13 research outputs found

    Theoretical Study on the Mechanism of Photoreduction of CO<sub>2</sub> to CH<sub>4</sub> on the Anatase TiO<sub>2</sub>(101) Surface

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    Artificial photosynthesis of CO<sub>2</sub> has recently attracted intense attention as a potential solution for the energy crisis and global warming. However, the molecular mechanism of the reaction is quite complicated and is far from understood. We performed a first-principles calculation on the thermodynamically feasible formaldehyde pathway: CO<sub>2</sub> → HCOOH → H<sub>2</sub>CO → CH<sub>3</sub>OH → CH<sub>4</sub>. The interconversion of the C1 molecules has been systematically investigated. We find that a two-electron process has a lower barrier than a one-electron process for the photoreduction of all of the molecules under investigation except for methanol. On the basis of the full potential energy surface for photoreduction of CO<sub>2</sub> to methane, the rate-limiting step is found to be the photoreduction of formic acid to formaldehyde, which contains the elementary step that has the largest kinetic barrier. It will be more efficient if CO instead of formic acid is the precursor of formaldehyde. Then the rate-limiting step becomes the photoreduction of CO<sub>2</sub> to CO. However, the barriers for the photoreduction of the organic molecules are all higher than the barriers for their photodecomposition reaction, which suggests that all of the C1 organic molecules are more easily oxidized than reduced. Thus, charge separation is crucial for improving the efficiency and selectivity of the reaction. The intertwining of photoreduction and photooxidation reactions might be one of the major reasons for the complexity and low efficiency of the reaction. On the basis of the calculations, a new mechanism for the reaction is proposed

    New Mechanism for Photocatalytic Reduction of CO<sub>2</sub> on the Anatase TiO<sub>2</sub>(101) Surface: The Essential Role of Oxygen Vacancy

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    Photocatalytic reduction of CO<sub>2</sub> into organic molecules is a very complicated and important reaction. Two possible pathways, the fast-hydrogenation (FH) path and the fast-deoxygenation (FdO) path, have been proposed on the most popular photocatalyst TiO<sub>2</sub>. We have carried out first-principles calculations to investigate both pathways on the perfect and defective anatase TiO<sub>2</sub>(101) surfaces to provide comprehensive understanding of the reaction mechanism. For the FH path, it is found that oxygen vacancy on defective surface can greatly lower the barrier of the deoxygenation processes, which makes it a more active site than the surface Ti. For the FdO path, our calculation suggests that it can not proceed on the perfect surface, nor can it proceed on the defective surface due to their unfavorable energetics. Based on the fact that the FH path can proceed both at the surface Ti site and the oxygen vacancy site, we have proposed a simple mechanism that is compatible with various experiments. It can properly rationalize the selectivity of the reaction and greatly simplify the picture of the reaction. The important role played by oxygen vacancy in the new mechanism is highlighted and a strategy for design of more efficient photocatalysts is proposed accordingly

    Dehydrogenation of Propane to Propylene by a Pd/Cu Single-Atom Catalyst: Insight from First-Principles Calculations

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    The catalytic properties of the single-Pd-doped Cu<sub>55</sub> nanoparticle toward propane dehydrogenation have been systemically investigated by first-principles calculations, and the possible reaction mechanisms and effects of the single and multiple Pd doping on the catalytic activity have been discussed. Calculations reveal that the low-energy catalytic conversion of propane to propylene by the Pd/Cu single-atom catalyst comprises the initial crucial C–H bond breaking at either the methyl or methylene group, the facile diffusion of detached H atoms on the Cu surface, and the subsequent C–H bond dissociation activation of the adsorbed propyl species. The single-Pd-doped Cu<sub>55</sub> nanoparticle shows remarkable activity toward C–H bond activation, and the presence of relatively inactive Cu surface is beneficial for the coupling and desorption of detached H atoms and can reduce side reactions such as deep dehydrogenation and C–C bond breaking. The single-Pd-doped Cu<sub>55</sub> cluster bears good balance between the maximum use of the noble metal and the activity, and it may serve as a promising single-atom catalyst toward selective dehydrogenation of propane

    Feasible Catalytic Strategy for Writing Conductive Nanoribbons on a Single-Layer Graphene Fluoride

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    An accessible method for local reduction of graphene fluoride catalyzed by the Pt-coated nanotip with the assistance of a mixture of hydrogen and ethylene atmosphere is proposed and fully explored theoretically. Detailed mechanisms and roles of hydrogen and ethylene molecules in the cyclic reduction is discussed based on extensive first-principles calculations. It is demonstrated that the proposed cyclic reduction strategy is energetically favorable. This new strategy can be effectively applied in scanning probe lithography to fabricate electronic circuits at the nanoscale on graphene fluoride under mild conditions

    Hydrophobicity and Hydrophilicity Balance Determines Shape Selectivity of Suzuki Coupling Reactions Inside Pd@meso-SiO<sub>2</sub> Nanoreactor

