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1.
Chem Soc Rev ; 53(6): 2972-3001, 2024 Mar 18.
Article in English | MEDLINE | ID: mdl-38345093

ABSTRACT

Nanofluidic channels with tailored ion transport dynamics are usually used as channels for ion transport, to enable high-performance ion regulation behaviors. The rational construction of nanofluidics and the introduction of external fields are of vital significance to the advancement and development of these ion transport properties. Focusing on the recent advances of nanofluidics, in this review, various dimensional nanomaterials and their derived homogeneous/heterogeneous nanofluidics are first briefly introduced. Then we discuss the basic principles and properties of ion transport in nanofluidics. As the major part of this review, we focus on recent progress in ion transport in nanofluidics regulated by external physical fields (electric field, light, heat, pressure, etc.) and chemical fields (pH, concentration gradient, chemical reaction, etc.), and reveal the advantages and ion regulation mechanisms of each type. Moreover, the representative applications of these nanofluidic channels in sensing, ionic devices, energy conversion, and other areas are summarized. Finally, the major challenges that need to be addressed in this research field and the future perspective of nanofluidics development and practical applications are briefly illustrated.

2.
Nano Lett ; 24(7): 2352-2359, 2024 Feb 21.
Article in English | MEDLINE | ID: mdl-38345565

ABSTRACT

Ion-selective membrane has broad application in various fields, while the present solution-processed techniques can only prepare uniform membrane with microscale thickness. Herein, a high-quality polymer membrane with nanoscale thickness and uniformity is precisely prepared by controlling solution spreading and solvent evaporation stability/rate. With the arrayed capillaries, the stable spreading of polymer solution with volume of microliter induces the formation of solution film with micrometers thickness. Moreover, the fast increase of solution dynamic viscosity during solvent evaporation inhibits nonuniform Marangoni flow and capillary flow in solution film. Consequently, the uniform Nafion-Li membranes with ∼200 nm thickness are prepared, while their Li+ conductivity is 2 orders of magnitude higher than that of commercially Nafion-117 membrane. Taking lithium-sulfur battery as a model device, the cells (capacities of 8-10 mAh cm-2) can stably operate for 150 cycles at a S loading of 12 mg cm-2 and an electrolyte/sulfur ratio of ∼7.

3.
J Am Chem Soc ; 146(19): 13191-13200, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38603609

ABSTRACT

Conventional solid ion channel systems relying on single one- or two-dimensional confined nanochannels enabled selective and ultrafast convective ion transport. However, due to intrinsic solid channel stacking, these systems often face pore-pore polarization and ion concentration blockage, thereby restricting their efficiency in macroscale ion transport. Here, we constructed a soft heterolayer-gel system that integrated an ion-selective hydrogel layer with a water-barrier organogel layer, achieving ultrahigh cation selectivity and flux and effectively providing high-efficiency gradient energy conversion on a macroscale order of magnitude. Specifically, the hydrogel layer featured an unconfined 3D network, where the fluctuations of highly hydrated polyelectrolyte chains driven by thermal dynamics enhanced cation selectivity and mitigated transfer energy barriers. Such chain fluctuation mechanisms facilitated ion-cluster internal transmission, thereby enhancing ion concentration hopping for more efficient ion-selective transport. Compared to the existing rigid nanochannel-based gradient energy conversion systems, such a heterogel-based power generator exhibited a record power density of 192.90 and 1.07 W/m2 at the square micrometer scale and square centimeter scale, respectively (under a 500-fold artificial solution). We anticipate that such heterolayer gels would be a promising candidate for energy separation and storage applications.

