Vertical Dipole Dominates Charge Carrier Lifetime in Monolayer Janus MoSSe.

Two-dimensional semiconductor materials with vertical dipoles are promising photocatalysts as vertical dipoles not only promote the electron-hole separation but also enhance the carrier redox ability. However, the influence of vertical dipoles on carrier recombination in such materials, especially the competing relationship between vertical dipoles and band gaps, is not yet clear. Herein, first-principles calculations and nonadiabatic molecular dynamics simulations were combined to clarify the influence of band gap and vertical dipole on the carrier lifetime in Janus MoSSe monolayer. By comparing with the results of MoS2 and MoSe2 as well as exploring the carrier lifetime of MoSSe under strain regulation, it has been demonstrated that the vertical dipole, rather than the band gap, is the dominant factor affecting the carrier lifetime. Strikingly, a linear relationship between the carrier lifetime and vertical dipole is revealed. These findings have important implications for the design of high-performance photocatalysts and optoelectronic devices.

Electron-Induced Synthesis of Dimethyl Ether in the Liquid-Vapor Interface of Methanol.

Ether synthesis from alcohol is known to be acid-catalyzed. Such a process could happen in the acidified liquid of alcohol, but hitherto lacking the experimental evidence. Here we demonstrate that dimethyl ether is spontaneously synthesized in the liquid-vapor interface of pure methanol after ionizing radiation with electrons. Using time-delayed tandem mass spectrometry measurements in combination with theoretical calculations, we further confirm that the protonated dimethyl ether is produced from the ion-molecule reactions not only in the dense vapor above the interface but also within the molecular clusters of the acidic interface. Our finding provides a convincing piece of evidence about the liquid-vapor interfacial acidification by the electron-impact ionizing radiation, exhibiting a promising way to control the chemical reactions in the liquid surface.

High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2.

Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity and durability, due to overoxidation of CH4 with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO2 photocatalyst, construction of Pd-O4 in surface reduces contribution of O sites to valence band, overcoming the limitations. In contrast to state of the art, 94.3% selectivity is achieved for C2H6 production at 0.91 mmol g-1 h-1 along with stoichiometric H2 production, approaching the level of thermocatalysis at relatively mild condition. As a benchmark, apparent quantum efficiency reaches 3.05% at 350 nm. Further elemental doping can elevate durability over 24 h by stabilizing lattice oxygen. This work provides new insights for high-performance photocatalytic NOCM by atomic engineering.

Promoting Water Activation by Photogenerated Holes in Monolayer C2N.

In photocatalytic reactions, the activation of H2O is very important for achieving high energy conversion efficiency. However, its activation mechanism under photoirradiation is still not fully understood. Here, on the basis of first-principles calculations, the role of photogenerated holes on the activation of H2O is investigated in a typical photocatalytic material C2N. The H2O molecule adsorbs at the six-membered N pore of C2N with a dual H-bonding configuration. Due to the electrostatic repulsion between the O atom of H2O and six N atoms of C2N, the energy level of the H2O molecule's highest occupied molecular orbital is raised significantly to exceed the valence band maximum of C2N, so that the photogenerated holes in C2N can be quickly captured by the H2O molecule. The captured photogenerated holes boost the activation of H2O and reduce the dissociation energy barrier from 1.61 to 0.69 eV. Besides, p-type defects of C2N have similar effects as photogenerated holes.

Designing Direct Z-Scheme Heterojunctions Enabled by Edge-Modified Phosphorene Nanoribbons for Photocatalytic Overall Water Splitting.

