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1.
PLoS Biol ; 22(1): e3002453, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38180950

RESUMO

To achieve a stable size distribution over multiple generations, proliferating cells require a means of counteracting stochastic noise in the rate of growth, the time spent in various phases of the cell cycle, and the imprecision in the placement of the plane of cell division. In the most widely accepted model, cell size is thought to be regulated at the G1/S transition, such that cells smaller than a critical size pause at the end of G1 phase until they have accumulated mass to a predetermined size threshold, at which point the cells proceed through the rest of the cell cycle. However, a model, based solely on a specific size checkpoint at G1/S, cannot readily explain why cells with deficient G1/S control mechanisms are still able to maintain a very stable cell size distribution. Furthermore, such a model would not easily account for stochastic variation in cell size during the subsequent phases of the cell cycle, which cannot be anticipated at G1/S. To address such questions, we applied computationally enhanced quantitative phase microscopy (ceQPM) to populations of cultured human cell lines, which enables highly accurate measurement of cell dry mass of individual cells throughout the cell cycle. From these measurements, we have evaluated the factors that contribute to maintaining cell mass homeostasis at any point in the cell cycle. Our findings reveal that cell mass homeostasis is accurately maintained, despite disruptions to the normal G1/S machinery or perturbations in the rate of cell growth. Control of cell mass is generally not confined to regulation of the G1 length. Instead mass homeostasis is imposed throughout the cell cycle. In the cell lines examined, we find that the coefficient of variation (CV) in dry mass of cells in the population begins to decline well before the G1/S transition and continues to decline throughout S and G2 phases. Among the different cell types tested, the detailed response of cell growth rate to cell mass differs. However, in general, when it falls below that for exponential growth, the natural increase in the CV of cell mass is effectively constrained. We find that both mass-dependent cell cycle regulation and mass-dependent growth rate modulation contribute to reducing cell mass variation within the population. Through the interplay and coordination of these 2 processes, accurate cell mass homeostasis emerges. Such findings reveal previously unappreciated and very general principles of cell size control in proliferating cells. These same regulatory processes might also be operative in terminally differentiated cells. Further quantitative dynamical studies should lead to a better understanding of the underlying molecular mechanisms of cell size control.


Assuntos
Ciclo Celular , Humanos , Divisão Celular , Tamanho Celular , Proliferação de Células , Homeostase
2.
Small ; 20(11): e2306836, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37932023

RESUMO

The synthesis and characterization of an FeII /FeIII metal-organic framework (MOF) nanocrystal with spatial heterogeneity that arises from the non-uniform distribution of different valence states is disclosed. The FeII /FeIII -Ni Prussian blue analog (PBA) delivers superior photocatalytic performance in the selective CO2 reduction reaction thanks to the strong FeII /FeIII coupling, with CO yield up to 12.27 mmol g-1 h-1 and 90.6% selectivity under visible-light irradiation. Density functional theory calculation and experimental studies prove that the spatial heterogeneity of FeII /FeIII in the individual MOF nanocrystal not only directs and expedites the charge transfer within a catalyst particle but also creates the heterogeneity of catalytically-active Ni sites for efficient CO2 photoreduction. The current findings add to a growing literature of materials with compositional heterogeneity and provide a reference for future research.

3.
Small ; : e2401559, 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38659393

RESUMO

A facile gaseous CO2 mediated solid-to-solid transformation principle is adopted to insert additional CO3 2- anions into the thin single-crystal nanosheets of Bi2O2CO3, which is built of periodic arrays of intrinsic CO3 2- anions and (Bi2O2)2+ layers. The additional CO3 2- anions create abundant defects. The Bi2O2CO3 nanosheets with rich interlayer CO3 2- exhibit superior electronic properties and charge transfer kinetics than the pristine single-crystal 2D Bi2O2CO3 and display enhanced catalytic activity in photocatalytic CO2 reduction reaction and the photocatalytic oxidative degradation of organic pollutants. This work thus illustrates interlayer engineering as a flexible means to build layered 2D materials with excellent properties.