4.
J Am Chem Soc ; 2024 Jun 06.
Article in English | MEDLINE | ID: mdl-38842082

ABSTRACT

Biological ion channels exhibit switchable cation transport with ultrahigh selectivity for efficient energy conversion, such as Ca2+-activated TRPM4 channels tuned by cation-π interactions, but achieving an analogous highly selective function is challenging in artificial nanochannels. Here, we design a TRPM4-inspired cation-selective nanochannel (CN) assembled by two poly(ether sulfone)s, respectively, with sulfonate acid and indole moieties, which act as cation-selective activators to manage Na+/Cl- selectivity via ionic and cation-π interactions. The cation selectivity of CNs can be activated by Na+, and thereby the Na+ transference number significantly improves from 0.720 to 0.982 (Na+/Cl- selectivity ratio from 2.6 to 54.6) under a 50-fold salinity gradient, surpassing the K+ transference number (0.886) and Li+ transference number (0.900). The TRPM4-inspired nanochannel membrane enabled a maximum output power density of 5.7 W m-2 for salinity-gradient power harvesting. Moreover, a record energy conversion efficiency of up to 46.5% is provided, superior to most nanochannel membranes (below 30%). This work proposes a novel strategy to biomimetic nanochannels for highly selective cation transport and high-efficiency salinity-gradient energy conversion.

5.
Small ; : e2401264, 2024 Apr 18.
Article in English | MEDLINE | ID: mdl-38634249

ABSTRACT

Biological photo-responsive ion channels play important roles in the important metabolic processes of living beings. To mimic the unique functions of biological prototypes, the transition metal dichalcogenides, owing to their excellent mechanical, electrical, and optical properties, are already used for artificial intelligent channel constructions. However, there remain challenges to building artificial bio-semiconductor nanochannels with finely tuned band gaps for accurately simulating or regulating ion transport. Here, two well-designed peptides are employed for the WS2 nanosheets functionalization with the sequences of PFPFPFPFC and DFDFDFDFC (PFC and DFC; P: proline, D: aspartate, and F: phenylalanine) through cysteine (Cys, C) linker, and an asymmetric peptide-WS2 membrane (AP-WS2M) could be obtained via self-assembly of peptide-WS2 nanosheets. The AP-WS2M could realize the photo-driven anti-gradient ion transport and vis-light enhanced osmotic energy conversion by well-designed working patterns. The photo-driven ion transport mechanism stems from a built-in photovoltaic motive force with the help of formed type II band alignment between the PFC-WS2 and DFC-WS2. As a result, the ions would be driven across the channels of the membrane for different applications. The proposed system provides an effective solution for building photo-driven biomimetic 2D bio-semiconductor ion channels, which could be extensively applied in the fields of drug delivery, desalination, and energy conversion.

6.
Langmuir ; 40(23): 11974-11987, 2024 Jun 11.
Article in English | MEDLINE | ID: mdl-38801162

ABSTRACT

Photocatalysis is a physiochemical effect arising from the relaxation of photoinduced electrons from the conduction band to the valence band. Controlling the electron relaxation to occur through photocatalytic pathways and prohibiting other relaxations is the main scientific thought for photocatalytic studies. It is needed to know the parallel relaxation pathways that can compete with photocatalytic reactions. By means of in situ photoconductances (PCs) and photoinduced absorptions (PAs), the current research studied the photoinduced electron relaxations of the Au/TiO2 in different atmospheres and at different temperatures. The PC and PA relaxations became different and fast when methanol, ethanol, isopropanol, and acetone were introduced; they also tend to decrease as temperature increases, while that of the undecorated TiO2 in all atmospheres and the Au/TiO2 in pure N2 increased. The results indicated that the organic adsorptions over the Au/TO2 perimeters change the relaxation pathway, and a hole-capturing organics adsorption-induced recombination over the Au/TiO2 perimeter was proposed to explain the relaxations. We found that this relaxation also exists for Ag/TiO2, Pt/TiO2, and Au/ZnO, so it is a commonly existing physical course for the metal/semiconductor (M/S) materials. The effect of the organics and M/S structures on the relaxation was discussed, and the relationship with photocatalytic reactions was also analyzed. Our finding means that blocking this relaxation pathway is an effective way to increase photocatalytic activities, which might open a door for highly active photocatalyst developments.

