Correction: Intelligent micro/nanorobots based on biotemplates.

Correction for 'Intelligent micro/nanorobots based on biotemplates' by Ting Chen et al., Mater. Horiz., 2024, https://doi.org/10.1039/d4mh00114a.

Automated marine oil spill detection algorithm based on single-image generative adversarial network and YOLO-v8 under small samples.

As marine resources and transportation develop, oil spill incidents are increasing, endangering marine ecosystems and human lives. Rapidly and accurately identifying marine oil spill is of utmost importance in protecting marine ecosystems. Marine oil spill detection methods based on deep learning and computer vision have the great potential significantly enhance detection efficiency and accuracy, but their performance is often limited by the scarcity of real oil spill samples, posing a challenging to train a precise detection model. This study introduces a detection method specifically designed for scenarios with limited sample sizes. First, the small sample dataset of marine oil spill taken by Landsat-8 satellite is used as the training set. Then, a single image generative adversarial network (SinGAN) capable of training with a single oil spill image is constructed for expanding the dataset, generating diverse marine oil spill samples with different shapes. Second, a YOLO-v8 model is pretrained via the method of transfer learning and then trained with dataset before and after augmentation separately for real-time and efficient oil spill detection. Experimental results have demonstrated that the YOLO-v8 model, trained on an expanded dataset, exhibits notable enhancements in recall, precision, and average precision, with improvements of 12.3 %, 6.3 %, and 11.3 % respectively, compared to the unexpanded dataset. It reveals that our marine oil spill detection model based on YOLO-v8 exhibits leading or comparable performance in terms of recall, precision, and AP metrics. The data augmentation technique based on SinGAN contributes to the performance of other popular object detection algorithms as well.

Intelligent micro/nanorobots based on biotemplates.

Intelligent micro/nanorobots based on natural materials as biotemplates are considered to be some of the most promising robots in the future in the microscopic field. Due to the advantages of biotemplates such as unique structure, abundant resources, environmental friendliness, easy removal, low price, easy access, and renewability, intelligent micro/nanorobots based on biotemplates can be endowed with both excellent biomaterial activity and unique structural morphology through biotemplates themselves and specific functions through artificial micro/nanotechnology. Thus, intelligent micro/nanorobots show excellent application potential in various fields from biomedical applications to environmental remediation. In this review, we introduce the advantages of using natural biological materials as biotemplates to build intelligent micro/nanorobots, and then, classify the micro/nanorobots according to different types of biotemplates, systematically detail their preparation strategies and summarize their application prospects. Finally, in order to further advance the development of intelligent micro/nanorobots, we discuss the current challenges and future prospects of biotemplates. Intelligent micro/nanorobots based on biotemplates are a perfect combination of natural biotemplates and micro/nanotechnology, which is an important trend for the future development of micro/nanorobots. We hope this review can provide useful references for developing more intelligent, efficient and safe micro/nanorobots in the future.

Chiral BINOL-phosphate assembled single hexagonal nanotube in aqueous solution for confined rearrangement acceleration.

Creating microenvironments that mimic an enzyme's active site is a critical aspect of supramolecular confined catalysis. In this study, we employ the commonly used chiral 1,1'-bi-2-naphthol (BINOL) phosphates as subcomponents to construct supramolecular hollow nanotube in an aqueous medium through non-covalent intermolecular recognition and arrangement. The hexagonal nanotubular structure is characterized by various techniques, including X-ray, NMR, ESI-MS, AFM, and TEM, and is confirmed to exist in a homogeneous aqueous solution stably. The nanotube's length in solution depends on the concentration of chiral BINOL-phosphate as a monomer. Additionally, the assembled nanotube can accelerate the rate of the 3-aza-Cope rearrangement reaction by up to 85-fold due to the interior confinement effect. Based on the detailed kinetic and thermodynamic analyses, we propose that the chain-like substrates are constrained and pre-organized into a reactive chair-like conformation, which stabilizes the transition state of the reaction in the confined nanospace of the nanotube. Notably, due to the restricted conformer with less degrees of freedom, the entropic barrier is significantly reduced compared to the enthalpic barrier, resulting in a more pronounced acceleration effect.

Ultrasound-propelled nanomotors for efficient cancer cell ferroptosis.

