Open-cage metallo-azafullerenes as efficient single-atom catalysts toward oxygen reduction reaction.

Very recently, open-cage metallo-azafullerenes PbC100N4H4 and Pb2C100N4H4 containing one Pb-N4-C moiety have been synthesized via the electron beam. Herein, we utilized density functional theory calculations in combination with ab initio molecular dynamics (AIMD) simulations to study the geometric and electronic structures, bonding properties, thermodynamic stability, and catalytic performance of MC100N4H4 and M2C100N4H4 (M = Ge, Sn, Pb). Metal-nitrogen distances and metal-metal distances increase along with the metal radius while the metal atom is positively charged. Energy decomposition analysis revealed that the bonding interactions between M and the C100N4H4 fragment could be described as the donor-acceptor interaction between M(ns0(n-1)d10np4) and C100N4H4 fragment, in which the orbital interactions terms contribute more than the electrostatic interactions. AIMD simulations demonstrate that those metallo-azafullerenes exhibit thermodynamic stability at room temperature. These metallo-azafullerenes, which could serve as typical carbon-supported single-atom catalysts, possess enhanced catalytic performance toward the oxygen reduction reaction (ORR) compared to the planar catalysts, which is attributed to the curvature of metallo-azafullerenes. GeC100N4H4 and SnC100N4H4 exhibit high catalytic performance in the 4e-ORR pathway to H2O, whereas only PbC100N4H4 is suitable for the 2e-ORR reaction pathway because of the difficulty in obtaining electrons. All M2C100N4H4 favors the 4e-reaction pathway due to the presence of the axial metal atom. Our finding of open-cage metallo-azafullerenes as efficient single-atom catalysts holds profound implications for both fundamental research in catalysis and practical applications in fuel cells and other electrochemical devices.

Synthesis of Multifunctional Organic Molecules via Michael Addition Reaction to Manage Perovskite Crystallization and Defect.

Additive engineering plays a pivotal role in achieving high-quality light-absorbing layers for high-performance and stable perovskite solar cells (PSCs). Various functional groups within the additives exert distinct regulatory effects on the perovskite layer. However, few additive molecules can synergistically fulfill the dual functions of regulating crystallization and passivating defects. Here, we custom-synthesized 2-ureido-4-pyrimidone (UPy) organic small molecules with diverse functional groups as additives to modulate crystallization and defects in perovskite films via the Michael addition reaction. Theoretical and experimental investigations demonstrate that the -OH groups in UPy exhibit significant effects in fixing uncoordinated Pb2+ ions, passivation of lead-iodide antisite defects, alleviating hysteresis, and reducing non-radiative recombination. Furthermore, the enhanced C=O and -NH2 motifs interact with the A-site cation via hydrogen bonding, which relieves residual strain and adjusts crystal orientation. This strategy effectively controls perovskite crystallization and passivates defects, ultimately enhancing the quality of perovskite films. Consequently, the open-circuit voltage of the UPy-based p-i-n PSCs reaches 1.20 V, and the fill factor surpasses 84%. The champion device delivers a power conversion efficiency of 25.75%. Remarkably, the unencapsulated device maintained 96.9% and 94.5% of its initial efficiency following 3,360 hours of dark storage and 1,866 hours of 1-sun illumination, respectively.

Tailoring component incorporation for homogenized perovskite solar cells.

Deep-level traps at the buried interface of perovskite and energy mismatch problems between the perovskite layer and heterogeneous interfaces restrict the development of ideal homogenized films and efficient perovskite solar cells (PSCs) using the one-step spin-coating method. Here, we strategically employed sparingly soluble germanium iodide as a homogenized bulk in-situ reconstruction inducing material preferentially aggregated at the perovskite buried interface with gradient doping, markedly reducing deep-level traps and withstanding local lattice strain, while minimizing non-radiative recombination losses and enhancing the charge carrier lifetime over 9 µs. Furthermore, this gradient doping assisted in modifying the band diagram at the buried interface into a desirable flattened alignment, substantially mitigating the energy loss of charge carriers within perovskite films and improving the carrier extraction equilibrium. As a result, the optimized device achieved a champion power conversion efficiency of 25.24% with a fill factor of up to 84.65%, and the unencapsulated device also demonstrated excellent light stability and humidity stability. This work provides a straightforward and reliable homogenization strategy of perovskite components for obtaining efficient and stable PSCs.