4.
Small ; 20(24): e2308016, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38308412

RESUMO

In modern heterogeneous catalysis, it remains highly challenging to create stable, low-cost, mesoporous 2D photo-/electro-catalysts that carry atomically dispersed active sites. In this work, a general shape-preserving amorphous-to-crystalline transformation (ACT) strategy is developed to dope various transition metal (TM) heteroatoms in ZrO2, which enabled the scalable synthesis of TMs/oxide with a mesoporous 2D structure and rich defects. During the ACT process, the amorphous MZrO2 nanoparticles (M = Fe, Ni, Cu, Co, Mn) are deposited within a confined space created by the NaCl template, and they transform to crystalline 2D ACT-MZrO2 nanosheets in a shape-preserving manner. The interconnected crystalline ACT-MZrO2 nanoparticles thus inherit the same structure as the original MZrO2 precursor. Owing to its rich active sites on the surface and abundant oxygen vacancies (OVs), ACT-CoZrO2 gives superior performance in catalyzing the CO2-to-syngas conversion as demonstrated by experiments and theoretical calculations. The ACT chemistry opens a general route for the scalable synthesis of advanced catalysts with precise microstructure by reconciliating the control of crystalline morphologies and the dispersion of heteroatoms.

5.
Sensors (Basel) ; 24(8)2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38676143

RESUMO

The swift advancements in robotics have rendered navigation an essential task for mobile robots. While map-based navigation methods depend on global environmental maps for decision-making, their efficacy in unfamiliar or dynamic settings falls short. Current deep reinforcement learning navigation strategies can navigate successfully without pre-existing map data, yet they grapple with issues like inefficient training, slow convergence, and infrequent rewards. To tackle these challenges, this study introduces an improved two-delay depth deterministic policy gradient algorithm (LP-TD3) for local planning navigation. Initially, the integration of the long-short-term memory (LSTM) module with the Prioritized Experience Re-play (PER) mechanism into the existing TD3 framework was performed to optimize training and improve the efficiency of experience data utilization. Furthermore, the incorporation of an Intrinsic Curiosity Module (ICM) merges intrinsic with extrinsic rewards to tackle sparse reward problems and enhance exploratory behavior. Experimental evaluations using ROS and Gazebo simulators demonstrate that the proposed method outperforms the original on various performance metrics.

6.
Nano Lett ; 23(21): 9872-9879, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37856869

RESUMO

Lithium metal deposition is strongly affected by the intrinsic properties of the solid-electrolyte interphase (SEI) and working electrolyte, but a relevant understanding is far from complete. Here, by employing multiple electrochemical techniques and the design of SEI and electrolyte, we elucidate the electrochemistry of Li deposition under mass transport control. It is discovered that SEIs with a lower Li ion transference number and/or conductivity induce a distinctive current transition even under moderate potentiostatic polarization, which is associated with the control regime transition of Li ion transport from the SEI to the electrolyte. Furthermore, our findings help reveal the creation of a space-charge layer at the electrode/SEI interface due to the involvement of the diffusion process of Li ions through the SEI, which promotes the formation of dendrite embryos that develop and eventually trigger SEI breakage and the control regime transition of Li ion transport. Our insight into the very initial dendritic growth mechanism offers a bridge toward design and control for superior SEIs.

7.
Angew Chem Int Ed Engl ; 63(20): e202402775, 2024 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-38468414

RESUMO

Tin-based perovskite solar cells (TPSCs) have received increasing attention due to their low toxicity, high theoretical efficiency, and potential applications as wearable devices. However, the inherent fast and uncontrollable crystallization process of tin-based perovskites results in high defect density in the film. Meanwhile, when fabricated into flexible devices, the prepared perovskite film exhibits inevitable brittleness and high Young's modulus, seriously weakening the mechanical stability. In this work, we design and synthesize a cross-linkable fullerene, thioctic acid functionalized C60 fulleropyrrolidinium iodide (FTAI), which has multiple interactions with perovskite components and can finely regulate the crystallization quality of perovskite film. The obtained perovskite film shows an increased grain size and a more matched energy level with the electron transport material, effectively improving the carrier extraction efficiency. The FTAI-based rigid device achieves a champion efficiency of 14.91 % with enhanced stability. More importantly, the FTAI located at the perovskite grain boundaries could spontaneously cross-link during the perovskite annealing process, which effectively improves the conductivity and elasticity of grain boundaries, thereby giving the film excellent bending resistance. Finally, the FTAI-based wearable device yields a record efficiency of 12.35 % and displays robust bending durability, retaining about 90 % of the initial efficiency after 10,000 bending times.

