Thermal Transport Properties of Two-Dimensional Janus MoXSiN2 (X = S, Se, and Te).

The design of Janus materials offers an effective means of regulating both their physical and chemical properties, leading to their application in various fields. However, the underlying mechanism governing the modulation of the thermal transport characteristics through the construction of Janus materials remains unclear. In this work, we introduce VI-group elements into the MoSi2N4 structure, yielding two-dimensional Janus MoXSiN2 (X = S, Se, and Te) and systematically investigate their thermal transport properties based on first-principles calculation methods. Our findings reveal that the lattice thermal conductivities (κl) of MoSSiN2, MoSeSiN2, and MoTeSiN2 are 47.2, 24.3, and 40.6 W/mK at 300 K, respectively, significantly lower than that of MoSi2N4 (224 W/mK). Such low κl values mainly come from the introduction of X atoms, which enhances phonon scattering and reduces phonon vibration frequencies. In addition, MoTeSiN2 exhibits a higher κl compared to MoSeSiN2, contrary to the trend observed in most materials containing VI-group elements, where κl decreases gradually from S to Te. This anomalous behavior can be attributed to the competitive result between its lower phonon vibrational frequency and weaker phonon anharmonicity of MoTeSiN2. This work elucidates the inherent mechanism governing the modulation of thermal transport properties in Janus materials, thereby enhancing the potential application of Janus MoXSiN2 in engineering thermal management.

Thermal Transport in Pentagonal CX2 (X = N, P, As, and Sb).

Two-dimensional (2D) materials with a pentagonal structure have many unique physical properties and great potential for applications in electrical, thermal, and optical fields. In this paper, the intrinsic thermal transport properties of 2D pentagonal CX2 (X = N, P, As, and Sb) are comparatively investigated. The results show that penta-CN2 has a high thermal conductivity (302.7 W/mK), while penta-CP2, penta-CAs2, and penta-CSb2 have relatively low thermal conductivities of 60.0, 36.9, and 11.8 W/mK, respectively. The main reason for the high thermal conductivity of penta-CN2 is that the small atomic mass of the N atom is comparable to that of the C atom, resulting in a preferable pentagonal structure with stronger bonds and thus a higher phonon group velocity. The reduction in the thermal conductivity of the other three materials is mainly due to the gradually increased atomic mass from P to Sb, which reduces the phonon group velocity. In addition, the large atomic mass difference does not result in a huge enhancement of the anharmonicity or weakening of the phonon relaxation time. The present work is expected to deepen the understanding of the thermal transport of main group V 2D pentagonal carbons and pave the way for their future applications, also, providing ideas for finding potential thermal management materials.

Monolayer 1T-Ag6S2 with Excellent Thermoelectric Properties.

We obtained a new material called monolayer 1T-Ag6S2 by replacing metal atoms in 1T phase transition-metal dichalcogenide sulfides (TMDs) with octahedral Ag6 clusters. Subsequently, the thermoelectric transport properties of monolayer 1T-Ag6S2 were systematically investigated using first-principles calculations and the generalized gradient approximation (GGA-PBE) exchange correlation functional. The findings demonstrate that monolayer 1T-Ag6S2 displays characteristics of a wide-bandgap semiconductor, with a bandgap of 2.48 eV. Notably, the incorporation of Ag6 clusters disrupts the structural symmetry, effectively enhancing the electronic structure and phonon properties of the material. Due to the flat valence band near the Fermi level, the extended relaxation time of the hole results in a greater effective mass compared to the electron, leading to a significant increase in the Seebeck coefficient. Under optimal doping conditions, the power factor of monolayer 1T-Ag6S2 can achieve 14.9 mW/mK2 at 500 K. The intricate crystal structure induces phonon path bending, reduces the overall frequency of phonon vibrations (<10 THz), and causes hybridization of low-frequency optical and acoustic branches, resulting in remarkably low lattice thermal conductivity (0.20 and 0.17 W/mK along the x and y axes at 500 K, respectively). The monolayer 1T-Ag6S2 demonstrates a remarkably high figure of merit ZT of 3.14 (3.15) on the x (y) axis at 500 K, significantly higher than those of conventional TMD materials. Such excellent thermoelectric properties suggest that monolayer 1T-Ag6S2 is a promising thermoelectric (TE) material. Our work reveals the deep mechanism of cluster substitution to optimize the thermoelectric properties of materials and provides a useful reference for subsequent research.

