ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
Subject(s)
Polygonatum , Solvents , Deep Eutectic Solvents , Water , Polysaccharides/pharmacologyABSTRACT
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.
Subject(s)
Metals, Heavy , Soil , Farms , Rivers , Lead , Risk Assessment , ChinaABSTRACT
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.
Subject(s)
Metal-Organic Frameworks , Plants, Medicinal , Copper , Deep Eutectic Solvents , Reproducibility of Results , Magnetic PhenomenaABSTRACT
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.
ABSTRACT
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.
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Supported metal catalysts often suffer from rapid degradation under harsh conditions due to material failure and weak metal-support interaction. Here we propose using reductive hydrogenated borophene to in-situ synthesize Pt/B/C catalysts with small sizes (~2.5 nm), high-density dispersion (up to 80 wt%Pt), and promising stability, originating from forming Pt-B bond which are theoretically ~5× stronger than Pt-C. Based on the Pt/B/C module, a series (~18 kinds) of carbon supported binary, ternary, quaternary, and quinary Pt intermetallic compound nanocatalysts with sub-4 nm size are synthesized. Thanks to the stable intermetallics and strong metal-support interaction, annealing at 1000 °C does not cause those nanoparticles sintering. They also show much improved activity and stability in electrocatalytic oxygen reduction reaction. Therefore, by introducing the boron chemistry, the hydrogenated borophene derived multielement catalysts enable the synergy of small size, high loading, stable anchoring, and flexible compositions, thus demonstrating high versatility toward efficient and durable catalysis.
ABSTRACT
The development of extreme performance and multifunctional electromagnetic (EM) wave absorption materials is essential to eliminating undesirable frequency EM pollution. As a promising rare-earth compound, gadolinium oxysulfide (Gd2O2S) has become a significant field of study among nanomaterials with multidisciplinary applications. Herein, the ultrathin Gd2O2S nanosheets with 1 nm thickness were fabricated via a facile hot injection method and then mixed with reduced graphene oxide (rGO) through coassemble and carbonization methods to form Gd2O2S/rGO composites. As a new kind of multifunction EM-wave absorption materials, Gd2O2S/rGO composites exhibited excellent EM-wave absorption performance with an absorption capacity of -65 dB (2.1 mm) and an adequate absorption bandwidth of 5.6 GHz at 1.9 mm. Additionally, their EM-wave absorption mechanisms have been unveiled for the first time. The outstanding EM-wave absorption performance of Gd2O2S/rGO composites could be attributed to the ultrathin Gd2O2S nanosheets with oxygen vacancy and rGO layers with high conductivity and large specific surface area, which will also facilitate the polarization loss, conductivity loss, and multiple reflection and scattering of EM waves between the rGO layer and Gd2O2S nanosheets. Overall, compared to previously reported rGO-based EM-wave absorption materials, this work provides a promising approach for the exploitation and synthesis of Gd2O2S/rGO composites with lightweight and high-performance microwave attenuation.
ABSTRACT
To boost the electrocatalytic methanol oxidation reaction (MOR) of Platinum (Pt), making binary PtM (M = transition metals, for example, Fe, Cu, and Ni) with specific morphology is known as a promising method. Although great progress has been made in the synthesis of shaped PtM catalysts toward MOR, enhancing the catalytic performance of the PtM to enable it to be commercialized is still a hotspot. In this work, the Au-doped PtNi dendritic nanoparticles (Au-PtNi DNPs) were obtained by doping a small amount of gold (Au) into initially prepared PtNi DNPs, greatly improving their MOR catalytic activity and durability. The energy-dispersive X-ray spectroscopy mapping (EDXS) indicates that the surface of DNPs is mainly composed of Au dopant and PtNi, while the core is mainly Pt, indicating the formation of Au-doped PtNi/Pt core-shell-like DNP structures. The electrocatalytic performance of the prepared Au-PtNi DNPs with different compositions for the MOR was evaluated using cyclic voltammetry, chronoamperometry, and CO-stripping tests. The experimental findings indicate that the Au-PtNi DNPs showed better MOR performance in comparison with PtNi DNPs and commercial Pt catalysts. Among all the catalysts, 6% Au-PtNi DNPs showed 4.3 times improved mass catalytic activity for the MOR in comparison with commercial Pt catalysts. In addition, all the prepared Au-PtNi DNPs display a remarkable CO tolerance compared to that of PtNi DNPs and commercial Pt catalysts. The dendritic structure of Au-PtNi DNPs can effectively enhance catalytic performance, combined with the electronic effect of Au, Pt, and Ni.