8.
J Am Chem Soc ; 145(22): 11959-11968, 2023 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-37216562

RESUMO

In the pursuit of a highly reversible lithium-oxygen (Li-O2) battery, control of reaction sites to maintain stable conversion between O2 and Li2O2 at the cathode side is imperatively desirable. However, the mechanism involving the reaction site during charging remains elusive, which, in turn, imposes challenges in recognition of the origin of overpotential. Herein, via combined investigations by in situ atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), we propose a universal morphology-dictated mechanism of efficient reaction sites for Li2O2 decomposition. It is found that Li2O2 deposits with different morphologies share similar localized conductivities, much higher than that reported for bulk Li2O2, enabling the reaction site not only at the electrode/Li2O2/electrolyte interface but also at the Li2O2/electrolyte interface. However, while the mass transport process is more enhanced at the former, the charge-transfer resistance at the latter is sensitively related to the surface structure and thus the reactivity of the Li2O2 deposit. Consequently, for compact disk-like deposits, the electrode/Li2O2/electrolyte interface serves as the dominant decomposition site, which causes premature departure of Li2O2 and loss of reversibility; on the contrary, for porous flower-like and film-like Li2O2 deposits bearing a larger surface area and richer surface-active structures, both the interfaces are efficient for decomposition without premature departure of the deposit so that the overpotential arises primarily from the sluggish oxidation kinetics and the decomposition is more reversible. The present work provides instructive insights into the understanding of the mechanism of reaction sites during the charge process, which offers guidance for the design of reversible Li-O2 batteries.

9.
Anal Chem ; 95(15): 6458-6466, 2023 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-37027511

RESUMO

The (5 × 5) Moiré pattern resulting from coadsorption of Cu atoms and chloride ions on the Au(111) electrode is one of the most classical structures for underpotential deposition (UPD) in electrochemical surface science. Although two models have been proposed to describe the pattern, the details of the structure remain ambiguous and controversial, leading to a question that remains to be answered. In this work, we investigate the UPD behaviors of Cu on the Au(111) electrode in a chloride-based deep eutectic solvent ethaline by in situ scanning tunneling microscopy (STM). Benefiting from the properties of the ultraconcentrated electrolyte, we directly image not only Cu but also Cl adlayers by finely tuning tunneling conditions. The structure is unambiguously determined for both Cu and Cl adlayers, where an incommensurate Cu layer is adsorbed on the Au(111) surface with a Cu coverage of 0.64, while the Cl coverage is 0.32 (only half of the expected value); i.e., the atomic arrangement of the observed (5 × 5) Moiré pattern in ethaline matches neither of the models proposed in the literature. Meanwhile, STM results confirm the origin of the cathodic peak in the cyclic voltammogram, which indicates that the underpotential shift of Cu UPD in ethaline indeed increases by ca. 0.40 V compared to its counterpart in a sulfuric acid solution, resulting in a significant deviation from the linear relation between the underpotential shift and the difference in work functions proposed in the literature. The unconventional electrochemical behaviors of Cu UPD reveal the specialty of both the bulk and the interface in the chloride-based deep eutectic solvent.

10.
Small ; 19(45): e2302683, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37466274

RESUMO

Orderly heterostructured catalysts, which integrate nanomaterials of complementary structures and dimensions into single-entity structures, have hold great promise for sustainability applications. In this work, it is showcased that air as green reagent can trigger in situ localized phase transformation and transform the metal carbonate hydroxide nanowires into ordered heterostructured catalyst. In single-crystal nanowire heterostructure, the in situ generated and nanosized Co3 O4 will be anchored in single-crystal Co6 (CO3 )2 (OH)8 nanowires spontaneously, triggered by the lattice matching between the (220) plane of Co3 O4 and the (001) plane of Co6 (CO3 )2 (OH)8 . The lattice matching allows intimate contact at heterointerface with well-defined orientation and strong interfacial coupling, and thus significantly expedites the transfer of photogenerated electrons from tiny Co3 O4 to catalytically active Co6 (CO3 )2 (OH)8 in single-crystal nanowire, which elevates the catalytic efficiency of metal carbonate catalyst in the CO2 reduction reaction (VCO = 19.46 mmol g-1 h-1 and VH2 = 11.53 mmol g-1 h-1 ). The present findings add to the growing body of knowledge on exploiting Earth-abundant metal-carbonate catalysts, and demonstrate the utility of localized phase transformation in constructing advanced catalysts for energy and environmental sustainability applications.