Direct Z-scheme photocatalyst possess promising potential to utilize solar radiation for photocatalytic overall water splitting; however, the design and characterization remain challenging. Here, we construct and verify a direct Z-scheme heterojunction using edge-modified phosphorene-nanoribbons (X-PNRs, where X = OH and OCN) with first-principles ground-state and excited-state density functional theory (DFT) calculations. The ground-state calculations provide fundamental properties such as geometric structure and band alignment. The linear-response time-dependent DFT (LR-TDDFT) calculations exhibit the photogenerated charge distribution and demonstrate the generation of interlayer excitons in heterojunctions, which are advantageous to the electron-hole recombination in Z-scheme heterojunctions. The ultrafast charge transfer at the interface studied by time-dependent ab initio nonadiabatic molecular dynamics (NAMD) simulations indicates that interlayer electron-hole recombination is prior to intralayer recombination for the OH/OCN-PNRs heterojunction, showing the characteristics of a Z-scheme heterojunction. Therefore, our computational work provides a universal strategy to design direct Z-scheme heterojunction photocatalysts for overall water splitting.

A rationally designed two-dimensional MoSe2/Ti2CO2 heterojunction for photocatalytic overall water splitting: simultaneously suppressing electron-hole recombination and photocorrosion.

Electron-hole recombination and photocorrosion are two challenges that seriously limit the application of two-dimensional (2D) transition metal dichalcogenides (TMDs) for photocatalytic water splitting. In this work, we propose a 2D van der Waals MoSe2/Ti2CO2 heterojunction that features promising resistance to both electron-hole recombination and photocorrosion existing in TMDs. By means of first-principles calculations, the MoSe2/Ti2CO2 heterojunction is demonstrated to be a direct Z-scheme photocatalyst for overall water splitting with MoSe2 and Ti2CO2 serving as photocatalysts for hydrogen and oxygen evolution reactions, respectively, which is beneficial to electron-hole separation. The ultrafast migration of photo-generated holes from MoSe2 to Ti2CO2 as well as the anti-photocorrosion ability of Ti2CO2 are responsible for photocatalytic stability. This heterojunction is experimentally reachable and exhibits a high solar-to-hydrogen efficiency of 12%. The strategy proposed here paves the way for developing 2D photocatalysts for water splitting with high performance and stability in experiments.

2D Heterostructured Nanofluidic Channels for Enhanced Desalination Performance of Graphene Oxide Membranes.

The two-dimensional (2D) lamellar membrane assembly technique shows substantial potential for sustainable desalination applications. However, the relatively wide and size-variable channels of 2D membranes in aqueous solution result in inferior salt rejections. Here we show the establishment of nanofluidic heterostructured channels in graphene oxide (GO) membranes by adding g-C3N4 sheets into GO interlamination. Benefiting from the presence of stable and sub-nanometer wide (0.42 nm) GO/g-C3N4 channels, the GO/g-C3N4 membrane exhibits salt rejections of ∼90% with water permeances of above 30 L h-1 m-2 bar-1, while the pure GO membrane only has salt rejections of below 30% accompanied by water permeances of below 4 L h-1 m-2 bar-1. Combining experimental and theoretical investigations, size exclusion has proved to be the dominating mechanism for high rejections, and the ultralow friction water flow along g-C3N4 sheets is responsible for permeation enhancements. Importantly, the GO/g-C3N4 membrane shows promising long-term, antioxidation, and antipressure stability.

Identifying the Molecular Orientation and Clusters in the Liquid-Vapor Interface of 1-Propanol by Time-Delayed Mass Spectrometry.

Structural inhomogeneity of the liquid-vapor interface, such as the spatial orientation of molecular specific groups and the non-uniform distribution of hydrogen-bonded (HB) clusters, is crucial for understanding the physicochemical processes therein. Although the molecular orientation at the outermost layer was authenticated, to date, direct experimental evidence of the in situ existence of different-sized HB clusters, as a long-standing theoretical argument, is still lacking. Here we report time-delayed electron-impact tandem mass spectrometry, and its powerful ability to identify the local structures of the liquid-vapor interface of 1-propanol is demonstrated not only by mapping the molecular orientations both in the outermost layer and in the subsurface but also by validating the existence of the HB molecular dimers in the subsurface by detecting their protonated ions. We further distinguish two different sources of the protonated dimer: the gas-phase protonation of the neutral dimer that evaporates in advance and the time-lag evaporation of the protonated dimer produced in the subsurface. This methodology is a brand-new way to explore the microstructures and the electron-driven chemical reactions in different local regions of the liquid-vapor interface.