ABSTRACT
Flexible perovskite solar cells (f-PSCs) as a promising power source have grabbed surging attention from academia and industry specialists by integrating with different wearable and portable electronics. With the development of low-temperature solution preparation technology and the application of different engineering strategies, the power conversion efficiency of f-PSCs has approached 24%. Due to the inherent properties and application scenarios of f-PSCs, the study of strain in these devices is recognized as one of the key factors in obtaining ideal devices and promoting commercialization. The strains mainly from the change of bond and lattice volume can promote phase transformation, induce decomposition of perovskite film, decrease mechanical stability, etc. However, the effect of strain on the performance of f-PSCs has not been systematically summarized yet. Herein, the sources of strain, evaluation methods, impacts on f-PSCs, and the engineering strategies to modulate strain are summarized. Furthermore, the problems and future challenges in this regard are raised, and solutions and outlooks are offered. This review is dedicated to summarizing and enhancing the research into the strain of f-PSCs to provide some new insights that can further improve the optoelectronic performance and stability of flexible devices.
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In this study, based on the assessment of soil heavy metals (HMs) pollution using relevant indices, a comprehensive approach combined network environ analysis (NEA), human health risk assessment (HHRA) method and positive definite matrix factor (PMF) model to quantify the risks among ecological communities in a special environment around mining area in northwest Yunnan, calculated the risk to human health caused by HMs in soil, and analyzed the pollution sources of HMs. The integrated risks for soil microorganisms, vegetations, herbivores, and carnivores were 2.336, 0.876, 0.114, and 0.082, respectively, indicating that soil microorganisms were the largest risk receptors. The total hazard indexes (HIT) for males, females, and children were 0.542, 0.591, and 1.970, respectively, revealing a relatively high and non-negligible non-carcinogenic risks (NCR) for children. The total cancer risks (TCR) for both females and children exceeded 1.00E-04, indicating that soil HMs posed carcinogenic risks (CR) to them. Comparatively, Pb was the high-risk metal, accounting for 53.76%, 57.90%, and 68.09% of HIT in males, females, and children, respectively. PMF analysis yielded five sources of pollution, F1 (industry), F2 (agriculture), F3 (domesticity), F4 (nature), and F5 (traffic).
Subject(s)
Metals, Heavy , Soil Pollutants , Child , Humans , Soil , China , Environmental Monitoring , Soil Pollutants/analysis , Risk Assessment , Metals, Heavy/analysis , CarcinogensABSTRACT
In this work, ultrasound-assisted rapidly synergistic cloud point extraction (UARS-CPE) and inductively coupled plasma optical emission spectrometry (ICP-OES) were combined to determine trace Pb in Gentiana rigescens Franch. ex Hemsl. (G. rigescens) samples. Under the optimal conditions, the enhancement factor (EF), limit of detection (LOD), limit of quantitation (LOQ) and precision were 33, 0.11 µg L-1, 0.37 µg L-1 and 1.3%, respectively. This method was applied to the analysis of G. rigescens samples, and the outcomes were in good agreement with the results determined by inductively coupled plasma mass spectrometry (ICP-MS). A mice model of immune liver injury induced by concanavalin A (ConA) was established, and the liver protection of G. rigescens and gentiopicroside (GPS) on it and the effects of various dosages of Pb exposure on its liver protection were studied. Pb at a dosage of 5 mg kg-1 had little effect on the liver protection of G. rigescens and GPS, while 25, 125 mg kg-1 dosages of Pb could significantly attenuate the liver protection of both. In addition, it aggravated the necrosis of hepatocytes and inflammatory cell infiltration, and these effects were dose-dependent.
Subject(s)
Gentiana , Animals , Mice , Gentiana/chemistry , Lead/toxicity , Iridoid Glucosides/chemistry , LiverABSTRACT
It is challenging to develop high-efficient and stable nonprecious metal-based electrocatalyst for oxygen evolution reaction (OER) in acid for proton exchange membrane (PEM) water splitting. Herein, P atoms were introduced into the lattice of spinel Co3O4 (P-Co3O4) to replace with octahedral coordinated Co3+ via a hydrothermal process following a thermal treatment. The formation of PO6 geometric configuration unit in Co3O4 can trigger electron rearrangement around Co ions, which resulted in the high-active Co2+ site on the surface, significantly decreasing the energy barrier of rate-determining step for OER. Moreover, the weaker covalency of the Co 3d-O 2p bond and higher formation energy of oxygen vacancy around Co2+ in P-Co3O4 inhibited the participation of lattice oxygen during OER process, enabling that P-Co3O4 can work stably in acidic media. The obtained P-Co3O4 afforded satisfying stability over 30 h in a PEM electrolysis device with an overpotential of 400 mV@10 mA/cm2 in 0.1 M HClO4.
