Understanding the growth mechanisms of metal-based core–shell nanostructures revealed by in situ liquid cell transmission electron microscopy

Metal-based core-shell nanostructures have garnered enduring interest due to their unique properties and functionalities.However,their growth and transformation mechanisms in liquid media remain largely unknown because they lack direct observation of the dynamic growth process with high spatial and temporal resolution.Developing the in situ liquid cell transmission electron microscopy(TEM)technique offers unprecedented real-time imaging and spectroscopy capabilities to directly track the evolution of structural and chemical transformation of metal-based core–shell nanostructures in liquid media under their working condition.Here,this review highlights recent progress in utilizing in situ liquid cell TEM characterization technique in investigating the dynamic evolution of material structure and morphology of metal-based core–shell nanostructures at the nano/atomic scale in real-time.A brief introduction of the development of liquid cells for in situ TEM is first given.Subsequently,recent advances in in situ liquid cell TEM for the fundamental study of growth mechanisms of metal based core–shell nanostructures are discussed.Finally,the challenge and future developments of metalbased core–shell nanostructures for in situ liquid cell TEM are proposed.Our review is anticipated to inspire ongoing interest in revealing unseen growth dynamics of core–shell nanostructures by in situ liquid cell TEM technique.

In Situ Liquid Cell Transmission Electron Microscopy Observations of Growth and Anticorrosion Behaviors of AuCl3 Shell on Au Nanobipyramids

Comprehensive Summary Designing new materials and architectures to maintain activity and stability requires a better understanding on the anticorrosion dynamics of nanoparticles.Under-coordinated atoms on the surface of nanoparticles can be protected by deposited shells.Real-time observation on how protective shells grow and play a role is challenging but worthwhile.Here,protective effects of AuCl_(3) shells on Au nanobipyramids(NBPs)are studied in HAuCl_(4) aqueous solutions by in-situ liquid cell transmission electron microscopy(LCTEM).This study is the first to observe the formation of Au-AuCl_(3) core-shell nanostructure and the corresponding anticorrosion behaviors of AuCl_(3) deposited shell.The presence of CTAB can substantially influence the growth mode and structure of AuCl_(3) shell,by a direct or indirect way,intervene the dissolution of Au NBP.These growth or dissolution kinetics here revealed at the nanoscale provide insights towards engineering of the surface anticorrosion to pursue Au nanoparticles with improved stability in acidic environment.

Transforming liquid flow fuel cells to controllable reactors for highlyefficient oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid at low temperature

Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.

Direct Observation of Growth and Self-assembly of Pt Nanoclusters in Water with the Aid of a Triblock Polymer Using in situ Liquid Cell Transmission Electron Microscopy （TEM）

Triblock copolymers are playing important roles in nanomaterial synthesis, and the nanomaterial forming mechanisms need to be studied in detail. In situ liquid cell transmission electron microscopy （TEM） is a powerful tool for real time observation of the dynamic growth behavior of nanomaterials in liquid with high resolution, and could be used for the above task. Here we report the observation of the growth and self-assembly of Pt nanoclusters with the aid of an ethylene oxide-propylene oxide-ethylene oxide triblock copolymer （PEO-PPO-PEO） F 127 using in situ liquid cell TEM, with the nanocluster growth and formation procedures being tracked. Nano objects were seen to appear, drift and rotate with time, and then form into certain shaped nanoclusters under the electron beam irradiation. Further interestingly, in the thicker liquid layer region, the nanoclusters appeared to be fluffy, with average size keeping increase with time, while in the thinner region, the clusters were thinner, and got densified with time. The difference in precursor availability due to liquid layer thickness and charging effects is attributed to such a phenomenon.

In-situ liquid cell TEM investigation on assembly and symmetry transformation of Pt superlattice

Two dimensional(2D)nanocrystal functional superlattices with a well controlled structure are of significant importance in photonic,plasmonic and optoelectronic applications and have been well studied,but it remains challenging to understand the formation mechanism and development pathway of the superlattice.In this study,we employed in-situ liquid cell transmission electron microscopy to study the formation of 2D superlattice and its local phase transition from hexagonal-to-square nanocrystal ordering.When colloidal nanocrystals flowed in the solution,long-range ordered hexagonal superlattice could be formed either through shrinking and rearrangement of nanocrystal aggregates or via nanocrystal attachment.As the nanocrystals’shape transformed from truncated octahedral to cube,the local superlattice rearranged to square geometry.Moreover,our observations and quantitative analyses reveal that the phase transition from hexagonal to square mainly originates from the strong van der Waals interactions between the vertical(100)facets.The tracking of 2D cube superlattice formation in real-time could provide unique insights on the governing force of superlattice assembling and stabilization.