Ferroptosis is a non-apoptotic form of cell death that is dependent on the accumulation of intracellular iron that causes elevation of toxic lipid peroxides. Therefore, it is crucial to improve the levels of intracellular iron and reactive oxygen species (ROS) in a short time. Here, we first propose ultrasound (US)-propelled Janus nanomotors (Au-FeOx/PEI/ICG, AFPI NMs) to accelerate cellular internalization and induce cancer cell ferroptosis. This nanomotor consists of a gold-iron oxide rod-like Janus nanomotor (Au-FeOx, AF NMs) and a photoactive indocyanine green (ICG) dye on the surface. It not only exhibits accelerating cellular internalization (∼4-fold) caused by its attractive US-driven propulsion but also shows good intracellular motion behavior. In addition, this Janus nanomotor shows excellent intracellular ROS generation performance due to the synergistic effect of the "Fenton or Fenton-like reaction" and the "photochemical reaction". As a result, the killing efficiency of actively moving nanomotors on cancer cells is 88% higher than that of stationary nanomotors. Unlike previous passive strategies, this work is a significant step toward accelerating cellular internalization and inducing cancer-cell ferroptosis in an active way. These novel US-propelled Janus nanomotors with strong propulsion, efficient cellular internalization and excellent ROS generation are suitable as a novel cell biology research tool.

Intermolecular Interactions, Morphology, and Photovoltaic Patterns in p-i-n Heterojunction Solar Cells With Fluorine-Substituted Organic Photovoltaic Materials.

During the layer-by-layer (LBL) processing of polymer solar cells (PSCs), the swelling and molecule interdiffusion are essential for achieving precise, controllable vertical morphology, and thus efficient PSCs. However, the influencing mechanism of material properties on morphology and correlated device performance has not been paid much attention. Herein, a series of fluorinated/non-fluorinated polymer donors (PBDB-T and PBDB-TF) and non-fullerene acceptors (ITIC, IT-2F, and IT-4F) are employed to investigate the performance of LBL devices. The impacts of fluorine substitution on the repulsion and miscibility between the donor and acceptor, as well as the molecular arrangement of the donor/acceptor and the vertical distribution of the LBL devices are systematically explored by the measurement of donor/acceptor Flory-Huggins interaction parameters, spectroscopic ellipsometry, and neutron reflectivity, respectively. With efficient charge transfer due to the ideal vertical and horizon morphology properties, devices based on PBDB-TF/IT-4F exhibit the highest fill factors (FFs) as well as champion power conversion efficiencies (PCEs). With this guidance, high-performance LBL devices with PCE of 17.2%, 18.5%, and 19.1% are obtained by the fluorinated blend of PBDB-TF/Y6, PBDB-TF/L8-BO, and D18/L8-BO respectively.

Green synthesis of bifunctional phthalocyanine-porphyrin cofs in water for efficient electrocatalytic CO2 reduction coupled with methanol oxidation.

Electrocatalytic CO2 reduction (ECR) coupled with organic oxidation is a promising strategy to produce high value-added chemicals and improve energy efficiency. However, achieving the efficient redox coupling reaction is still challenging due to the lack of suitable electrocatalysts. Herein, we designed two bifunctional polyimides-linked covalent organic frameworks (PI-COFs) through assembling phthalocyanine (Pc) and porphyrin (Por) by non-toxic hydrothermal methods in pure water to realize the above catalytic reactions. Due to the high conductivity and well-defined active sites with different chemical environments, NiPc-NiPor COF performs efficient ECR coupled with methanol oxidation reaction (MOR) (Faradaic efficiency of CO (FECO) = 98.12%, partial current densities of CO (jCO) = 6.14 mA cm-2 for ECR, FEHCOOH = 93.75%, jHCOOH = 5.81 mA cm-2 for MOR at low cell voltage (2.1 V) and remarkable long-term stability). Furthermore, experimental evidences and density functional theory (DFT) calculations demonstrate that the ECR process mainly conducts on NiPc unit with the assistance of NiPor, meanwhile, the MOR prefers NiPor conjugating with NiPc. The two units of NiPc-NiPor COF collaboratively promote the coupled oxidation-reduction reaction. For the first time, this work achieves the rational design of bifunctional COFs for coupled heterogeneous catalysis, which opens a new area for crystalline material catalysts.

Relative Local Electron Density Tuning in Metal-Covalent Organic Frameworks for Boosting CO2 Photoreduction.

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, the systematic studies on the structure-functional relationship regarding the above two factors based on precisely structure model are rarely reported. Herein, as a proof-of-concept, we developed a new strategy on the evaluation of local electron density by controlling the relative electron-deficient (ED) and electron-rich (ER) intensity of monomer at a molecular level based on three rational-designed vinylene-linked sp2 carbon-covalent organic frameworks (COFs). As expected, the as-prepared vinylene-linked sp2 carbon-conjugated metal-covalent organic framework (MCOFs) (VL-MCOF-1) with molecular junction exhibited excellent activities for CO2 -to-HCOOH conversion (283.41 µmol g-1 h-1 ) and high selectivity of 97.1 %, much higher than the VL-MCOF-2 and g-C34 N6 -COF, which is due to the synergistic effect of the multi-electronic metal clusters (Cu3 (PyCA)3 ) (PyCA=pyrazolate-4-carboxaldehyde) as strong ER roles and cyanopyridine units as ED roles and active sites, as well as the boosted photo-induced charge separation efficiency of vinyl connection and increased light utilization ability. These results not only provide a strategy for regulating the electron-density distribution of photocatalysts at the molecular level but also offers profound insights for metal clusters-based COFs to effective CO2 conversion.