7.
Phys Chem Chem Phys ; 26(14): 11113-11125, 2024 Apr 03.
Article in English | MEDLINE | ID: mdl-38530657

ABSTRACT

Electron transfer and its kinetics play a major role in the photocatalysis of metal/semiconductor systems. Using in situ photoconductances, in situ photoabsorption, and photoinduced spectroscopic techniques, the present research aimed to gain a deep insight into electron transfer pathways and their kinetics for Ag/TiO2 systems under sub-bandgap light illumination and gaseous conditions. The results revealed that electrons generated in TiO2 can transfer to Ag nanoparticles at fast rates, and plasmon-generated electrons in Ag nanoparticles can also transfer to TiO2. However, it was found that plasmon-assisted hot electron transfer efficiency is much lower than the electron transition from the valence band to the conduction band of TiO2. Rather than plasmonic active spots, the results showed that Ag nanoparticles acted as co-catalyst sites bridging electron transfer to recombination in a methanol-containing N2 atmosphere. As a result, photocatalytic isopropanol dehydrogenation was decreased. Independent of Ag decorations, it was also indicated that isopropanol dehydrogenation mainly occurred over TiO2 surfaces; therefore, Ag nanoparticles did not increase photocatalytic activities. Our results may provide a different viewpoint on sub-bandgap light-induced Ag/TiO2 photocatalysis under gaseous conditions; this may also facilitate the understanding of the photocatalytic mechanism of metal/semiconductor systems.

8.
Angew Chem Int Ed Engl ; 63(5): e202315087, 2024 Jan 25.
Article in English | MEDLINE | ID: mdl-38087471

ABSTRACT

The reaction rate bottleneck during interconversion between insulating S8 (S) and Li2 S fundamentally leads to incomplete conversion and restricted lifespan of Li-S battery, especially under high S loading and lean electrolyte conditions. Herein, we demonstrate a new catalytic chemistry: soluble semiquinone, 2-tertbutyl-semianthraquinone lithium (Li+ TBAQ⋅- ), as both e- /Li+ donor and acceptor for simultaneous S reduction and Li2 S oxidation. The efficient activation of S and Li2 S by Li+ TBAQ⋅- in the initial discharging/charging state maximizes the amount of soluble lithium polysulfide, thereby substantially improve the rate of solid-liquid-solid reaction by promoting long-range electron transfer. With in situ Raman spectra and theoretical calculations, we reveal that the activation of S/Li2 S is the rate-limiting step for effective S utilization under high S loading and low E/S ratio. Beyond that, the S activation ratio is firstly proposed as an accurate indicator to quantitatively evaluate the reaction rate. As a result, the Li-S batteries with Li+ TBAQ⋅- deliver superior cycling performance and over 5 times higher S utilization ratio at high S loading of 7.0 mg cm-2 and a current rate of 1 C compared to those without Li+ TBAQ⋅- . We hope this study contributes to the fundamental understanding of S redox chemical and inspires the design of efficient catalysis for advanced Li-S batteries.

9.
Electrophoresis ; 44(23): 1847-1858, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37401641

ABSTRACT

In recent years, researchers have made significant strides in understanding the ion transport characteristics of nanochannels, resulting in the development of various materials, modifications, and shapes of nano ion channel membranes. The aim is to create a nanochannel membrane with optimal ion transport properties and high stability by adjusting factors, such as channel size, surface charge, and wettability. However, during the nanochannel film fabrication process, controlling the geometric structures of nanochannels can be challenging. Therefore, exploring the stability of nanochannel performance under different geometric structures has become an essential aspect of nanochannel design. This article focuses on the study of cylindrical nanochannel structures, which are categorized based on the different methods for generating bipolar surface charges on the channel's inner surface, either through pH gradient effects or different material types. Through these two approaches, the study designed and analyzed the stability of ion transport characteristics in two nanochannel models under varying geometric structures. Our findings indicate that nanochannels with bipolar properties generated through pH gradients demonstrate more stable ion selection, whereas nanochannels with bipolar properties generated through different materials show stronger stability in ion rectification. This conclusion provides a theoretical foundation for future nanochannel designs.