11.
Small ; 19(16): e2206873, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36609921

RESUMO

Preparation of holey, single-crystal, 2D nanomaterials containing in-plane nanosized pores is very appealing for the environment and energy-related applications. Herein, an in situ topological transformation is showcased of 2D layered double hydroxides (LDHs) allows scalable synthesis of holey, single-crystal 2D transition metal oxides (TMOs) nanomesh of ultrathin thickness. As-synthesized 2D Co/NiO-2 nanomesh delivers superior photocatalytic CO2 -syngas conversion efficiency (i.e., VCO of 32460 µmol h-1 g-1 CO and V H 2 ${V_{{{\rm{H}}_2}}}$ of 17840 µmol h-1 g-1 H2 ), with VCO about 7.08 and 2.53 times that of NiO and 2D Co/NiO-1 nanomesh containing larger pore size, respectively. As revealed in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the high performance of Co/NiO-2 nanomesh primarily originates from the edge sites of nanopores, which carry more defect structures (e.g., atomic steps or vacancies) than basal plane for CO2 adsorption, and from its single-crystal structure adept at charge transport. Theoretical calculation shows the topological transformation from 2D hydroxide to holey 2D oxide can be achieved, probably since the trace Co dopant induces a lattice distortion and thus a sharp decrease of the dehydration energy of hydroxide precursor. The findings can advance the design of intriguing holey 2D materials with well-defined geometric and electronic properties.

12.
J Synchrotron Radiat ; 30(Pt 4): 662-670, 2023 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-37163304

RESUMO

Transmission measurements of the soft X-ray beamline to the Small Quantum Systems (SQS) scientific instrument at the SASE3 undulator of European XFEL are presented. Measurements are reported for a wide range of photon energies (650 eV to 2400 eV), using X-ray gas monitors as well as a bolometric radiometer. The results are in good agreement with simulations for the beam transport and show a transmission of up to 80% over the whole photon energy range. The contribution of second- and third-harmonic radiation of the soft X-ray undulator is determined at selected photon energies by performing transmission measurements using a gas absorber to provide variable attenuation of the incoming photon flux. A comparison of the results with semi-analytic calculations for the generation of free-electron laser pulses in the SASE3 undulator reveals an influence of apertures along the beam transport on the exact harmonic content to be accounted for at the experiment. The second-harmonic content is measured to be in the range of 0.1% to 0.3%, while the third-harmonic contributed a few percent to the SASE3 emission. For experiments at the SQS instrument, these numbers can be reduced through specific selections of the mirror reflection angles.


Assuntos
Lasers , Síncrotrons , Raios X , Radiografia , Fótons
13.
Sensors (Basel) ; 23(22)2023 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-38005559

RESUMO

Variational auto-encoders (VAE) have been widely used in process modeling due to the ability of deep feature extraction and noise robustness. However, the construction of a supervised VAE model still faces huge challenges. The data generated by the existing supervised VAE models are unstable and uncontrollable due to random resampling in the latent subspace, meaning the performance of prediction is greatly weakened. In this paper, a new multi-layer conditional variational auto-encoder (M-CVAE) is constructed by injecting label information into the latent subspace to control the output data generated towards the direction of the actual value. Furthermore, the label information is also used as the input with process variables in order to strengthen the correlation between input and output. Finally, a neural network layer is embedded in the encoder of the model to achieve online quality prediction. The superiority and effectiveness of the proposed method are demonstrated by two real industrial process cases that are compared with other methods.

14.
Molecules ; 28(5)2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36903545

RESUMO

Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Meanwhile, we employed atomic force microscopy (AFM) to image the evolution of the surface morphology of the Au electrode during its dissolution and passivation process. The obtained AFM data help to explain the observations about the effect of water content on the Au anodic process from the microscopic perspective. High water contents make the occurrence of anodic dissolution of gold at higher potential, but enhances the rate of the electron transfer and gold dissolution. AFM results reveal the occurrence of massive exfoliation, which confirms that the gold dissolution reaction is more violent in ethaline with higher water contents. In addition, AFM results illustrate that the passive film and its average roughness could be tailored by changing the water content of ethaline.

