Supported Cu cluster on N-doped graphene: An efficient triatom catalyst for CO electroreduction to propanol at low potential.

Electroreduction of carbon monoxide into high-energy fuel is an excellent energy strategy for sustainable development, but the high yield of multi-carbon products remains a difficult challenge. Inspired by the successful synthesis of various trimer metal clusters and studies on electrocatalysis of CO to C3 products by Cu-based catalysts, Cu supported on N-doped graphene structures (Cu@NG) are investigated as electrocatalysts for CORR toward propanol in this paper. Due to the appropriate Cu-Cu bond length, the moderate charge of the Cu site, mild CO adsorption energy, and 100 % CO coverage, the absorbed 3*CO substance can form the critical *CO-CO-CO intermediate with a rather low kinetic barrier of 0.

Cu@CuO/WO with photo-regulated singlet oxygen and oxygen adatoms generation for selective photocatalytic aromatic amines to imines.

Photocatalysts can absorb light and activate molecular O under mild conditions, but the generation of unsuitable reactive oxygen species often limits their use in synthesizing fine chemicals. To address this issue, we disperse 1 wt% copper on tungsten trioxide (WO) support to create an efficient catalyst for selective oxidative coupling of aromatic amines to imines under sunlight irradiation at room temperature. Copper consists of a metallic copper core and an oxide shell.

Computational Discovery of High-Temperature Ferromagnetic Semiconductor Monolayer H-MnN.

In the past few years, two-dimensional (2D) high-temperature ferromagnetic semiconductor (FMS) materials with novelty and excellent properties have attracted much attention due to their potential in spintronics applications. In this work, using first-principles calculations, we predict that the H-MnN monolayer with the H-MoS-type structure is a stable intrinsic FMS with an indirect band gap of 0.79 eV and a high Curie temperature () of 380 K.

Fe-induced crystalline-amorphous interface engineering of a NiMo-based heterostructure for enhanced water oxidation.

Engineering heterostructures with a unique surface/interface structure is one of the effective strategies to develop highly active noble-metal-free catalysts for the oxygen evolution reaction (OER), because the surface/interface of catalysts is the main site for the OER. Herein, we design a coralloid NiMo(Fe)-20 catalyst with a crystalline-amorphous interface through combining a hydrothermal method and an Fe-induced surface reconfiguration strategy. That is, after Fe impregnation treatment, the Ni(OH)-NiMoO pre-catalyst with a complete crystalline surface is restructured into a trimetallic heterostructure with a crystalline-amorphous interface, which facilitates mass diffusion and charge transfer during the OER.

Cooperative adsorption of interfacial Ga-N dual-site in GaOOH@N-doped carbon nanotubes for enhanced electrocatalytic reduction of carbon dioxide.

To reduce activation energy barrier and promote the kinetics of electrocatalytic CO reduction reaction (eCORR), the performance of CO adsorption and activation on electrocatalysts should be optimized. Here, GaOOH is successfully coupled with N-doped carbon nanotubes (NC) via a facile self-assembly-calcination process. The obtained GaOOH@N-doped carbon nanotubes (Ga-NC) display the best CO faradaic efficiency of 96.

In-situ fabrication of bimetallic FeCoO-FeCoS heterostructure for high-efficient alkaline freshwater/seawater electrolysis.

Rational construction of bifunctional electrocatalysts with long-term stability and high electrocatalytic activity is of great importance, but it is challenging to obtain highly efficient non-precious metal-based catalysts for overall seawater electrolysis. Herein, a nickel foam (NF) self-supporting CoFe-layered double hydroxide (CoFe-LDH/NF) was directly converted into FeCoO-FeCoS heterostructure via hydrothermal method in 50 mM NaS solution, instead of FeCoO@FeCoS core-shell structure. The FeCoO-FeCoS heterojunction shows nanosheets structure with rough surface (the thickness of ∼ 198.

Isolation of coumarins with anti-Trichophyton rubrum activity from Heracleum vicinum Boiss.

Heracleum vicinum Boiss., a perennial plant of Angelica in Umbelliferae, is mainly distributed in Sichuan and Hunan of China. Trichophyton rubrum is a common skin fungus causing dermatophyte.

Immobilized triatomic CuB clusters on 2D carbon nitride: highly selective conversion of CO to ethanol at low potentials.

A promising pathway for carbon usage and energy storage is electrocatalytic reduction of CO to form high-value multi-carbon products. Herein, the d-p coupled triatomic catalyst CuB@g-CN with significant activity and selectivity for ethanol is presented for the first time. Density functional theory calculations elucidate that these spatially confined triatomic centers are capable of immobilizing multiple CO molecules, providing an exclusive reaction channel for direct C-C coupling.

Synergistically boosting the anchoring effect and catalytic activity of MXenes as bifunctional electrocatalysts for sodium-sulfur batteries by single-atom catalyst engineering.