ABSTRACT
Metal halide hybrid perovskite solar cells (PSCs) have received considerable attention over the past decade owing to their potential for low-cost, solution-processable, earth-abundant, and high-performance superiority, increasing power conversion efficiencies of up to 25.7%. Solar energy conversion into electricity is highly efficient and sustainable, but direct utilization, storage, and poor energy diversity are difficult to achieve, resulting in a potential waste of resources. Considering its convenience and feasibility, converting solar energy into chemical fuels is regarded as a promising pathway for boosting energy diversity and expanding its utilization. In addition, the energy conversion-storage integrated system can efficiently sequentially capture, convert, and store energy in electrochemical energy storage devices. However, a comprehensive overview focusing on PSC-self-driven integrated devices with a discussion of their development and limitations remains lacking. Here, focus is on the development of representative configurations of emerging PSC-based photo-electrochemical devices including self-charging power packs, unassisted solar water splitting/CO2 reduction. The advanced progresses in this field, including configuration design, key parameters, working principles, integration strategies, electrode materials, and their performance evaluations are also summarized. Finally, scientific challenges and future perspectives for ongoing research in this field are presented.
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In this work, deep eutectic solvent (DES) was used to modify GO-TiO2 to synthesize new adsorption material GO-TiO2-DES nanocomposites. It was first used for dispersive micro solid phase extraction (DMSPE) and combined with inductively coupled plasma optical emission spectrometry (ICP-OES) for simultaneous determination of trace cobalt (Co) and lead (Pb) in natural medicine P. polyphylla var. yunnanensis. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), and the Brunauer-Emmett-Teller (BET) specific surface area were used to characterize. The results showed that GO-TiO2-DES nanocomposites were successfully prepared and had better adsorption effect on metal ions. The factors affecting the extraction and elution of Co and Pb were optimized, including the type of DES, pH, adsorption time, amount of adsorbent, adsorption temperature, and elution time. Under the optimum conditions, the enhancement factors (EFs) of Co and Pb were 31 and 28, the limits of detection (LODs) were 0.11 and 0.24 µg L-1, and the limits of quantification (LOQs) were 0.36 and 0.82 µg L-1, respectively. The results of Co and Pb determined by the established method were in good agreement with those of inductively coupled plasma mass spectrometry (ICP-MS), which verified the accuracy and reliability of the method.
Subject(s)
Cobalt , Lead , Spectroscopy, Fourier Transform Infrared , Reproducibility of Results , Solid Phase Extraction/methodsABSTRACT
The ensemble effect due to variation of Pd content in Pd-Au alloys have been widely investigated for several important reactions, including CO2 reduction reaction (CO2 RR), however, identifying the stable Pd arrangements on the alloyed surface and picking out the active sites are still challenging. Here we use a density functional theory (DFT) based machine-learning (ML) approach to efficiently find the low-energy configurations of Pd-Au(111) surface alloys and the potentially active sites for CO2 RR, fully covering the Pd content from 0 to 100 %. The ML model is actively learning process to improve the predicting accuracy for the configuration formation energy and to find the stable Pd-Au(111) alloyed surfaces, respectively. The local surface properties of adsorption sites are classified into two classes by the K-means clustering approach, which are closely related to the Pd content on Au surface. The classification is reflected in the variation of adsorption energy of CO and H: In the low Pd content range (0-60 %) the adsorption energies over the surface alloys can be tuned significantly, and in the medium Pd content (37-68 %), the catalytic activity of surface alloys for CO2 RR can be increased by increase the Pd content and attributed to the meta-stable active site over the surface. Thus, the active site-dependent reaction mechanism is elucidated based on the ensemble effect, which provides new physical insights to understand the surface-related properties of catalysts.
ABSTRACT
It is of great importance to promote charge separation in photocatalysts for enhanced photocatalytic activity under visible light irradiation. In this work, a type-II heterostructured photocatalyst was constructed by compositing phosphorus-doped g-C3N4 (P-CN) and Rh-doped SrTiO3 (Rh-STO) via a thermal calcination treatment. A series of characterizations were conducted to investigate the structure of heterostructured P-CN/Rh-STO. It was found that Rh-STO interacted with in situ generated P atoms from the decomposition of P-CN during the calcination process, thus leading to the formation of heterojunction of P-CN/Rh-STO. Compared with the single component, i.e., P-CN or Rh-STO, the obtained P-CN/Rh-STO showed superior photocatalytic activity to that of both P-CN and Rh-STO due to the effective charge separation across the heterojunction between P-CN and Rh-STO.