Five in One: Multi-Engine Highly Integrated Microrobot.

A multi-engine highly integrated microrobot, which is a Janus hemispherical shell structure composed of Pt and α-Fe2 O3 , is successfully developed. The microrobot can be efficiently driven and flexibly regulated by five stimuli, including an optical field, an acoustic field, magnetic field, an electric field, and chemical fuel. In addition, no matter which way it is driven by, the direction can be effectively controlled through the magnetic field regulation. Furthermore, this microrobot can also utilize magnetic or acoustic fields to achieve excellent aggregation control and swarm movement. Finally, this study demonstrates that the microrobots' propulsion can be effectively synergistically enhanced through the simultaneous action of two driving mechanisms, which can greatly improve the performance of the motor in applications, such as pollutant degradation. This multi-engine, highly integrated microrobot not only can adapt to more complex environments and has a wider application range, better application prospects, but also provides important ideas for designing future advanced micro/nanorobots.

Catalytic micromotors as self-stirring microreactors for efficient dual-mode colorimetric detection.

A catalytic micromotor-based (MIL-88B@Fe3O4) colorimetric detection system which exhibit rapid color reaction for quantitative colorimetry and high-throughput testing for qualitative colorimetry have been successfully developed. Taking the advantages of the micromotor with dual roles (micro-rotor and micro-catalyst), under rotating magnetic field, each micromotor represents a microreactor which have micro-rotor for microenvironment stirring and micro-catalyst for the color reaction. Numerous self-string micro-reactions rapidly catalyze the substance and show the corresponding color for the spectroscopy testing and analysis. Additionally, owing to the tiny motor can rotate and catalyze within microdroplet, a high-throughput visual colorimetric detection system with 48 micro-wells has been innovatively conducted. The system enables up to 48 microdroplet reactions based on micromotors run simultaneously under the rotating magnetic field. Multi-substance, including their species difference and concentration strength, can be easily and efficiently identified by observing the color difference of the droplet with naked eye after just one test. This novel catalytic MOF-based micromotor with attractive rotational motion and excellent catalytic performance not only endowed a new nanotechnology to colorimetry, but also shows hold great potentials in other fields, such as refined production, biomedical analysis, environmental governance etc., since such micromotor-based microreactor can be easily applied to other chemical microreactions.

An Amphiphilic Molecule-Regulated Core-Shell-Solvation Electrolyte for Li-Metal Batteries at Ultra-Low Temperature.

Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ultra-low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2-tetrafluoro-3-methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li+ to induce self-assembly of the electrolyte solution to form a peculiar core-shell-solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li+ transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to -40 °C at high current densities. Meanwhile, anode-free high-voltage cell retains 87 % capacity after 100 cycles.

Demystifying the roles of single metal site and cluster in CO2 reduction via light and electric dual-responsive polyoxometalate-based metal-organic frameworks.

Photo- or electroreduction of carbon dioxide into highly valued products offers a promising strategy to achieve carbon neutrality. Here, a series of polyoxometalate-based metal-organic frameworks (M-POMOFs) were constructed by metalloporphyrins [tetrakis(4-carboxyphenyl)-porphyrin-M (M-TCPPs)] and reductive POM for photo- and electrocatalytic carbon dioxide reductions (PCR and ECR, respectively), and the mysteries between the roles of single metal site and cluster in catalysis were disclosed. Iron-POMOF exhibited an excellent selectivity (97.2%) with high methane production of 922 micromoles per gram in PCR, together with superior Faradaic efficiency for carbon dioxide to carbon monoxide (92.1%) in ECR. The underlying mechanisms were further clarified. Photogenerated electrons transferred from iron-TCPP to the POM cluster for methane generation under irradiation, while the abundant electrons flowed to the center of iron-TCPP for carbon monoxide formation under the applied electric field. The specific multielectron products generated on iron-POMOF through switching driving forces to control electron flow direction between single metal site and cluster catalysis.

Recent Advances in One-Dimensional Micro/Nanomotors: Fabrication, Propulsion and Application.

Due to their tiny size, autonomous motion and functionalize modifications, micro/nanomotors have shown great potential for environmental remediation, biomedicine and micro/nano-engineering. One-dimensional (1D) micro/nanomotors combine the characteristics of anisotropy and large aspect ratio of 1D materials with the advantages of functionalization and autonomous motion of micro/nanomotors for revolutionary applications. In this review, we discuss current research progress on 1D micro/nanomotors, including the fabrication methods, driving mechanisms, and recent advances in environmental remediation and biomedical applications, as well as discuss current challenges and possible solutions. With continuous attention and innovation, the advancement of 1D micro/nanomotors will pave the way for the continued development of the micro/nanomotor field.