Atomic mechanisms of hexagonal close-packed Ni nanocrystallization revealed by in situ liquid cell transmission electron microscopy

The fundamental understanding of the mechanism underlying the early stages of crystallization of hexagonal-close-packed(hcp)nanocrystals is crucial for their synthesis with desired properties,but it remains a significant challenge.Here,we report using in situ liquid cell transmission electron microscopy(TEM)to directly capture the dynamic nucleation process and track the real-time growth pathway of hcp Ni nanocrystals at the atomic scale.It is demonstrated that the growth of amorphous-phase-mediated hcp Ni nanocrystals is from the metal-rich liquid phases.In addition,the reshaped preatomic facet development of a single nanocrystal is also imaged.Theoretical calculations further identify the non-classical features of hcp Ni crystallization.These discoveries could enrich the nucleation and growth model theory and provide useful information for the rational design of synthesis pathways of hcp nanocrystals.

Atomically dispersed catalysts for small molecule electrooxidation in direct liquid fuel cells

Direct liquid fuel cells(DLFCs) have received increasing attention because of their high energy densities,instant recharging abilities, simple cell structure, and facile storage and transport. The main challenge for the commercialization of DLFCs is the high loading requirement of platinum group metals(PGMs) as catalysts. Atomically dispersed catalysts(ADCs) have been brought into recent focus for DLFCs due to their well-defined active sites, high selectivity, maximal atom-utilization, and anti-poisoning property. In this review, we summarized the structure–property relationship for unveiling the underlying mechanisms of ADCs for DLFCs. More specifically, different types of fuels used in DLFCs such as methanol, formic acid,and ethanol were discussed. At last, we highlighted current challenges, research directions, and future outlooks towards the practical application of DLFCs.

Tracking the atomic pathways of Pt3Ni-Ni(OH)2 core-shell structures at the gas-liquid interface by in-situ liquid cell TEM

Using the in-situ liquid cell transmission electron microscopy, the three-stage growth of Pt3Ni-Ni(OH)2 core-shell structures at the gas-liquid interfaces was clearly observed, which consists of(1) a thermodynamically driven Pt3Ni alloy core by the monomer attachment,(2) a nickel(Ni) shell formation due to the depletion of the Pt salt precursor, and(3) the oxidation and of the Ni shell into Ni(OH)2 flakes. We also further observed the nucleation and growth of the Ni(OH)2 flakes on an existing layer either at the middle part or at the step edge. More interestingly, the dynamic transformation among a Pt3Ni alloy, Ni clusters and Ni(OH)2 flakes was also imaged even at a high electron dose rate.

Extraction Kinetics of Lanthanum in Chloride Medium by Bifunctional Ionic Liquid [A336][CA-12] Using a Constant Interfacial Cell with Laminar Flow

The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12](tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated using a constant interfacial cell with laminar flow. The effects of stirring speed, temperature and specific interfacial area on the extraction rate were examined. The results indicate that mass transfer kinetics of La(III) is a mixed-controlled process influenced by interfacial reaction. On the basis of mass transfer kinetic results in the extraction of La(III) by [A336][CA-12], the extraction rate equation of La(III) is proposed in terms of pseudo-firstorder constants, which is supported by the measured thermodynamic equations. The mass-transfer kinetic model deduced from the rate controlling step is adequate to interpret the experimental data qualitatively.

Brand-new Function of Well-designed Ionic Liquid: Inhibitor of Tumor Cell Growth

An investigation into the effect of several novel well-designed guanidinium salt ionic liquids（GILs） on inhibitting tumor growth is described. The GILs which have longer alkyl chain（6-18 carbon atoms） exhibit the high cytotoxicity to Hela299, B16 and SMMC-7721 cells so as to inhibit their proliferation. The inhibitory effect of the most effective GILl2 is about 10-fold higher than that of MMC（a common chemotherapy drug in clinic）.

