength of the graphene sheet is not strongly affected by the presence of epoxy chain and an epoxy line defect only weakens the fracture stress of the sheet by approximately 16%. vii This result indicates that, although the epoxy chain breaks the underlying C-C bonds, it does not really cause a breakup of the material by itself. The chemistry of the whole breakup process is still not clear.Previous experimental study on GO has suggested the existence of carbonyl groups, viii and a very recent two dimensional NMR experiment shows that the carbonyl groups are spatially separated from the majority sp 2 , C-OH, and epoxide carbons. ix This result indicates that carbonyl groups mainly distribute at the GO edge, and may thus be closely related to the oxidative break process. In this communication, based on density functional theory (DFT), we reveal how the oxygen attacks can break up atomic structure of graphene. Both the middle-site-initiated and the edge-site-initiated processes are studied, and the former based on i...
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