Subject(s)
Ion Channels , Ion Transport , Hydrogen-Ion Concentration
10.
Phys Chem Chem Phys ; 25(29): 20134-20144, 2023 Jul 26.
Article in English | MEDLINE | ID: mdl-37463042

ABSTRACT

Noble metal nanoparticles are widely used as co-catalysts for storing and separating electrons in semiconductor photocatalysis. Thus, evaluating this ability is important and meaningful to understand the photocatalytic mechanism. Employing Ag nanoparticles, the present study combined in situ photoconductance and theoretical analysis to evaluate the Fermi-level (EF) shift in a UV-illuminated Ag/TiO2 system under gaseous conditions. Based on this, the role of the Ag nanoparticles in storing and separating electrons was discussed. It was found that the EF of Ag/TiO2 is located deeper in the gap and a variation in temperature has less effect on the EF of Ag/TiO2 compared to the undecorated TiO2. The analysis showed that ∼46 electrons can be stored in 10 nm Ag nanoparticles under our experimental conditions, which does not change with temperature. The electron traps in TiO2 can affect the electron distribution in the TiO2 and Ag nanoparticles. It was observed that the localized surface plasmon resonance (LSPR) of the Ag nanoparticles exhibited a blue-shift under UV light illumination, which is generally ascribed to the electron storage in the Ag nanoparticles. However, we showed that the blue-shift is not related to the electron storage in the Ag nanoparticles, and thus it cannot be used as an indicator for evaluating their electron-storage ability. The in situ XPS analysis also does not support that the LSPR blue shift is associated with the reduction in the Ag2O layer and TiO2.

11.
BMC Public Health ; 23(1): 1475, 2023 08 02.
Article in English | MEDLINE | ID: mdl-37532982

ABSTRACT

BACKGROUND: One in seven UK children have obesity when starting school, with higher prevalence associated with deprivation. Most pre-school children do not meet UK recommendations for physical activity and nutrition. Formal childcare settings provide opportunities to deliver interventions to improve nutritional quality and physical activity to the majority of 3-4-year-olds. The nutrition and physical activity self-assessment for childcare (NAP SACC) intervention has demonstrated effectiveness in the USA with high acceptability in the UK. The study aims to evaluate the effectiveness and cost-effectiveness of the NAP SACC UK intervention to increase physical activity, reduce sedentary time and improve nutritional intake. METHODS: Multi-centre cluster RCT with process and economic evaluation. Participants are children aged 2 years or over, attending UK early years settings (nurseries) for ≥ 12 h/week or ≥ 15 h/week during term time and their parents, and staff at participating nurseries. The 12-month intervention involves nursery managers working with a Partner (public health practitioner) to self-assess policies and practices relating to physical activity and nutrition; nursery staff attending one physical activity and one nutrition training workshop and setting goals to be achieved within 6 months. The Partner provides support and reviews progress. Nursery staff receive a further workshop and new goals are set, with Partner support for a further 6 months. The comparator is usual practice. Up to 56 nurseries will be stratified by area and randomly allocated to intervention or comparator arm with minimisation of differences in level of deprivation. PRIMARY OUTCOMES: accelerometer-assessed mean total activity time on nursery days and average total energy (kcal) intake per eating occasion of lunch and morning/afternoon snacks consumed within nurseries. SECONDARY OUTCOMES: accelerometer-assessed mean daily minutes of moderate-to-vigorous physical activity and sedentary time per nursery day, total physical activity on nursery days compared to non-nursery days, average serving size of lunch and morning/afternoon snacks in nursery per day, average percentage of core and non-core food in lunch and morning/afternoon snacks, zBMI, proportion of children who are overweight/obese and child quality-of-life. A process evaluation will examine fidelity, acceptability, sustainability and context. An economic evaluation will compare costs and consequences from the perspective of the local government, nursery and parents. TRIAL REGISTRATION: ISRCTN33134697, 31/10/2019.


Subject(s)
Child Care , Nurseries, Infant , Humans , Child, Preschool , Child , Infant , Self-Assessment , Cost-Benefit Analysis , Health Promotion/methods , Exercise , Obesity , United Kingdom , Randomized Controlled Trials as Topic , Multicenter Studies as Topic
12.
Proc Natl Acad Sci U S A ; 117(29): 16743-16748, 2020 07 21.
Article in English | MEDLINE | ID: mdl-32611809

ABSTRACT

Mammalian nervous systems, as natural ionic circuitries, stand out in environmental perception and sophisticated information transmission, relying on protein ionic channels and additional necessary structures. Prosperously emerged ionic regulated biomimetic nanochannels exhibit great potentialities in various application scenarios, especially signal transduction. Most reported direct current systems possess deficiencies in informational density and variability, which are superiorities of alternating current (AC) systems and necessities in bioinspired nervous signal transmission. Here, inspired by myelinated saltatory conduction, alternating electrostatic potential controlled nanofluidics are constructed with a noncontact application pattern and MXene nanosheets. Under time-variant external stimuli, ions confined in the interlaminar space obtain the capability of carriers for the AC ionic circuit. The transmitted information is accessible from typical sine to a frequency-modulated binary signal. This work demonstrates the potentiality of the bioinspired nervous signal transmission between electronics and ionic nanofluidics, which might push one step forward to the avenue of AC ionics.