Liquid biopsy in patients with pancreatic cancer: Circulating tumor cells and cell-free nucleic acids

Despite recent advances in surgical techniques and perioperative management, the prognosis of pancreatic cancer(PCa) remains extremely poor. To provide optimal treatment for each patient with Pca, superior biomarkers are urgently needed in all phases of management from early detection to staging, treatment monitoring, and prognosis. In the blood of patients with cancer, circulating tumor cells(CTCs) and cell-free nucleic acids(cf NAs), such as DNA, m RNA, and noncoding RNA have been recognized. In the recent years, their presence in the blood has encouraged researchers to investigate their potential use as novel blood biomarkers, and numerous studies have demonstrated their potential clinical utility as a biomarker for certain types of cancer. This concept, called "liquid biopsy" has been focused on as a less invasive, alternative approach to cancer tissue biopsy for obtaining genetic and epigenetic aberrations that contribute to oncogenesis and cancer progression. In this article, we review the available literature on CTCs and cfN As in patients with cancer, particularly focusing on PCa, and discuss future perspectives in this field.

A Direct Liquid Fuel Cell with High Power Density Using Reduced Phosphotungstic Acid as Redox Fuel

Direct liquid fuel cells(DLFCs)are proposed to address the problems of high cost and complex storage and transportation of hydrogen in traditional hydrogen-oxygen proton exchange membrane fuel cells.However,present fuels of organic small molecules used in DLFCs are restricted to problems of sluggish electrochemical kinetics and easily poisoning of precious metal catalysts.Herein,we demonstrate reduced phosphotungstic acid as a liquid fuel for DLFCs based on its advantages of high chemical and electrochemical stability,high electrochemical activity on common carbon material electrodes,and low permeability through proton exchange membranes.The application of phosphotungstic acid fuel effectively solves the problems of high cost of anode catalysts and serious fuel permeation loss in traditional DLFCs.A phosphotungstic acid fuel cell achieves a peak power density of466 mW cm^(-2)at a cell voltage of 0.42 V and good stability at current densities in the range from 20 to 200 mA cm^(-2).

CFD simulation of effect of anode configuration on gas–liquid flow and alumina transport process in an aluminum reduction cell

Numerical simulations of gas–liquid two-phase flow and alumina transport process in an aluminum reduction cell were conducted to investigate the effects of anode configurations on the bath flow, gas volume fraction and alumina content distributions. An Euler–Euler two-fluid model was employed coupled with a species transport equation for alumina content. Three different anode configurations such as anode without a slot, anode with a longitudinal slot and anode with a transversal slot were studied in the simulation. The simulation results clearly show that the slots can reduce the bath velocity and promote the releasing of the anode gas, but can not contribute to the uniformity of the alumina content. Comparisons of the effects between the longitudinal and transversal slots indicate that the longitudinal slot is better in terms of gas–liquid flow but is disadvantageous for alumina mixing and transport process due to a decrease of anode gas under the anode bottom surface. It is demonstrated from the simulations that the mixing and transfer characteristics of alumina are controlled to great extent by the anode gas forces while the electromagnetic forces(EMFs) play the second role.

Liquid waveguide capillary cell for the spectrophotometric determination of nanomolar iodate concentrations in marine waters

A new spectrophotometric method based on a liquid waveguide capillary cell for an enhanced detection was developed to measure nanomolar iodate concentrations.This method has a detection limit and precision of 1-2 nmol/L,which is equivalent to 10%that of conventional methods,a recovery of 97.7%-104.0%,and a working range of 10-120 nmol/L.Water samples were collected from three estuaries and one coastal ocean for testing,and the proposed technique detected as low as 11 nmol/L and 18 nmol/L iodate in these samples.This newly developed method is helpful in understanding the biogeochemical cycle of iodine in nature.

Interfacial charge-transfer engineering by ionic liquid for high performance planar CH3NH3PbBr3 solar cells

The energy barrier at the CH3NH3Pb Br3/TiO2interface hinders the electron transfer from CH3NH3Pb Br3to compact TiO2（cp-TiO2）.Ionic liquid（IL）,that forms dipoles pointing away from TiO2,can adjust the work function of TiO2resulting in suitable energy level for charge transfer from CH3NH3Pb Br3to TiO2.The time-resolved photoluminescence spectroscopy（TRPL）measurements confirm faster electron transfer from the CH3NH3Pb Br3film to TiO2after modification by IL.Solar cells based on IL modified cp-TiO2demonstrate efficiency of～6%,much higher than the devices（0.2%）fabricated using untreated cp-TiO2as the electron transport layer.

