New Insights into Gas-Solid Interactions of NO2/MoS2 Monolayers: a Comparative Study with MoSe2 and MoTe2 Monolayers.

Understanding the microscopic electronic structure determines the macroscopic properties of the materials. Sufficient sampling has the same foundational importance in understanding the interactions. The NO2/MoS2 interaction is well known, but there are still many inconsistencies in the basic data, and the source of the NO2 direct dissociation activity has not been revealed. Based on a large-scale sampling density functional theory (DFT) study, the optimal adsorption of the NO2/MoS2 monolayer system is determined. The impurity state on the top of the valence band of the S-vacancy monolayer (MoS2-VS) was determined by cross-analysis of the band structure and density of states, which has been neglected for a long time. This provides a reasonable explanation for the direct dissociation of NO2 on the MoX2 monolayers. Further atomic structure analysis reveals that the impurity state originates from the not-fully occupied valence orbitals. This also corroborates the fact that the Mo material has dissociation activity, while the W material does not. There is no impurity state on the top of the valence band of the X-vacancy WS2 and WSe2 monolayers. Interestingly, NO2 dissociation did not occur in the MoTe2-VTe monolayer. This may be related to the 6s inert electron pair effect of the Te atom. The double-oriented adsorption behavior of NO2is also revealed. In contrast to the MoSe2 and MoTe2 monolayers, NO2-oriented adsorption on the MoS2 perfect monolayer deviates obviously, which is speculated to be related to space limitation and larger electronegativity of the S atom. The oriented adsorption ability of the MoX2 monolayers followed the order MoTe2 (64.4%) > MoSe2 (44.8%) > MoS2 (42.7%), according to the directed proportion. Renewed insights into the adsorption basic data and the understanding of the electronic structure of NO2/MoX2 (X = S, Se, Te) monolayer systems provide a basic understanding of the gas-surface interactions and various future surface-related advanced applications.

Low-voltage and fast-response SnO2nanotubes/perovskite heterostructure photodetector.

One-dimensional metal-oxides (1D-MO) nanostructure has been regarded as one of the most promising candidates for high-performance photodetectors due to their outstanding electronic properties, low-cost and environmental stability. However, the current bottlenecks are high energy consumption and relatively low sensitivity. Here, Schottky junctions between nanotubes (NTs) and FTO were fabricated by electrospinning SnO2NTs on FTO glass substrate, and the bias voltage of SnO2NTs photodetectors was as low as ∼1.76 V, which can effectively reduce energy consumption. Additionally, for improving the response and recovery speed of SnO2NTs photodetectors, the NTs were covered with organic/inorganic hybrid perovskite. SnO2NTs/perovskite heterostructure photodetectors exhibit fast response/recovery speed (∼0.075/0.04 s), and a wide optical response range (∼220-800 nm). At the same time, the bias voltage of heterostructure photodetectors was further reduced to 0.42 V. The outstanding performance is mainly attributed to the formation of type-II heterojunctions between SnO2NTs and perovskite, which can facilitate the separation of photogenerated carriers, as well as Schottky junction between SnO2NTs and FTO, which reduce the bias voltage. All the results indicate that the rational design of 1D-MO/perovskite heterostructure is a facile and efficient way to achieve high-performance photodetectors.

Mechanistical investigation on the self-enhanced photocatalytic activity of CuO/Cu2O hybrid nanostructures by density functional theory calculations.

The photocatalytic mechanism of a Cu2O/CuO hybrid system is disclosed in detail by density functional theory (DFT) calculations. The synergistic relationship of the two counterparts is confirmed by hydrogen peroxide (H2O2) formation on the CuO nanowires and dissociation on the Cu2O nanoparticles; this enables the system to self-sufficiently produce hydroxyl radicals, which is highly efficient in the photocatalytic degradation of methyl orange. The exposed surfaces are found to be crucial in the cooperative photocatalytic system, especially the Cu2O(111) surface, in the dissociation of H2O2. The distinct positions of the conduction band minimum and valence band maximum for CuO and Cu2O and synergic surface reactions enable the effective utilization of the electrons and holes generated by visible-light irradiation. Our results will contribute to a greater understanding of the specific mechanism of photodegradation catalyzed by Cu2O/CuO heterostructures, which may lead to promising directions in structure optimization for photocatalysts with high photocatalytic efficiency.

Human Serum Albumin Mediated Controllable Synthesis of Defect-Rich Copper Hydroxide Nanowire for Cuproptosis-Based Anti-Tumor Therapy.