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    Molecular sorting and catalysis directed by shape selectivity have been extensively applied in porous extended frameworks for a low-carbon, predictable, renewable component of modern industry. A comprehensive understanding of the underlying recognition mechanism toward different shapes is unfortunately still missing, owing to the lack of structural and dynamic information under operating conditions. We demonstrate here that such difficulties can be overcome by state-of-the-art molecular dynamics simulations which provide atomistic details that are not accessible experimentally, as exemplified by our interpretation for the experimentally observed aggregation-induced shape selectivity for Suzuki C–C coupling reaction catalyzed by Pd particles in mesoporous silica. It is found that both aggregation ability and aggregating pattern of the reactants play the decisive role in controlling the shape selectivity, which are in turn determined by the balance between the hydrophobicity and hydrophilicity of the reactants, or in other words, by the balance between the noncovalent hydrogen bonding interaction and van der Waals forces. A general rule that allows prediction of the shape selectivity of a reactant has been proposed and verified against experiments. We show that molecular modeling is a powerful tool for rational design of new mesoporous systems and for the control of catalytic reactions that are important for the petrochemical industry

    Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst

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    Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H<sub>2</sub>SO<sub>4</sub> solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications

    Theoretical Modeling of Plasmon-Enhanced Raman Images of a Single Molecule with Subnanometer Resolution

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    Under local plasmonic excitation, Raman images of single molecules can now surprisingly reach subnanometer resolution. However, its physical origin has not been fully understood. Here we report a quantum-mechanical description of the interaction between a molecule and a highly confined plasmonic field. We show that when the spatial distribution of the plasmonic field is comparable to the size of the molecule, the optical transition matrix of the molecule becomes dependent on the position and distribution of the plasmonic field, resulting in a spatially resolved high-resolution Raman image of the molecule. The resonant Raman image reflects the electronic transition density of the molecule. In combination with first-principles calculations, the simulated Raman image of a porphyrin derivative adsorbed on a silver surface nicely reproduces its experimental counterpart. The present theory provides the basic framework for describing linear and nonlinear responses of molecules under highly confined plasmonic fields

    Negative Differential Resistance in a Hybrid Silicon-Molecular System: Resonance between the Intrinsic Surface-States and the Molecular Orbital

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    It has been a long-term desire to fabricate hybrid silicon-molecular devices by taking advantages of organic molecules and the existing silicon-based technology. However, one of the challenging tasks is to design applicable functions on the basis of the intrinsic properties of the molecules, as well as the silicon substrates. Here we demonstrate a silicon-molecular system that produces negative differential resistance (NDR) by making use of the well-defined intrinsic surface-states of the Si (111)-√3 × √3-Ag (R3-Ag/Si) surface and the molecular orbital of cobalt(II)–phthalocyanine (CoPc) molecules. From our experimental results obtained using scanning tunneling microscopy/spectroscopy, we find that NDR robustly appears at the Co<sup>2+</sup> ion centers of the CoPc molecules, independent of the adsorption configuration of the CoPc molecules and irrespective of doping type and doping concentration of the silicon substrates. Joint with first principle calculations, we conclude that NDR is originated from the resonance between the intrinsic surface-state band S<sub>1</sub> of the R3-Ag/Si surface and the localized unoccupied Co<sup>2+</sup> <i>d</i><sub><i>z</i><sup>2</sup></sub> orbital of the adsorbed CoPc molecules. We expect that such a mechanism can be generally used in other silicon-molecular systems

    Coagulation Behavior of Graphene Oxide on Nanocrystallined Mg/Al Layered Double Hydroxides: Batch Experimental and Theoretical Calculation Study

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    Graphene oxide (GO) has attracted considerable attention because of its remarkable enhanced adsorption and multifunctional properties. However, the toxic properties of GO nanosheets released into the environment could lead to the instability of biological system. In aqueous phase, GO may interact with fine mineral particles, such as chloridion intercalated nanocrystallined Mg/Al layered double hydroxides (LDH–Cl) and nanocrystallined Mg/Al LDHs (LDH–CO<sub>3</sub>), which are considered as coagulant molecules for the coagulation and removal of GO from aqueous solutions. Herein the coagulation of GO on LDHs were studied as a function of solution pH, ionic strength, contact time, temperature and coagulant concentration. The presence of LDH–Cl and LDH–CO<sub>3</sub> improved the coagulation of GO in solution efficiently, which was mainly attributed to the surface oxygen-containing functional groups of LDH–Cl and LDH–CO<sub>3</sub> occupying the binding sites of GO. The coagulation of GO by LDH–Cl and LDH–CO<sub>3</sub> was strongly dependent on pH and ionic strength. Results of theoretical DFT calculations indicated that the coagulation of GO on LDHs was energetically favored by electrostatic interactions and hydrogen bonds, which was further evidenced by FTIR and XPS analysis. By integrating the experimental results, it was clear that LDH–Cl could be potentially used as a cost-effective coagulant for the elimination of GO from aqueous solutions, which could efficiently decrease the potential toxicity of GO in the natural environment

    Visualizing Large Facet-Dependent Electronic Tuning in Monolayer WSe<sub>2</sub> on Au Surfaces

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    Two-dimensional transition metal dichalcogenides (TMDs) have shown great importance in the development of novel ultrathin optoelectronic devices owing to their exceptional electronic and photonic properties. Effectively tuning their electronic band structures is not only desired in electronics applications but also can facilitate more novel properties. In this work, we demonstrate that large electronic tuning on a WSe2 monolayer can be realized by different facets of a Au-foil substrate, forming in-plane p–n junctions with remarkable built-in electric fields. This facet-dependent tuning effect is directly visualized by using scanning tunneling microscopy and differential conductance (dI/dV) spectroscopy. First-principles calculations reveal that the atomic arrangement of the Au facet effectively changes the interfacial coupling and charge transfer, leading to different magnitudes of charge doping in WSe2. Our study would be beneficial for future customized fabrication of TMD-junction devices via facet-specific construction on the substrate
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