Fullerene solar cells with cholesteric liquid crystal doping

This paper reports the doping effect of cholesteric liquid crystal 3β-Hydroxy-5-cholestene 3-oleate on polymer solar cells composed of the poly 3-hexyl thiophene and the fullerene derivative.With a doping ratio of 0.3 wt%,the device achieves an ideal improvement on the shunt resistor and the fill factor.Compared with the reference cell,the power conversion efficiency of the doped cell is improved 24%.The photoelectric measurement and the active layer characterization indicate that the self-assembly liquid crystal can improve the film crystallization and reduce the membrane defect.

Modified electronic structure and enhanced hydroxyl adsorption make quaternary Pt-based nanosheets efficient anode electrocatalysts for formic acid-/alcohol-air fuel cells

Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.

Guanidinium Iodides-based Ionic Liquids: Synthesis and Application for Dye-sensitized Solar Cells(DSSCs)

A series of guanidinium ionic liquids（GILs） was designed, synthesized, and used as electrolytes for dye-sensitized solar cells（DSSCs）. The effect of electrolytes containing GILs on the photovoltaic performance of DSSCs was investigated. It is demonstrated that these GILs are promising for being used as electrolytes for DSSCs and a conversion efficiency of 4.1% can be obtained under AM 1.5 sun light irradiation.

Research of Anti-Cancer Components in Traditional Chinese Medicine on Hollow Fibre Cell Fishing and Hollow Fibre Liquid Phase Microextraction

Hollow fibre cell fishing with HPLC (HFCF-HPLC) based on the human ovarian cancer cell line SKOV-3, human renal tubular cell line ACHN or hepatoma cell line HepG-2 was employed to screen active groups of coumarin and volatile oil in Radix angelicae sinensis, Radix angelicae dahuricae and Fructus citri sarcodactylis. Simultaneously, hollow fibre liquid phase microextraction with HPLC (HFLPME-HPLC) was conducted to enrich and determine the contents of active components in the same sample solution. Before application, for HFCF-HPLC, cells growth states and survival rates on the fibre, effect of ethanol concentration in the extract of samples on cell survival rates, non-specific binding between fibre active centres and the target components, positive and negative controls and repeatabilities were validated;for HFLPME, extraction solvent, sample phase pH, agitation speed, extraction time and sample phase volume were investigated. Many active components were screened from three medicines. Some of them, such as scoparone, psoralen, bergapten, oxypeucedanin, imperatorin, ligustilide, were identified by MS. The target fishing factors of active components and the cell apoptosis rates of three cells under the medicines effect were researched. The binding sites of active groups on HepG-2 cells were preliminarily determined. The results demonstrated that HFCF-HPLC, coupled with HFLPME-HPLC, is a simple and universal approach to find bioactive components at the cellular level, determine their content and research traditional Chinese medicines (TCMs) entirety effect of multi-component and multi-target. The approach may provide us a new and good solution to clarify the material basis of anti-cancer effect and conduct personalized quality control for the components associated with efficacy in TCMs.

Guided Wave Studies of Reflective MTN Liquid Crystal Cell

The fully-leaky guided wave technique has been used to study the reflective 90? MTN liquid crystal cell used for LCOS. The cell is comprised of upper substrate with indium-tin-oxide coating and lower substrate with aluminum coating. Reflective angle-dependent signals (Rss, Rpp, Rsp and Rps) were recorded over a range of angles of incidence with the cell under application of 0 - 7 Vrms ac electric fields. From the recorded experimental data, we found the reflective signals are quite strong, especially the polarization conversion signals. Fitting the data in reflection with the results of the modeling-program gives the information about the pre-tilt and twist of the director as well as the parameters of different optical layers. We found that the pre-tilt angle on the upper substrate is different from that on the bottom in the best fits, which suggests that the indium-tin-oxide and the aluminum coatings have different effects on the alignment layers.