Subject(s)
Action Potentials , Biomimetic Materials/chemistry , Electric Conductivity , Microfluidics/methods , Models, Neurological , Nanostructures/chemistry , Dimethylpolysiloxanes/chemistry , Electrical Equipment and Supplies , Ion Transport , Microfluidics/instrumentation
13.
Chem Biodivers ; 20(12): e202301806, 2023 Dec.
Article in English | MEDLINE | ID: mdl-38009836

ABSTRACT

Picroside III (Pic), an iridoid glycoside derived from Picrorhiza scrophulariiflora, exhibits therapeutic potential in mending damage to the intestinal mucosa. This study aimed to explore Pic's regulatory impact on intestinal inflammation and the gut microbiota in mice with dextran sulfate sodium (DSS)-induced colitis. The findings revealed that pretreatment with Pic mitigated the DSS-induced escalation of the disease activity index (DAI), alleviated intestinal damage, and attenuated intestinal inflammation in mice. RNA-seq analysis, complemented by experimental validation, elucidated that Pic significantly hindered Akt phosphorylation in the colon tissues of colitis-afflicted mice. Furthermore, 16S rRNA sequencing demonstrated that Pic pretreatment effectively rectified microbial dysbiosis in colitis mice by elevating the abundance of Lactobacillus murinus and Lactobacillus gasseri. These observations suggest that Pic's efficacy in colitis treatment stems from its inhibition of intestinal inflammation via the suppression of the PI3K-Akt pathway and modulation of gut microbiota. This study contributes novel scientific insights into the potential application of Pic in the management of inflammatory bowel disease (IBD).


Subject(s)
Colitis , Phosphatidylinositol 3-Kinases , Mice , Animals , RNA, Ribosomal, 16S/genetics , Phosphatidylinositol 3-Kinases/metabolism , Proto-Oncogene Proteins c-akt/metabolism , Transcriptome , Colitis/chemically induced , Colitis/drug therapy , Inflammation , Disease Models, Animal
14.
Nano Lett ; 22(3): 1129-1137, 2022 02 09.
Article in English | MEDLINE | ID: mdl-35040647

ABSTRACT

Mechano-bactericidal surfaces deliver lethal effects to contacting bacteria. Until now, cell death has been attributed to the mechanical stress imparted to the bacterial cell envelope by the surface nanostructures; however, the process of bacterial death encountering nanostructured surfaces has not been fully illuminated. Here, we perform an in-depth investigation of the mechano-bactericidal action of black silicon (bSi) surfaces toward Gram-negative bacteria Pseudomonas aeruginosa. We discover that the mechanical injury is not sufficient to kill the bacteria immediately due to the survival of the inner plasma membrane. Instead, such sublethal mechanical injury leads to apoptosis-like death (ALD) in affected bacteria. In addition, when the mechanical stress is removed, the self-accumulated reactive oxygen species (ROS) incur poststress ALD in damaged cells in a nonstressed environment, revealing that the mechano-bactericidal actions have sustained physiological effects on the bacterium. This work creates a new facet and can introduce many new regulation tools to this field.


Subject(s)
Nanostructures , Pseudomonas aeruginosa , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Gram-Negative Bacteria , Nanostructures/chemistry , Pseudomonas aeruginosa/physiology , Surface Properties
15.
J Ment Health ; 32(3): 541-550, 2023 Jun.
Article in English | MEDLINE | ID: mdl-35775503