Effect of atomic substitution and structure on thermal conductivity in monolayers H-MN and T-MN (M = B, Al, Ga).

Finding materials with suitable thermal conductivity (κ) is crucial for improving energy efficiency, reducing carbon emissions, and achieving sustainability. Atomic substitution and structural adjustments are commonly used methods. By comparing the κ of two different structures of two-dimensional (2D) IIIA-nitrides and their corresponding carbides, we explored whether atomic substitution has the same impact on κ in different structures. All eight materials exhibit normal temperature dependence, with κ decreasing as the temperature rises. Both structures are single atomic layers of 2D materials, forming M-N bonds, with the difference being that H-MN consists of hexagonal rings, while T-MN consists of tetragonal and octagonal rings. 2D IIIA-nitrides provide a good illustration of the impact of atomic substitution and structure on κ. On a logarithmic scale of κ, it approximates two parallel lines, indicating that different structures exhibit similar trends of κ reduction under the same conditions of atomic substitution. We analyzed the mechanisms behind the decreasing trend in κ from a phonon mode perspective. The main reason for the decrease in κ is that heavier atoms lower lattice vibrations, reducing phonon frequencies. Electronegativity increases, altering bonding characteristics and increasing anharmonicity. Reduced symmetry in complex structures decreases phonon group velocities and enhances phonon anharmonicity, leading to decreased phonon lifetimes. It's noteworthy that we found that atomic substitution and structure significantly affect hydrodynamic phonon transport as well. Both complex structures and atomic substitution simultaneously reduce the effects of hydrodynamic phonon transport. By comparing the impact of κ on two different structures of 2D IIIA-nitrides and their corresponding carbides, we have deepened our understanding of phonon transport in 2D materials. Heavier atomic substitution and more complex structures result in reduced κ and decreased hydrodynamic phonon transport effects. This research is likely to have a significant impact on the study of micro- and nanoscale heat transfer, including the design of materials with specific heat transfer properties for future applications.

Transition metals anchored on nitrogen-doped graphdiyne for an efficient oxygen reduction reaction: a DFT study.

The search for highly active and low-cost single-atom catalysts for the oxygen reduction reaction (ORR) is essential for the widespread application of proton exchange membrane fuel cells. Transition metals anchored on nitrogen-doped graphdiyne (GDY) have attracted considerable interest as potentially excellent catalysts for the ORR. However, the relationship between the active site and nitrogen-doped GDY remains unclear. In this work, we conducted a systematic investigation of sp-hybridized N atoms anchoring single transition metal atoms of 3d and 4d on GDY (TMC2N2) as electrocatalysts for the ORR. Firstly, 18 kinds of TMC2N2 were determined to have good thermodynamic stability. Due to the extremely strong adsorption of *OH, TMC2N2 exhibits inferior ORR performance compared to traditional Pt(111). Considering that *OH adsorption hinders the catalytic activity of TMC2N2, we modified the OH ligand of TMC2N2 to develop the high-valent metal complex (TMC2N2-OH) aiming to enhance the electrocatalytic activity. The adsorption of intermediates on most TMC2N2-OH is weakened after the modification of the OH ligand, especially for the adsorption of *OH. Thus, by comparing the ORR overpotential of catalysts before and after ligand modification, we find that the catalytic activity of different TMC2N2-OHs improves to various degrees. MnC2N2-OH, TMC2N2-OH, and TcC2N2-OH exhibit relatively high ORR catalytic activity, with overpotentials of 0.93 V, 1.19 V, and 0.92 V, respectively. Furthermore, we investigated the cause of improved catalytic activity of TMC2N2-OH and found that the modified coordination environment of the catalyst led to adjusted adsorption of ORR intermediates. In summary, our work sheds light on the relationship between nitrogen-doped GDY and transition metal sites, thus contributing to the development of more efficient catalysts.