MXene based sulfur hosts have attracted enormous attention in room temperature sodium-sulfur (RT Na-S) batteries due to their strong affinity towards soluble sodium polysulfides (NaPSs). However, their electrocatalytic performance needs further improvement. Here, a series of single non-noble transition metal (TM = Fe, Co, Ni, and Cu) atoms anchored on TiCS (TM@TiCS) were proposed as bifunctional sulfur hosts for Na-S batteries.

A density functional theory study of a water gas shift reaction on Ag(111): potassium effect.

Density functional theory (DFT) calculations are executed to investigate the effect of a potassium (K) promoter on the activity of the water gas shift reaction (WGSR) over an Ag(111) surface. It is found that the WGSR proceeds mainly through the OH(O)-assisted carboxy pathway in which HO dehydrogenation is the rate-controlling step on both Ag(111) and K/Ag(111) surfaces. Energetic span model analysis shows that K addition can enhance the activity of the WGSR by reducing the apparent activation energy of the whole reaction since it can promote HO dissociation and stabilize the adsorption of the reactants (CO and HO).

Covalent surface modification of bifunctional two-dimensional metal carbide MXenes as sulfur hosts for sodium-sulfur batteries.

Room temperature sodium-sulfur (RT Na-S) batteries show extraordinary potential in large-scale energy storage. MXenes have been demonstrated to be promising sulfur hosts for Na-S batteries, and their surface functional groups play a pivotal role in their performance. However, the effect of different surface functional groups of MXenes on their anchoring effect and catalytic performance has not been systematically investigated.

Adsorption Characteristics of Gas Molecules Adsorbed on Graphene Doped with Mn: A First Principle Study.

Herein, the adsorption characteristics of graphene substrates modified through a combined single manganese atom with a vacancy or four nitrogen to CHO, HS and HCN, are thoroughly investigated via the density functional theory (DFT) method. The adsorption structural, electronic structures, magnetic properties and adsorption energies of the adsorption system have been completely analyzed. It is found that the adsorption activity of a single vacancy graphene-embedded Mn atom (MnSV-GN) is the largest in the three graphene supports.

Immobilization of bismuth oxychloride on cellulose nanocrystal for sunlight-driven superior photosensitized degradation.

Semiconductor photocatalysis is considered to be an important green technology for sewage treatment. However, most of the pollutant degradation studies used simulated sunlight in a laboratory, which has great energy cost with limited applications in industry. Herein, cellulose nanocrystal (CNC) with rich hydroxyl groups and high specific surface area are used as the matrix to construct composites with BiOCl, which improves the dispersibility with an increased number of oxygen vacancies on BiOCl.

The Adsorption Behavior of Gas Molecules on Co/N Co-Doped Graphene.

Herein, we have used density functional theory (DFT) to investigate the adsorption behavior of gas molecules on Co/N co-doped graphene (Co/N-gra). We have investigated the geometric stability, electric properties, and magnetic properties comprehensively upon the interaction between Co/N-gra and gas molecules. The binding energy of Co is -5.

Pd Nanoparticles Coupled to NiMoO-C Nanorods for Enhanced Electrocatalytic Ethanol Oxidation.

The interfacial interaction including chemical bonding or electron transfer and even physisorption in composite electrocatalysts has a considerable effect on electrocatalytic oxidation reaction. Herein, we report a tremendously enhanced catalytic activity and excellent durability for the ethanol electro-oxidation reaction in NiMoO-C-supported Pd composites (Pd/NiMoO-C) compared to the commercial Pd/C (10%) catalyst. The X-ray powder diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy measurements disclose that the strong electron transfer between NiMoO nanorods and Pd nanoparticles likely induces the formation of more electrochemical active centers and improves the adsorption-desorption capacity of reactants and corresponding intermediates.

Electrosynthesized CuO/graphene by a four-electrode electrolysis system for the oxygen reduction reaction to hydrogen peroxide.

Here a facile four-electrode electrolysis system is firstly applied to synthesize a CuOx/graphene hybrid. The exfoliation of graphite via high electrolytic voltage and dissolution of copper via low electrolytic voltage are achieved simultaneously. CuOx/G with the highest content of CuOx shows superior electrocatalytic activity for oxygen reduction to hydrogen peroxide.

Structural dependence of electrosynthesized cobalt phosphide/black phosphorus pre-catalyst for oxygen evolution in alkaline media.

The integration of black phosphorus (BP) with metal phosphides is known to produce high-performance electrocatalysts for oxygen evolution reduction (OER), although increased stability and prevention of the degradation of their lone pairs would be desirable improvements. In this work, cobalt phosphide (CoP)/BP heterostructures were electrochemically synthesized with a two-electrode system, where cobalt ions were generated in situ at a Co anode, and non-aggregated BP nanosheets (NSs) were exfoliated from the bulky BP cathode. With an electrolysis voltage of 30 V, the CoP/BP heterostructure exhibited a superior and stable OER performance (e.

A label-free electrochemical aptasensor based on the core-shell Cu-MOF@TpBD hybrid nanoarchitecture for the sensitive detection of PDGF-BB.