ABSTRACT

BACKGROUND: Adverse childhood experiences (ACEs) affect children's development, and their harm to health is pervasive throughout the life course. AIMS: To identify ACEs and their risk factors in Chinese household with or without parental mental illness. METHODS: A controlled study was conducted among 181 young adults with parental mental illness (positive group) and 201 demographically matched individuals without parental mental illness (negative group). Univariate and multivariate analyses were performed to study the correlation between ACEs and their risk factors. RESULTS: The positive group suffered emotional abuse, domestic violence, bullying, and cumulative ACEs more frequently than the negative group. In the positive group, living in rural areas and having a low household economic status during childhood were identified as risk factors for cumulative ACEs, whereas a higher education level of the mother was a protective factor for cumulative ACEs in univariate analyses. Low household economic status remained an independent risk factor for cumulative ACEs in the positive group in multivariate analyses. CONCLUSIONS: Children living with parental mental illness are more vulnerable to ACEs, and our findings highlight the importance of socioeconomic factors in increasing the risk of ACEs. To alleviate the deleterious impact of parental mental illness on offspring, multidimensional supports are needed.


Subject(s)
Adverse Childhood Experiences , Mental Disorders , Child , Young Adult , Humans , Parents , Research Design , China/epidemiology , Mental Disorders/epidemiology
16.
Angew Chem Int Ed Engl ; 62(18): e202300167, 2023 Apr 24.
Article in English | MEDLINE | ID: mdl-36882908

ABSTRACT

Biological proton channels play important roles in the delicate metabolism process, and have led to great interest in mimicking selective proton transport. Herein, we designed a bioinspired proton transport membrane by incorporating flexible 14-crown-4 (14C4) units into rigid frameworks of polyimine films by an interfacial Schiff base reaction. The Young's modulus of the membrane reaches about 8.2 GPa. The 14C4 units could grab water, thereby forming hydrogen bond-water networks and acting as jumping sites to lower the energy barrier of proton transport. The molecular chains present a vertical orientation to the membrane, and the ions travel between the quasi-planar molecular sheets. Furthermore, the 14C4 moieties could bond alkali ions through host-guest interactions. Thus, the ion conductance follows H+ ≫K+ >Na+ >Li+ , and an ultrahigh selectivity of H+ /Li+ (ca. 215) is obtained. This study provides an effective avenue for developing ion-selective membranes by embedding macrocycle motifs with inherent cavities.

17.
Angew Chem Int Ed Engl ; 62(1): e202212120, 2023 01 02.
Article in English | MEDLINE | ID: mdl-36329000

ABSTRACT

Biological ion channels existing in organisms are critical for many biological processes. Inspired by biological ion channels, the heterogeneous electrospinning nanofiber membranes (HENM) with functional ion channels are constructed by electrospinning technology. The HENM successfully realizes ion-gating effects, which can be used for tunable energy conversions. Introduction of pyridine and carboxylic acid groups into the HENM plays an important role in generating unique and stable ion transport behaviors, in which gates become alternative states of open and close, responding to symmetric/asymmetric pH stimulations. Then we used the HENM to convert osmotic energy into electric energy which reach a maximum value up to 12.34 W m-2 and the output power density of HENM-based system could be regulated by ion-gating effects. The properties of the HENM provide widespread potentials in application of smart nanofluidic devices, energy conversion, and water treatment.


Subject(s)
Nanofibers , Nanotechnology , Ion Transport , Ion Channels/chemistry , Hydrogen-Ion Concentration
18.
Angew Chem Int Ed Engl ; 62(23): e202302938, 2023 Jun 05.
Article in English | MEDLINE | ID: mdl-37029469

ABSTRACT

Nanofluidic reverse electrodialysis provides an attractive way to harvest osmotic energy. However, most attention was paid to monotonous membrane structure optimization to promote selective ion transport, while the role of external fields and relevant mechanisms are rarely explored. Here, we demonstrate a Kevlar-toughened tungsten disulfide (WS2 ) composite membrane with bioinspired serosa-mimetic structures as an efficient osmotic energy generator coupling light. As a result, the output power could be up to 16.43 W m-2 under irradiation, outperforming traditional two-dimensional (2D) membranes. Both the experiment and simulation uncover that the generated photothermal and photoelectronic effects could synergistically promote the confined ion transport process. In addition, this membrane also possesses great anti-fouling properties, endowing its practical application. This work paves new avenues for sustainable power generation by coupling solar energy.