Construction of highly active FeN4@Fex(OH)y cluster composite sites for the oxygen reduction reaction and the oxygen evolution reaction.

Seeking cost-effective and earth-abundant electrocatalysts with excellent activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in zinc-air batteries (ZABs) is critically important. In this work, the ORR and OER performance of the Fex cluster supported on FeN4 composite sites (FeN4@Fex) is investigated based on density functional theory. Based on the charge density difference between the Fex cluster and the FeN4 substrate, the conclusion that the decreased charge density of the chemical bond between the metal and the adsorbate can weaken the adsorption of the adsorbate can be drawn. The results of the d-band center also confirm this. Furthermore, the ORR and OER free energy change profiles show that FeN4@Fe8 exhibits the best ORR and OER activity. This is because the electronic environment regulated by the Fex cluster can improve the adsorption of intermediates, which is conducive to enhancing catalytic activity. Further considering the solution environment, the activity of FeN4@Fex with preadsorbed OH (FeN4@Fex(OH)y) was studied. It is found that FeN4@Fe8(OH)6 is still the best catalyst. This work introduces new highly active composite sites for catalyzing the ORR in an acid medium.

Efficient Removal of Antimony(V) from Antimony Mine Wastewater by Micrometer Zero-Valent Iron.

This paper investigates the effectiveness of two commercial micron zero-valent irons (mZVIs) in removing Sb(V) from antimony mine wastewater. The wastewater contains a range of complex components and heavy metal ions, including As(V), which can impact the removal efficiency of mZVI. The study aims to provide insights into actual working conditions and focuses on influencing factors and standard conditions. The results demonstrate that mZVI can reduce Sb(V) concentration in the mine wastewater from 3875.7 µg/L to below the drinking water standard of 5 µg/L within 2 h. Adding a small amount of mZVI every 30 min helps to maintain a high removal rate. The study confirms the existence of a reduction reaction by changing the atmospheric conditions of the reaction, and the addition of 1,10-phenanthroline highlights the important role of active Fe(II) in the adsorption and removal of Sb(V) by mZVI. Additionally, the paper presents an innovative experimental method of acid treatment followed by alkali treatment, which proves the interfacial reaction between mZVI and Sb(V). Overall, the study demonstrates that the removal of Sb(V) by mZVI entails a dual function of reduction and adsorption, highlighting the potential of mZVI in repairing Sb(V) in antimony mine wastewater.

Amylase degradation enhanced NIR photothermal therapy and fluorescence imaging of bacterial biofilm infections.

Effective treatment of bacterial biofilm-related infections is a great challenge for the medical community. During the formation of biofilms, bacteria excrete extracellular polymeric substances (EPS), including polysaccharides, proteins, nucleic acids, etc., to encapsulate themselves and form a "fort-like" structure, which greatly reduces the efficiency of therapeutic agents. Herein, we prepared a nanoagent (MnO2-amylase-PEG-ICG nanosheets, MAPI NSs) with biofilm degradation capability for efficient photothermal therapy and fluorescence imaging of methicillin-resistant Staphylococcus aureus (MRSA) biofilm infections. MAPI NSs were constructed by sequentially modifying α-amylase, polyethylene glycol (PEG), and indocyanine green (ICG) on manganese dioxide nanosheets (MnO2 NSs). Experimental results exhibited that MAPI NSs could accumulate in infected tissues after intravenous injection, degrade in the acidic biofilm microenvironment, and release the loaded ICG for near-infrared (NIR) fluorescence imaging of the infected tissues. Importantly, MAPI NSs could efficiently eliminate MRSA biofilm infections in mice by α-amylase enhanced photothermal therapy. In addition, MAPI NSs exhibited neglectable toxicity towards mice. Given the superior properties of MAPI NSs, the enzyme-degradation enhanced therapeutic strategy presented in this work offers a promising solution for effectively combating biofilm infectious diseases.