Transparent Recombination Layers Design and Rational Characterizations for Efficient Two-Terminal Perovskite-Based Tandem Solar Cells.

Two-terminal (2T) perovskite-based tandem solar cells (TSCs) arouse burgeoning interest in breaking the Shockley-Queisser (S-Q) limit of single-junction solar cells by combining two subcells with different bandgaps. However, the highest certified efficiency of 2T perovskite-based TSCs (33.9%) lags behind the theoretical limit (42-43%). A vital challenge limiting the development of 2T perovskite-based TSCs is the transparent recombination layers/interconnecting layers (RLs) design between two subcells. To improve the performance of 2T perovskite-based TSCs, RLs simultaneously fulfill the optical loss, contact resistance, carrier mobility, stress management, and conformal coverage requirements. In this review, the definition, functions, and requirements of RLs in 2T perovskite-based TSCs are presented. The insightful characterization methods applicable to RLs, which are inspiring for further research on the RLs both in 2T perovskite-based two-junction and multi-junction TSCs, are also highlighted. Finally, the key factors that currently limit the performance enhancement of RLs and the future directions that should be continuously focused on are summarized.

Investigation of natural deep eutectic solvent for the extraction of crude polysaccharide from Polygonatum kingianum and influence of metal elements on its immunomodulatory effects.

In this study, natural deep eutectic solvent (NADES) was used to extract Polygonatum kingianum crude polysaccharide (PKCP) and response surface methodology (RSM) was designed to optimize the extraction procedure. The immunomodulatory effect of PKCP and the influence of metal elements on its immunomodulatory effect were further discussed. The optimum conditions for PKCP extraction were obtained by RSM optimization: NADES were synthesized with a 1:2 choline chloride-glycerol molar ratio, then extracted at a liquid-solid ratio of 16.6 mL g-1 and water content of 31.2 % for 60 min at 60 °C. This method was used for the extraction of PKCP, and the extraction efficiency was 29.69 %, which was 2.5 times greater than the conventional method of water extraction. In the concentration range of 200-800 µg mL-1, PKCP could activate macrophages, promoting NO secretion and mRNA expression of interleukin-6 (IL-6) and inducible nitric oxide synthase (iNOS) in a dose-dependent way. NO secretion and cytokine expression were not affected when the metal elements were spiked to the equivalent of the metal elements contained in Polygonatum kingianum. When the content of metal elements was higher, the secretion of NO and the gene expression of iNOS were both decreased, which may affect the immunomodulatory effect of Polygonatum kingianum.

A novel deep eutectic solvent modified magnetic covalent organic framework for the selective separation and determination of trace copper ion in medicinal plants and environmental samples.

BACKGROUND: Pretreatment techniques should be introduced before metal ion determination because there is very low content of heavy metals in Chinese medicinal plants and environmental samples. Magnetic dispersive micro solid phase extraction (MDMSPE) has been widely used for the separation and adsorption of heavy metal pollutants in medicinal plants and environmental samples. However, the majority of MDMSPE adsorbents have certain drawbacks, including low selectivity, poor anti-interference ability, and small adsorption capacity. Therefore, modifying currently available adsorption materials has gained attention in research. RESULTS: In this study, a novel adsorbent MCOF-DES based on a magnetic covalent organic framework (MCOF) modified by a new deep eutectic solvent (DES) was synthesized for the first time and used as an adsorbent of MDMSPE. The MDMSPE was combined with inductively coupled plasma optical emission spectrometry (ICP-OES) for selective separation, enrichment, and accurate determination of trace copper ion (Cu2+) in medicinal plants and environmental samples. Various characterization results show the successful preparation of new MCOF-DES. Under the optimal conditions, the enrichment factor (EF) of Cu2+ was 30, the limit of detection (LOD) was 0.16 µg L-1, and the limit of quantitation (LOQ) was 0.54 µg L-1. The results for the determination of Cu2+ were highly consistent with those of inductively coupled plasma mass spectrometry (ICP-MS), which verified the accuracy and reliability of the method. SIGNIFICANCE: The established method based on a new adsorption material MCOF-DES has achieved the selective separation and determination of trace Cu2+ in medicinal and edible homologous medicinal materials (Phyllanthus emblica Linn.) and environmental samples (soil and water), which provides a promising, selective, and sensitive approach for the determination of trace Cu2+ in other real samples.

