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The possibility of using transition metal (TM)/MXene as a catalyst for the nitrogen reduction reaction (NRR) was studied by density functional theory, in which TM is an Fe atom, and MXene is pure Ti3C2O2 or Ti3C2O2−x doped with N/F/P/S/Cl. The adsorption energy and Gibbs free energy were calculated to describe the limiting potentials of N2 activation and reduction, respectively. N2 activation was spontaneous, and the reduction potential-limiting step may be the hydrogenation of N2 to *NNH and the desorption of *NH3 to NH3. The charge transfer of the adsorbed Fe atoms to N2 molecules weakened the interaction of N≡N, which indicates that Fe/MXene is a potential catalytic material for the NRR. In particular, doping with nonmetals F and S reduced the limiting potential of the two potential-limiting steps in the reduction reaction, compared with the undoped pure structure. Thus, Fe/MXenes doped with these nonmetals are the best candidates among these structures. [ABSTRACT FROM AUTHOR]

As a typical two-dimensional (2D) MXene, Ti3C2O2 has been considered as a potential material for high-performance hydrogen evolution reaction (HER) catalyst, due to its anticorrosion and hydrophilic surface. However, it is still a challenge to improve the Ti3C2O2 surficial HER catalytic activity. In this work, we investigated the HER activity of Ti3C2O2 after the surface was doped with S, Se, and Te by the first principles method. The results indicated that the HER activity of Ti3C2O2 is improved after being doped with S, Se, Te because the Gibbs free energy of hydrogen adsorption (ΔGH) is increased from −2.19 eV to 0.08 eV. Furthermore, we also found that the ΔGH of Ti3C2O2 increased from 0.182 eV to 0.08 eV with the doping concentration varied from 5.5% to 16.7%. The HER catalytic activity improvement of Ti3C2O2 is attributed to the local crystal structure distortion in catalytic active sites and Fermi level shift leads to the p-d orbital hybridization. Our results pave a new avenue for preparing a low-cost and high performance HER catalyst. [ABSTRACT FROM AUTHOR]

Ag@ZnS nanoparticles display enhanced photocatalytic efficiency and good photoelectric properties compared to their single-component counterparts in the process of forming a core-shell structure using an Ag cluster as the inner core of a ZnS outer shell. In this study, first-principles calculations were used to investigate the structural, electronic, and optical properties of Ag n @(ZnS) 42 (n = 6-16) core-shell nanocomposites. The calculated results show significant even-odd oscillations in the structural stability, that is, Ag@ZnS nanostructures with an even number of Ag n core atoms are relatively more stable than those with an odd number of core atoms. The second-order differences in the total energies (Δ 2 E) and the core-shell interaction energy E cs indicate that a Ag 12 @(ZnS) 42 nanostructure is the most stable configuration. A significant red shift was found in Ag n @(ZnS) 42 nanoparticles in the absorption spectrum compared with a (ZnS) 48 nanostructure, which is likely attributed to the strong electron interactions between the Ag core and the ZnS shell. Image 1 • The DFT method was firstly used to investigate Ag@(ZnS) core-shell nanostructure. • The method to construct Ag n @(ZnS) 42 core-shell structure is very novel. • Ag n @(ZnS) 42 has higher visible light absorption efficiency than ZnS structure. [ABSTRACT FROM AUTHOR]

Motivated by the recent successful synthesis of Janus monolayer of transition metal (TM) dichalcogenides, MXenes with Janus structures are worthy of further study, concerning its electronic structure and magnetic properties. Here, we study the effect of different transition metal atoms on the structure stability and magnetic and electronic properties of M'MCO2 (M' and M = V, Cr and Mn). The result shows the output magnetic moment is contributed mainly by the d orbitals of the V, Cr, and Mn atoms. The total magnetic moments of ferromagnetic (FM) configuration and antiferromagnetic (AFM) configuration are affected by coupling types. FM has a large magnetic moment output, while the total magnetic moments of AFM2's (intralayer AFM/interlayer FM) configuration and AFM3's (interlayer AFM/intralayer AFM) configuration are close to 0. The band gap widths of VCrCO2, VMnCO2, CrMnCO2, V2CO2, and Cr2CO2 are no more than 0.02 eV, showing metallic properties, while Mn2CO2 is a semiconductor with a 0.7071 eV band gap width. Janus MXenes can regulate the size of band gap, magnetic ground state, and output net magnetic moment. This work achieves the control of the magnetic properties of the available 2D materials, and provides theoretical guidance for the extensive design of novel Janus MXene materials. [ABSTRACT FROM AUTHOR]

2D MXenes have been found to be one of the most promising catalysts for hydrogen evolution reaction (HER) due to their excellent electronic conductivity, hydrophilic nature, porosity and stability. Nonmetallic (NM) element doping is an effective approach to enhance the HER catalytic performance. By using the density functional theory (DFT) method, we researched the effect of nonmetallic doping (different element types, variable doping concentrations) and optimal hydrogen absorption concentration on the surface of NM-Ti3C2O2 for HER catalytic activity and stability. The calculation results show that doping nonmetallic elements can improve their HER catalytic properties; the P element dopants catalyst especially exhibits remarkable HER performance (∆GH = 0.008 eV when the P element doping concentration is 100% and the hydrogen absorption is 75%). The origin mechanism of the regulation of doping on stability and catalytic activity was analyzed by electronic structures. The results of this work proved that by controlling the doping elements and their concentrations we can tune the catalytic activity, which will accelerate the further research of HER catalysts. [ABSTRACT FROM AUTHOR]

Tungsten carbide (WC) has received widespread attention as a new type of nonprecious metal catalyst for hydrogen evolution reaction (HER). However, it is still a challenge to improve the surface HER catalytic activity. In this work, the effects of different nonmetallic dopants on the catalytic activity and stabilities of WC (0001) surface for HER were studied by first principles methods. The effects of different types of non-metal (NM = B; N; O; P and S) and doping concentrations (ni = 25–100%) on HER catalytic activity and stability were investigated by calculating the Gibbs free energy of hydrogen adsorption (∆GH) and substitution energy. It was found that the catalytic performance can be improved by doping O and P non-metallic elements. Especially, the ∆GH with P doped is −0.04eV better than Pt (−0.085 eV), which is a potential ideal catalyst for HER. Furthermore, the electronic structure analysis was used to explore the origin of the regulation of doping on stability and catalytic activity. The results show that nonmetallic doping is an effective strategy to control the catalytic activity, which provides theoretical support for the future research of HER catalysts. [ABSTRACT FROM AUTHOR]