As one of the significant serum cytokines, platelet-derived growth factor-BB (PDGF-BB) is a crucial protein biomarker overexpressed in human life-threatening tumors, the sensitive identification and quantification of which are urgently desired but challenging. Herein we report a novel core-shell nanoarchitecture consisting of Cu-based metal-organic frameworks (Cu-MOFs) and covalent organic frameworks (denoted as TpBD-COFs), which was used to prepare an aptasensor for the detection of platelet-derived growth factor-BB (PDGF-BB). The central Cu-MOFs function as signal labels with no need for extra redox media, whereas the porous TpBD serves as the shell to immobilize the PDGF-BB-targeted aptamer strands in abundance via strong interactions involving π-π stacking, electrostatic, and hydrogen bonding interactions.

Multicenter electron-sharing σ-bonding in the AgFe(CO) complex.

The heterodinuclear silver tetracarbonyl-iron anion was generated in the gas phase and studied by joint photoelectron velocity map imaging spectroscopy and quantum chemical calculations. The AgFe(CO)4- anion is characterized to be an 18-electron complex with the silver atom covalently bonded to the anionic tetracarbonyl-iron, an isolobal analogue of the methyl radical. The bonding analyses using a range of state-of-the-art quantum chemistry methods revealed a peculiar decentralized bonding situation, where the silver atom is covalently bonded to both the iron center and the vicinal carbon atoms in the form of an electron-sharing σ bond.

Cooperative physisorption and chemisorption of hydrogen on vanadium-decorated benzene.

3d TM-decorated carbon composites have been proved to be a new generation of hydrogen storage materials. However, detailed hydrogen storage mechanisms are still unclear. Investigation of the H dissociation and H migration on the 3d TM-decorated six-membered carbocycles is very critical for better understanding the hydrogen storage mechanism.

Triply Carbonyl-Bridged Ni(CO) Featuring Triple Three-Center Two-Electron Ni-C-Ni Bonds Instead of Ni≡Ni Triple Bond.

Motivated by the predicted unusual short Ni-Ni bond length that is comparable to the intermetallic distance anticipated for the triple bond, the nature of Ni-Ni bonding interaction in the triply carbonyl-bridged geometry of the neutral Ni(CO) complex has been investigated using a range of state-of-the-art quantum chemistry methods. The elaborate analyses manifest that the tribridged Ni(CO) features triple three-center two-electron Ni-C-Ni bonds instead of Ni≡Ni triple bond. The electron pair donated by the bridging carbonyl ligand should be shared by both nickel centers to achieve the favored (18, 18) configuration.

The effect of group-substitution on the sensitization properties of alkynylrhenium(I) tricarbonyl diimine complexes adsorbed to TiO(101) film surface: a theoretical study.

A series of dyes are designed by adding the different electron-donating (-CH, -NH, -OH) and electron-withdrawing groups (-Br, -Cl, -NO) to the different ancillary ligands in the alkynylrhenium(I) tricarbonyl diimine complexes [Re(CO)(N^N){C≡C-CH-CH=C(CN)(COOH)}], where N^N = 1,10-phenanthroline (phen)(1) and then investigated the sensitization properties of dyes linked to the TiO(101) surface. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were used to study the electronic structure, frontier molecular orbitals, and absorption spectral properties. The effect of group-substitution on sensitization properties is obvious.

Thermodynamics and Kinetics of Gas-Phase CO Oxidation on the Scandium Monoxide Carbonyl Complexes.

The CO chemisorption onto the ScO cation was investigated using infrared photodissociation spectroscopy combined with density functional theory calculations. The spectra were recorded in the CO stretching vibrational region for the OSc(CO) ( = 4-6) complex series. Comparisons of the experimental spectra with the simulated ones have established the geometries and present strong evidence that all of the CO ligands are chemisorbed, which could not be readily oxidized by scandium monoxide core into CO.

Theoretical Insights on the High Pressure Behavior of Pentazolate Anion Complex [Co(HO)(N)]·4HO.

Periodic dispersion corrected density functional theory (DFT) calculations were carried out to examine the Hirshfeld surface, two dimensional (2D) fingerprint plots, crystal structure, molecular structure and density of state of all-nitrogen pentazolate anion complex [Co(HO)(N)]·4HO under hydrostatic pressure from 0 to 20 GPa. The GGA/PW91-OBS method was applied in the present study. The intercontacts in [Co(HO)(N)]·4HO were analyzed by Hirshfeld surfaces and 2D fingerprint plots.

High pressure behavior of crystal [2,2'-bi(1,3,4-oxadiazole)]-5,5'-dinitramide: A DFT investigation.

Density functional theory (DFT) computation was carried out to investigate the crystal, molecular and electronic structures of high energy crystal [2,2'-bi(1,3,4-oxadiazole)]-5,5'-dinitramide (BODN) with the pressure 0-120 GPa. The relaxed crystal structure by the GGA/PBE-TS functional matches well with the experimental data at ambient pressure condition. With the intensifying of pressure, the lattice parameters, volumes, bond lengths, H-bond energies, atomic charges, bond populations, band gaps and density of states of crystal BODN change gently.