15.
PLoS Pathog ; 16(9): e1008796, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32913364

RESUMO

There is an urgent need for effective treatment and preventive vaccine to contain this devastating global pandemic, which requires a comprehensive understanding of humoral responses specific to SARS-CoV-2 during the disease progression and convalescent phase of COVID-19 patients. We continuously monitored the serum IgM and IgG responses specific to four SARS-CoV-2 related antigens, including the nucleoprotein (NP), receptor binding domain (RBD), S1 protein, and ectodomain (ECD) of the spike protein among non-severe and severe COVID-19 patients for seven weeks since disease onset. Most patients generated humoral responses against NP and spike protein-related antigens but with their distinct kinetics profiles. Combined detection of NP and ECD antigens as detecting antigen synergistically improved the sensitivity of the serological assay, compared to that of using NP or RBD as detection antigen. 80.7% of convalescent sera from COVID-19 patients revealed that the varying extents of neutralization activities against SARS-CoV-2. S1-specific and ECD-specific IgA responses were strongly correlated with the neutralization activities in non-severe patients, but not in severe patients. Moreover, the neutralizing activities of the convalescent sera were shown to significantly decline during the period between 21 days to 28 days after hospital discharge, accompanied by a substantial drop in RBD-specific IgA response. Our data provide evidence that are crucial for serological testing, antibody-based intervention, and vaccine design of COVID-19.


Assuntos
Anticorpos Neutralizantes/farmacologia , Anticorpos Antivirais/farmacologia , Betacoronavirus/efeitos dos fármacos , Infecções por Coronavirus/tratamento farmacológico , Pneumonia Viral/tratamento farmacológico , Glicoproteína da Espícula de Coronavírus/antagonistas & inibidores , Anticorpos Neutralizantes/imunologia , Anticorpos Antivirais/imunologia , Betacoronavirus/patogenicidade , COVID-19 , Humanos , Imunoglobulina G/sangue , Estudos Longitudinais , Pandemias , SARS-CoV-2 , Testes Sorológicos , Glicoproteína da Espícula de Coronavírus/imunologia
16.
Faraday Discuss ; 233(0): 190-205, 2022 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-34889342

RESUMO

Copper is the most widely used substrate for Li deposition and dissolution in lithium metal anodes, which is complicated by the formation of solid electrolyte interphases (SEIs), whose physical and chemical properties can affect Li deposition and dissolution significantly. However, initial Li nucleation and growth on bare Cu creates Li nuclei that only partially cover the Cu surface so that SEI formation could proceed not only on Li nuclei but also on the bare region of the Cu surface with different kinetics, which may affect the follow-up processes distinctively. In this paper, we employ in situ atomic force microscopy (AFM), together with X-ray photoelectron spectroscopy (XPS), to investigate how SEIs formed on a Cu surface, without Li participation, and on the surface of growing Li nuclei, with Li participation, affect the components and structures of the SEIs, and how the formation sequence of the two kinds of SEIs, along with Li deposition, affect subsequent dissolution and re-deposition processes in a pyrrolidinium-based ionic liquid electrolyte containing a small amount of water. Nanoscale in situ AFM observations show that sphere-like Li deposits may have differently conditioned SEI-shells, depending on whether Li nucleation is preceded by the formation of the SEI on Cu. Models of integrated-SEI shells and segmented-SEI shells are proposed to describe SEI shells formed on Li nuclei and SEI shells sequentially formed on Cu and then on Li nuclei, respectively. "Top-dissolution" is observed for both types of shelled Li deposits, but the integrated-SEI shells only show wrinkles, which can be recovered upon Li re-deposition, while the segmented-SEI shells are apparently top-opened due to mechanical stresses introduced at the junctions of the top regions and become "dead" SEIs, which forces subsequent Li nucleation and growth in the interstice of the dead SEIs. Our work provides insights into the impact mechanism of SEIs on the initial stage Li deposition and dissolution on foreign substrates, revealing that SEIs could be more influential on Li dissolution and that the spatial integration of SEI shells on Li deposits is important to improving the reversibility of deposition and dissolution cycling.