Risk assessment and source identification of soil heavy metals: a case study of farmland soil along a river in the southeast of a mining area in Southwest China.

To investigate the heavy metals (HMs) contamination of surface farmland soil along the river in the southeast of a mining area in southwest China and identify the contamination sources, 54 topsoil samples were collected and the concentrations of seven elements (Zn, Ni, Pb, Cu, Hg, Cr, and Co) were determined by inductively coupled plasma optical emission spectrometry (ICP-OES) and atomic fluorescence spectrometry (AFS). The geo-accumulation index ([Formula: see text]) and comprehensive potential ecological risk index ([Formula: see text]) were used for analysis to determine the pollution degree of HMs and the risk level of the study area. Meanwhile, the Positive Matrix Factorization (PMF) model was combined with a variety of statistical methods to determine the sources of HMs. To explore the influence of the river flowing through the mining area on the concentrations of HMs in the farmland soil, 15 water samples were collected and the concentrations of the above seven elements were determined. The results showed that the concentrations of Pb, Cu, and Zn in soil all exceeded the risk screening value, and Pb in soil of some sampling sites exceeded control value of "Agricultural Land Soil Pollution Risk Control Standard".[Formula: see text] showed that Pb was heavily contaminated, while Cu and Zn were moderately contaminated. RI showed that the study area was at moderate risk. PMF and various statistical methods showed that the main source of HMs was the industrial source. In the short term, the river flowing through the mine has no significant influence on the concentration of HMs in the soil. The results provide a reference for the local government to control contamination and identify the sources of HMs.

Na Substitution Steering RuO6 Unit in Ruthenium Pyrochlores for Enhanced Oxygen Evolution in Acid.

Although Ruthenium-based pyrochlore oxides can function as promising catalysts for acidic water oxidation, their limitations in terms of stability and activity still need to be addressed for further application in practical conditions. In this work, the possibility to enhance both oxygen evolution reaction activity and durability of Gd2Ru2O7- δ through partial replacement with Na+ in Gd3+ sites is first offered, leading to the electronic and geometric regulation of active center RuO6. Na+ triggers the emergence of Ru<4+ and the electron rearrangement of active-centered RuO6. Specifically, Ru ions with a negative d-band center after Na+ doping exhibit weaker adsorption energies of *O and result in the conversion of the rate-limiting step from *O/*OOH to *OH/O*, reducing energy barriers for boosting activities. Therefore, the NaxGd2- xRu2O7- δ requires a low overpotential of 260 mV at 10 mA cm-2 in 0.1 m HClO4 electrolyte. Moreover, the higher formation energy of Ru vacancy and less distorted RuO6 enable the as-prepared NaxGd2- xRu2O7- δ to operate steadily at 10 mA cm-2 for 300 h and multi-current chronopotentiometry with current densities from 20 to 100 mA cm-2 for 60 h in acidic proton exchange membrane electrolyzer, respectively.

Large-n quasi-phase-pure two-dimensional halide perovskite: A toolbox from materials to devices.

Despite their excellent environmental stability, low defect density, and high carrier mobility, large-n quasi-two-dimensional halide perovskites (quasi-2DHPs) feature a limited application scope because of the formation of self-assembled multiple quantum wells (QWs) due to the similar thermal stabilities of large-n phases. However, large-n quasi-phase-pure 2DHPs (quasi-PP-2DHPs) can solve this problem perfectly. This review discusses the structures, formation mechanisms, and photoelectronic and physical properties of quasi-PP-2DHPs, summarises the corresponding single crystals, thin films, and heterojunction preparation methods, and presents the related advances. Moreover, we focus on applications of large-n quasi-PP-2DHPs in solar cells, photodetectors, lasers, light-emitting diodes, and field-effect transistors, discuss the challenges and prospects of these emerging photoelectronic materials, and review the potential technological developments in this area.