Endowing g-C3 N4 Membranes with Superior Permeability and Stability by Using Acid Spacers.

g-C3 N4 membranes were modulated by intercalating molecules with SO3 H and benzene moieties between layers. The intercalation molecules break up the tightly stacking structure of g-C3 N4 laminates successfully and accordingly the modified g-C3 N4 membranes give rise to two orders magnitude higher water permeances without sacrificing the separation efficiency. The sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO)/g-C3 N4 with a thickness of 350 nm presents an exceptionally high water permeance of 8867 L h-1 m-2 bar-1 and 100 % rejection towards methyl blue, while the original g-C3 N4 membrane with a thickness of 226 nm only exhibits a permeance of 60 L h-1 m-2 bar-1 . Simultaneously, SO3 H sites firmly anchor nitrogen with base functionality distributing onto g-C3 N4 through acid-base interactions. This enables the nanochannels of g-C3 N4 based membranes to be stabilized in acid, basic, and also high-pressure environments for long periods.

Construction of direct Z-Scheme photocatalysts for overall water splitting using two-dimensional van der waals heterojunctions of metal dichalcogenides.

The direct Z-scheme system constructed by two-dimensional (2D) materials is an efficient route for hydrogen production from photocatalytic water splitting. In the present work, the 2D van der Waals (vdW) heterojunctions of MoSe2 /SnS2 , MoSe2 /SnSe2 , MoSe2 /CrS2 , MoTe2 /SnS2 , MoTe2 /SnSe2 , and MoTe2 /CrS2 are proposed to be promising candidates for direct Z-scheme photocatalysts and verified by first principles calculations. Perpendicular electric field is induced in these 2D vdW heterojunctions, which enhances the efficiency of solar energy utilization. Replacing MoSe2 with MoTe2 not only facilitates the interlayer carrier migration, but also improves the optical absorption properties for these heterojunctions. Excitingly, the 2D vdW MoTe2 /CrS2 heterojunction is demonstrated, for the first time, to be 2D near-infrared-light driven photocatalyst for direct Z-scheme water splitting. © 2018 Wiley Periodicals, Inc.

Material Design for Photocatalytic Water Splitting from a Theoretical Perspective.

Currently, problems associated with energy and environment have become increasingly serious. Producing hydrogen, a clean and renewable resource, through photocatalytic water splitting using solar energy is a feasible and efficient route for resolving these problems, and great efforts have been devoted to improve the solar-to-hydrogen efficiency. Light harvesting and electron-hole separation are key in enhancing the efficiency of solar energy utilization, which stimulates the development of new photocatalytic materials. Here, recent advances in material design for photocatalytic water splitting are presented from a theoretical perspective. Specifically, aiming to enhance the photocatalytic performance, general strategies of materials design are discussed, including codoping and introducing a built-in electric field to improve the light harvesting of materials, reducing the dimension of materials to shorten the migration pathway of carriers to inhibit electron-hole recombination, and constructing heterojunctions to enhance light harvesting and electron-hole separation. Future opportunities and challenges in the theoretical design of photocatalytic materials toward water splitting are also included.

Intrinsic Electric Fields in Two-dimensional Materials Boost the Solar-to-Hydrogen Efficiency for Photocatalytic Water Splitting.

Two-dimensional (2D) materials with the vertical intrinsic electric fields show great promise in inhibiting the recombination of photogenerated carriers and widening light absorption region for the photocatalytic applications. For the first time, we investigated the potential feasibility of the experimentally attainable 2D M2X3 (M = Al, Ga, In; X = S, Se, Te) family featuring out-of-plane ferroelectricity used in photocatalytic water splitting. By using first-principles calculations, all the nine members of 2D M2X3 are verified to be available photocatalysts for overall water splitting. The predicted solar-to-hydrogen efficiency of Al2Te3, Ga2Se3, Ga2Te3, In2S3, In2Se3, and In2Te3 are larger than 10%. Excitingly, In2Te3 is manifested to be an infrared-light driven photocatalyst, and its solar-to-hydrogen efficiency limit using the full solar spectrum even reaches up to 32.1%, which breaks the conventional theoretical efficiency limit.