Cuproptosis, as a newly identified form of programmed cell death, shows great promise in cancer treatment. Efficient Cu+ delivery while avoiding systemic toxicity and elimination of the resistance from over-expressed intracellular copper chelator glutathione (GSH) are critical for cuproptosis. Herein, this work innovatively constructs a biocompatible and defect-rich copper hydroxide nanowire (HCu nanowire) through a human serum albumin (HSA) mediated biomineralization method. This work finds that the morphology and size of HCu nanowires can be controlled adjusted by the feed ratio of HSA and Cu2+. Remarkably, except for outstanding biocompatibility, HSA coordination endows HCu nanowires abundant oxygen vacancies (OVs), and the defect-rich HCu nanowire possesses excellent GSH consumption efficiency. Density functional theory studies indicate that OVs change GSH absorption energy on defective HCu nanowires. In cancer cells, HCu nanowires deplete GSH and simultaneously produce sufficient free Cu+ for enhanced cuproptosis. Meanwhile, Cu+ can catalyze endogenous H2O2 into hydroxyl radicals (·OH) via a Fenton-like reaction. Thus, synergetic cuproptosis and ROS mediated apoptosis against tumor are achieved. The experimental results show that HCu nanowires have a better performance in both antitumor efficiency and safety compared with chemotherapeutic drug Dox at the same dose, demonstrating its great potential in clinical applications.

Density functional study of organocatalytic cross-aldol reactions between two aliphatic aldehydes: insight into their functional differentiation and origins of chemo- and stereoselectivities.

The chemo-, diastereo-, and enantioselectivities in proline and axially chiral amino sulfonamide-catalyzed direct aldol reactions between two enolizable aldehydes with different electronic nature have been studied with the aid of density functional theory (DFT) method. The potential energy profiles for the enamine formation between each aliphatic aldehyde and the catalyst confirm that two subject catalysts can successfully differentiate between 3-methylbutanal as an enamine component and α-chloroaldehydes as a carbonyl component. Transition states associated with the stereochemistry-determining C-C bond-forming step with the enamine intermediate addition to the aldehyde acceptor for proline and chiral amino sulfonamide-promoted aldol reactions are reported. DFT calculations not only provide a good explanation for the formation of the sole cross-aldol product between two aliphatic aldehydes both bearing α-methylene protons but also well reproduce the opposite syn vs anti diastereoselectivities in the chiral amino sulfonamide and proline-catalyzed aldol reactions.

Location of Si vacancies and [Ti(OSi)4] and [Ti(OSi)3OH] sites in the MFI framework: a large cluster and full ab initio study.

Titanium silicalite-1 (TS-1) is an important catalyst for selective oxidation reactions. However, the nature and structure of the active sites and the mechanistic details of the catalytic reactions over TS-1 have not been well-understood, leaving a continuous debate on the genesis of active sites on the TS-1 surface in the literature. In this work, the location of Si vacancies and [Ti(OSi)(4)] and [Ti(OSi)(3)OH] sites in the MFI (Framework Type Code of ZSM-5 (Zeolite Socony Mobile-Five)) framework has been studied using a full ab initio method with 40T clusters with a Si:Ti molar ratio of 39:1. It was shown that the former four energetically favorable sites for Si vacancies are T6, T12, T4, and T8 and for Ti centers of [Ti(OSi)(4)] are T10, T4, T8 and T11, being partially the same sites. Whether by replacing Si vacancies or substituting the fully coordinated Si sites, the most preferential site for Ti is T10, which indicates that the insertion mechanism does not affect the favorable sites of Ti in the MFI lattice. For the defective [Ti(OSi)(3)OH] sites, it was found that the Si vacancy at T6 with a Ti at its neighboring T9 site (T6-def-T9-Ti pair) is the most energetically favorable one, followed by a T6-def-T5-Ti pair with a small energy gap. These findings are significant to elucidate the nature of the active sites and the mechanism of reactions catalyzed by TS-1 and to design the TS-1 catalyst.