17.
J Chem Phys ; 157(7): 074101, 2022 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-35987599

RESUMO

When a physical system is driven away from equilibrium, the statistical distribution of its dynamical trajectories informs many of its physical properties. Characterizing the nature of the distribution of dynamical observables, such as a current or entropy production rate, has become a central problem in nonequilibrium statistical mechanics. Asymptotically, for a broad class of observables, the distribution of a given observable satisfies a large deviation principle when the dynamics is Markovian, meaning that fluctuations can be characterized in the long-time limit by computing a scaled cumulant generating function. Calculating this function is not tractable analytically (nor often numerically) for complex, interacting systems, so the development of robust numerical techniques to carry out this computation is needed to probe the properties of nonequilibrium materials. Here, we describe an algorithm that recasts this task as an optimal control problem that can be solved variationally. We solve for optimal control forces using neural network ansatz that are tailored to the physical systems to which the forces are applied. We demonstrate that this approach leads to transferable and accurate solutions in two systems featuring large numbers of interacting particles.


Assuntos
Redes Neurais de Computação , Física , Algoritmos , Entropia , Fatores de Tempo
18.
Phys Rev Lett ; 126(8): 084801, 2021 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-33709748

RESUMO

The spectroscopic techniques for time-resolved fine analysis of matter require coherent x-ray radiation with femtosecond duration and high average brightness. Seeded free-electron lasers (FELs), which use the frequency up-conversion of an external seed laser to improve temporal coherence, are ideal for providing fully coherent soft x-ray pulses. However, it is difficult to operate seeded FELs at a high repetition rate due to the limitations of present state-of-the-art laser systems. Here, we report a novel self-modulation method for enhancing laser-induced energy modulation, thereby significantly reducing the requirement of an external laser system. Driven by this scheme, we experimentally realize high harmonic generation in a seeded FEL using an unprecedentedly small external laser-induced energy modulation. An electron beam with a laser-induced energy modulation as small as 1.8 times the slice energy spread is used for lasing at the seventh harmonic of a 266-nm seed laser in a single-stage high-gain harmonic generation (HGHG) setup and the 30th harmonic of the seed laser in a two-stage HGHG setup. The results mark a major step toward a high-repetition-rate, fully coherent x-ray FEL.

19.
Inorg Chem ; 60(23): 17635-17640, 2021 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-34747595

RESUMO

Catalytic chemical degradations and many other methodologies have been explored for the removal and/or degradation of organophosphorus agents (OPs) that are often used as pesticides, nerve agents, and plasticizers. To explore more efficient and recyclable catalysts for the removal and/or degradation of OPs, we fabricate the composites of cobalt nanoparticles and three-dimensional nitrogen-doped graphene (Co/3DNG). We demonstrate that OPs can be hydrolyzed efficiently at ambient temperature by the Co/3DNG. Because of the unique structural and chemical properties of the supporting matrix 3DNG and active species Co-N, the catalytic activities of Co/3DNG composites are much higher than those of bare 3DNG, Co nanoparticles, or the Co nanoparticles physically mixed with 3DNG. We conclude that in the Co/3DNG composites, the interaction between 3DNG and Co stabilizes and distributes well the Co nanoparticles and affords the active catalytic species Co-N.

20.
J Chem Phys ; 155(24): 244702, 2021 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-34972352

RESUMO

Choline chloride (ChCl)-based-deep eutectic solvents (DESs) are widely used in electrochemical fields. In this work, the effect of two types of hydrogen bond donor (HBD) molecules, ethylene glycerol and lactic acid (LA), on electrochemical interfaces between the Au electrode and DESs has been investigated by employing voltammetry and electrochemical impedance spectroscopy. The anodic dissolution and passivation behaviors of the Au electrode are revealed in both ethaline and ChCl:LA. In ChCl:LA, the anodic dissolution of Au is slowed down, and the passivation film is relatively dense and stable due to the existence of the carboxyl group in HBD molecule LA. In the double layer region, the lifting and formation of Au(111) surface reconstruction and a disorder-order phase transition of the chloride ion adlayer were observed in the two DESs. Moreover, compared with ethaline, an extra pair of current peaks appears in ChCl-LA possibly due to the adsorption and desorption of LA on the Au(111) surface, which might imply the stronger interaction of LA with the Au electrode in ChCl:LA. HBD LA could even have marked an impact on the disorder-order phase transition of the chloride ion adlayer. The above results provide new insight into the significant effect of HBD molecules on the anodic dissolution and the passivation of the Au electrode and the electrochemical behaviors in the double layer region.

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