On the shuttling mechanism of a chlorine atom in a chloroaluminum phthalocyanine based molecular switch.

An intermediate shuttling structure of a chloroaluminum phthalocyanine(ClAlPc)-based molecular switch is transiently created and analyzed by combined scanning tunneling microcopy/spectroscopy and density-functional theory calculations, which suggests that the Cl atom is squeezed into the space between the central Al atom and the inner N-containing ring in ClAlPc.

Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry.

Controlling the bimetal nanoparticle with atomic monodispersity is still challenging. Herein, a monodisperse bimetal nanoparticle is synthesized in 25% yield (on gold atom basis) by an unusual replacement method. The formula of the nanoparticle is determined to be Au24Hg1(PET)18 (PET: phenylethanethiolate) by high-resolution ESI-MS spectrometry in conjunction with multiple analyses including X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray single-crystal diffraction reveals that the structure of Au24Hg1(PET)18 remains the structural framework of Au25(PET)18 with one of the outer-shell gold atoms replaced by one Hg atom, which is further supported by theoretical calculations and experimental results as well. Importantly, differential pulse voltammetry (DPV) is first employed to estimate the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO) energies of Au24Hg1(PET)18 based on previous calculations.

Different aggregation dynamics of benzene-water mixtures.

All-atom molecular dynamics simulations for benzene-water mixtures are performed, aiming to explore the relationship between the microscopic structures and the thermodynamic properties, in particular, the transformation dynamics from the mutually soluble state to the phase-separated state. We find that the molecular aggregation of benzene in the water-rich mixture is distinctly different from that of water in the benzene-rich mixture. This aggregation difference is attributed to the different intermolecular interactions: the clustering of benzene molecules in the water-rich mixture is primarily driven by weak short-distance π-π interactions; while the formation of water clusters in the benzene-rich solution is triggered by long-range dipole-dipole electrostatic interactions. Moreover, the molecular aggregations show double-scaled features: firstly assembling in a quasi-plane at a low concentration, then bulking in three dimensions with an increase in concentration.

A Comparative Study for Molecular Dynamics Simulations of Liquid Benzene.

The classical equilibrium and nonequilibrium molecular dynamics simulations for liquid benzene, the prototypical aromatic π-π interaction system, are performed using a variety of molecular force fields, OPT-FF, AMBER 03, general AMBER force field (GAFF), OPLS-AA, OPLS-CS, CHARMM27, GROMOS 53A5, and GROMOS 53A6. The simulated results of the molecular structure and thermodynamic properties of liquid benzene are compared with the experimental data available in the literature, accounting for the superiority of each force field in the descriptions of the π-π interaction system. The OPLS-AA force field is recommended to be the best one, which reproduces quite well the properties examined in this work, while the others fail in predicting either the local structure or the thermodynamic properties. Such distinct discrepancies for the above force fields are discussed within the scheme of the pairwise interaction construction of the standard force field, which will stimulate searching for a force field with generally good quality not only in terms of microstructure descriptions but also in the predictions of the thermodynamic properties of the liquids.

Molecular dynamics study of solvation differences between cis- and transplatin molecules in water.

The classical molecular dynamics (MD) simulations for the solvation properties of cis- and transplatins in water are performed with the Lennard-Jones plus Coulomb electrostatic potential parameters that are optimized with ab initio potential energies of the water-platin systems. Two hydration shells are found both for cis- and transplatins. The first shell of water molecules is closer to transplatin than cisplatin. The average number and lifetime of the intermolecular hydrogen bonds (HBs) estimated from the MD trajectories indicate that the Cl and NH(3) ligands are the main groups involved in the intermolecular HBs with water. In comparison with cisplatin, there are more HBs around transplatin and these HBs show the longer lifetime. The distinctly different solvation structures between cis- and transplatins are further revealed with the spatially anisotropic distributions of the first hydration shells.