Edge-enriched WS2 nanosheets on carbon nanofibers boosts NO2 detection at room temperature.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) hold great promise for room temperature (RT) NO2 sensors. However, the exposure of the edges of TMDs with high adsorption capability and electronic activity remains a great obstacle to achieve high sensor sensitivity. Herein, we demonstrate a high-performance RT NO2 gas sensor based on WS2 nanosheets/carbon nanofibers (CNFs) composite with abundant intentionally exposed WS2 edges. Few-layer WS2 nanosheets are anchored on CNFs through a hydrothermal process. The approach permits to achieve a coating presenting an optimized active surface area and accessibility of the sensing layers. The exposure of WS2 edges remarkably improves the sensing properties. Consequently, the WS2@CNFs composite exhibits excellent selectivity to NO2 at RT with improved response and much lower detection limit in comparison to the WS2 and CNFs counterparts. Density functional theory (DFT) calculations verify a surprisingly strong NO2 adsorption on WS2 edge sites (adsorption energy 3.40 eV) with a partial charge transfer of 0.394e, while a week adsorption on the basal surface of WS2 (adsorption energy 0.25 eV) with a partial charge transfer of 0.171e. The strategy proposed herein will be instructive to the design of efficient material structures for low-power NO2 sensors with optimized performances.

On the origin of the visible-light activity of titanium dioxide doped with carbonate species.

Plane-wave-based pseudopotential density functional theory (DFT) calculations are used to elucidate the origin of the high photocatalytic efficiency of carbonate-doped TiO(2). Two geometrically possible doping positions are considered, including interstitial and substitutional carbon atoms on Ti sites. From the optical absorption properties calculations, we believe that the formation of carbonates after doping with interstitial carbon atoms is crucial, whereas the contribution from the cationic doping on Ti sites is negligible. The carbonate species doped TiO(2) exhibits excellent absorption in the visible-light region of 400-800 nm, in good agreement with experimental observations. Electronic structure analysis shows that the carbonate species introduce an impurity state from Ti 3d below the conduction band. Excitations from the impurity state to the conduction band may be responsible for the high visible-light activity of the carbon doped TiO(2) materials.

A graphyne-like porous carbon-rich network synthesized via alkyne metathesis.

The synthesis of graphyne has been considered challenging, especially when it comes to adopting new topologies and obtaining thinner layers. Herein, we report the synthesis and characterization of a graphyne-like porous carbon-rich network via alkyne metathesis reactions, which resulted in a sp2/sp hybridized 2D thin film structure with a layer to layer distance of 0.37 nm. This graphyne-like porous carbon-rich network is an n-type semiconductor with a low work function of 3.9 eV and a reduction potential of -0.54 V vs. SHE, which could be applied as an excellent reducing agent for metal electroless deposition. In addition, this material has a narrow pore size distribution of 2 to 4 nm, a high surface area of 675 m2 g-1 and a large pore volume of 0.795 cm3 g-1 favoring gas adsorption. It shows the selective absorption of CO2 over N2 owing to the strong affinity between CO2 and the carbon-carbon triple bond.

Pt-Enhanced Mesoporous Ti3+/TiO2 with Rapid Bulk to Surface Electron Transfer for Photocatalytic Hydrogen Evolution.

Pt-doped mesoporous Ti3+ self-doped TiO2 (Pt-Ti3+/TiO2) is in situ synthesized via an ionothermal route, by treating metallic Ti in an ionic liquid containing LiOAc, HOAc, and a H2PtCl6 aqueous solution under mild ionothermal conditions. Such Ti3+-enriched environment, as well as oxygen vacancies, is proven to be effective for allowing the in situ reduction of Pt4+ ions uniformly located in the framework of the TiO2 bulk. The photocatalytic H2 evolution of Pt-Ti3+/TiO2 is significantly higher than that of the photoreduced Pt loaded on the original TiO2 and commercial P25. Such greatly enhanced activity is due to the various valence states of Pt (Ptn+, n = 0, 2, or 3), forming Pt-O bonds embedded in the framework of TiO2 and ultrafine Pt metal nanoparticles on the surface of TiO2. Such Ptn+-O bonds could act as the bridges for facilitating the photogenerated electron transfer from the bulk to the surface of TiO2 with a higher electron carrier density (3.11 × 1020 cm-3), about 2.5 times that (1.25 × 1020 cm-3) of the photoreduced Pt-Ti3+/TiO2 sample. Thus, more photogenerated electrons could reach the Pt metal for reducing protons to H2.

DFT description on electronic structure and optical absorption properties of anionic S-doped anatase TiO2.

Plane-wave-based pseudopotential density functional theory (DFT) calculations are used to characterize the doping effect of S substituting for O in anatase TiO(2). Through band structure calculation, a direct band gap is predicted in TiO(2)(-)(x)S(x). Electronic structure analysis shows that the doping S could substantially lower the band gap of TiO(2) by the presence of an impurity state of S 3p on the upper edge of the valence band. Excitations from the impurity state of S 3p to the conduction band may be responsible for the red shift of the absorption edge observed in the S-doped TiO(2). The band gap lowering and red shift of the absorption edge are found to increase as the sulfur concentration increases.