Biofilm Microenvironment-Responsive Nanotheranostics for Dual-Mode Imaging and Hypoxia-Relief-Enhanced Photodynamic Therapy of Bacterial Infections.

The formation of bacterial biofilms closely associates with infectious diseases. Until now, precise diagnosis and effective treatment of bacterial biofilm infections are still in great need. Herein, a novel multifunctional theranostic nanoplatform based on MnO2 nanosheets (MnO2 NSs) has been designed to achieve pH-responsive dual-mode imaging and hypoxia-relief-enhanced antimicrobial photodynamic therapy (aPDT) of bacterial biofilm infections. In this study, MnO2 NSs were modified with bovine serum albumin (BSA) and polyethylene glycol (PEG) and then loaded with chlorin e6 (Ce6) as photosensitizer to form MnO2-BSA/PEG-Ce6 nanosheets (MBP-Ce6 NSs). After being delivered into the bacterial biofilm-infected tissues, the MBP-Ce6 NSs could be decomposed in acidic biofilm microenvironment and release Ce6 with Mn2+, which subsequently activate both fluorescence (FL) and magnetic resonance (MR) signals for effective dual-mode FL/MR imaging of bacterial biofilm infections. Meanwhile, MnO2 could catalyze the decomposing of H2O2 in biofilm-infected tissues into O2 and relieve the hypoxic condition of biofilm, which significantly enhances the efficacy of aPDT. An in vitro study showed that MBP-Ce6 NSs could significantly reduce the number of methicillin-resistant Staphylococcus aureus (MRSA) in biofilms after 635 nm laser irradiation. Guided by FL/MR imaging, MRSA biofilm-infected mice can be efficiently treated by MBP-Ce6 NSs-based aPDT. Overall, MBP-Ce6 NSs not only possess biofilm microenvironment-responsive dual-mode FL/MR imaging ability but also have significantly enhanced aPDT efficacy by relieving the hypoxia habitat of biofilm, which provides a promising theranostic nanoplatform for bacterial biofilm infections.

Antibody-Functionalized MoS2 Nanosheets for Targeted Photothermal Therapy of Staphylococcus aureus Focal Infection.

Bacterial biofilm-related diseases cause serious hazard to public health and bring great challenge to the traditional antibiotic treatment. Photothermal therapy (PTT) has been recognized as a promising alternative solution. However, the therapeutic efficacy of PTT is often compromised by the collateral damage to normal tissues due to the lack of bacteria-targeting capability. Here, a Staphylococcus aureus (S. aureus)-targeted PTT nanoagent is prepared based on antibody (anti-protein A IgG), polydopamine (PDA), and PEG-SH (thiolated poly (ethylene glycol)) functionalized MoS2 nanosheets (MoS2@PDA-PEG/IgG NSs, MPPI NSs). The PDA was used as bio-nano interface to facilitate the covalent conjugation of antibody and PEG-SH onto the surface of MoS2 NSs via facile catechol chemistry. Targeted PTT of MPPI NSs shows excellent inactivation efficiency of larger than 4 log (>99.99%) to S. aureus both in biofilms (in vitro) and in infected tissues (in vivo) without causing damage to normal mammalian cells. By contrast, non-targeted PTT of MoS2@PDA-PEG NSs (MPP NSs) only kills S. aureus by <90% in vitro and <50% in vivo. As a result, S. aureus focal infection in mice healed much faster after PTT of MPPI NSs than that of MPP NSs. The superiority of targeted PTT may originate from the efficient accumulation and close binding of PTT agents to bacterial cells. Therefore, MPPI NSs with bacteria-targeting capability are promising photothermal agents for effective treatment of S. aureus focal infection.