19.
J Am Chem Soc ; 144(25): 11168-11177, 2022 Jun 29.
Article in English | MEDLINE | ID: mdl-35658470

ABSTRACT

Coulombic efficiency (CE) and cycle life of metal anodes (lithium, sodium, zinc) are limited by dendritic growth and side reactions in rechargeable metal batteries. Here, we proposed a concept for constructing an anion concentration gradient (ACG)-assisted solid-electrolyte interphase (SEI) for ultrahigh ionic conductivity on metal anodes, in which the SEI layer is fabricated through an in situ chemical reaction of the sulfonic acid polymer and zinc (Zn) metal. Owing to the driving force of the sulfonate concentration gradient and high bulky sulfonate concentration, a promoted Zn2+ ionic conductivity and inhibited anion diffusion in the SEI layer are realized, resulting in a significant suppression of dendrite growth and side reaction. The presence of ACG-SEI on the Zn metal enables stable Zn plating/stripping over 2000 h at a high current density of 20 mA cm-2 and a capacity of 5 mAh cm-2 in Zn/Zn symmetric cells, and moreover an improved cycling stability is also observed in Zn/MnO2 full cells and Zn/AC supercapacitors. The SEI layer containing anion concentration gradients for stable cycling of a metal anode sheds a new light on the fundamental understanding of cation plating/stripping on metal electrodes and technical advances of rechargeable metal batteries with remarkable performance under practical conditions.

20.
Acc Chem Res ; 54(22): 4154-4165, 2021 11 16.
Article in English | MEDLINE | ID: mdl-34719227

ABSTRACT

The salinity gradient between seawater and river water has been identified as a promising, clean, renewable, and sustainable energy source that can be converted into electricity using ion-selective membranes in a reverse electrodialysis (RED) configuration. However, the major hindrance to current salinity gradient power (SGP) conversion is its poor energy efficiency due to the use of low-performance membrane processes, which affords power for neither miniaturized devices nor industrial-level applications. Nanofluidics, which combines strong confinement and surface charge effects at the nanoscale, contributes to novel transport properties, including excellent ion selectivity and high ion throughput; thus, nanofluidics may lead to technological breakthroughs and act as an emerging platform for harnessing SGP. Recently, two-dimensional (2D) materials have provided impressive energy extraction performance and further insight into fundamental transport mechanisms and theoretical feasibility. To reach the commercialization benchmark and real-world applications, an array of nanopores and channels that can be scaled up to industrial sizes is in high demand; additionally, it remains challenging to develop macroscale nanofluidic membranes that meet the "selectivity versus throughput" dual requirement. In the first section, we start with our understanding of the underlying mechanism of ion-channel interactions and transport characteristics in nanofluidic channel systems from the microscale to the macroscale. We review our recent efforts in this field by constructing a heterojunction with asymmetric ion transport behavior that generates rectification of the ion flux and creates an osmotic diode, which is composed of two nanofluidic layers with opposite polar charges and different chemical compositions. Another efficient way to improve the performance of the system is introducing charged functional materials intercalated into laminar 2D nanosheets. The intercalated nanofluidic material can be explained by two classical models to account for the synergistic effects that (i) improve the stability and mechanical properties of 2D materials with a fixed interlayer spacing and (ii) provide space charge for modulating ion diffusion; both of these effects contribute to its considerable energy conversion performance. Further, layer-by-layer membranes are superior to traditional membranes consisting of a simple stack because they retain their repulsion effect toward co-ions, largely strengthening the efficiency of ion separation and conversion. In particular, we highlight our views on the role of the 2D phase structure (e.g., semiconductor 2H phase and metallic 1T phase) in which the two phases differ from each other in physical and chemical properties, including ionic conductance, surface charge, and wetting, thereby presenting a state-of-the-art avenue for controlling ion transport. In view of the nature of 2D materials, we also report improved osmotic energy harvesting by exploiting the photoinduced heat gradient and electrons that increase ion mobility and surface charge, respectively. Finally, we point out specific research topics in which a combined project can certainly come into the limelight. For example, we discuss the combination of SGP with desalination systems and water splitting. We expect that this Account will stimulate further efforts toward functionalized 2D nanoporous materials and facilitate interdisciplinary efforts in chemistry, material engineering, environmental science, and nanotechnology.

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