Tuning the Solvent Alkyl Chain to Tailor Electrolyte Solvation for Stable Li-Metal Batteries.

1,2-Dimethoxyethane (DME) has been considered as the most promising electrolyte solvent for Li-metal batteries (LMBs). However, challenges arise from insufficient Li Coulombic efficiency (CE) and poor anodic stability associated with DME-based electrolytes. Here, we proposed a rational molecular design methodology to tailor electrolyte solvation for stable LMBs, where shortening the middle alkyl chain of the solvent could reduce the chelation ability, while increasing the terminal alkyl chain of the solvent could increase the steric hindrance, affording a diethoxymethane (DEM) solvent with ultra-weak solvation ability. When serving as a single solvent for electrolyte, a peculiar solvation structure dominated by contact ion pairs (CIPs) and aggregates (AGGs) was achieved even at a regular salt concentration of 1 m, which gives rise to anion-derived interfacial chemistry. This illustrates an unprecedentedly high Li||Cu CE of 99.1% for a single-salt single-solvent (non-fluorinated) electrolyte at ∼1 m. Moreover, this 1 m DEM-based electrolyte also remarkably suppresses the anodic dissolution of Al current collectors and significantly improves the cycling performance of high-voltage cathodes. This work opens up new frontiers in engineering electrolytes toward stable LMBs with high energy densities.

Rapid and Specific Enhanced Luminescent Switch of Aniline Gas by MOFs Assembled from a Planar Binuclear Cadmium(II) Metalloligand.

Due to the low vapor pressure of aniline, it is challenging to develop a specific rapid fluorescence detection material for low concentrations of aniline gas, which is suspected to result in carcinogenicity when people are exposed by ingestion, inhalation, and skin contact. Herein, the easy-preparing Schiff base ligands were employed to construct the binuclear cadmium(II) compounds featuring a good plane and fine luminescent property, and then, the end groups were changed, making the compounds metalloligands to further build the 3D metal-organic frameworks (MOFs), named MECS-2. It is found that MECS-2 can achieve specific luminescent enhancement response for aniline gas. Furthermore, a large-scale MECS-2a film could be easily prepared by electrospinning nanoMECS-2, which presents the highly efficient and visual detection for aniline gas with the luminescent enhancement effect up to 20 times and good repeatability. Our work provides a good example for the efficient construction of MOF-based films with the fluorescence detection function for organic aromatic gases.

Tuning the Metal Ions of Prussian Blue Analogues in Separators to Enable High-Power Lithium Metal Batteries.

The Li dendrite issue is the major barrier that limits the implement of Li metal anode practically, especially at high current density. From the perspective of the nucleation and growth mechanism of the Li dendrite, we rationally develop a novel Prussian blue analogues (PBA)-derived separator, where tuning the metal ions bestows the PBAs with open metal site to confine anion movement and thereby afford a high Li+ transference number (0.78), and PBA with ordered micropores could act as an ionic sieve to selectively extract Li+ and thereby homogenize Li+ flux. This demonstrates a highly reversible Li plating/stripping cycling for 3000 h at a practically high current density (5.0 mA cm-2). Consequently, a high loading Li||LiFeO4 battery (∼10.0 mg cm-2) demonstrates ultralong cycling life at high current densities (∼5.1 mA cm-2). This work highlights the prospect of optimizing PBAs in regulating ion transport behavior to enable high-power Li metal batteries.

Single-Metal Hybrid Micromotor.

Multimode stimuli-regulated propulsions are extremely useful for artificial micro-/nanomotors in performing specialized tasks in different microscopic environments. However, it is still a great challenge to develop a simple and efficient micro/nanosystem which can operate in complicated environments, either with fuel or without fuel. Here, we report a novel hybrid micromotor which only needs one metal with a special structure: micro-spherical shell with a hole. Since we attractively combine the inherently catalytic properties of Pt for chemical propulsion with a designed concave structure for acoustic propulsion, the micromotors can not only move rapidly in H2O2 fueled environment due to the chemical reaction between Pt and H2O2 but also can exhibit excellent acoustic propulsion in a fuel-free environment due to the non-uniform stress caused by ultrasound. In addition, the attractive group motion behavior of the motors, including aggregation, group migration, and dispersion, is easily realized by acoustic field regulation. The brand-new single-metal hybrid micromotors with a dual driving mode, flexible propulsion regulation, and efficient group motion regulation, which are essential for making micro-/nanomotors compatible with different surrounding environments, are expected to advance the field of artificial nanomachines.

Adiponitrile (ADN): A Stabilizer for the LiNi0.8Co0.1Mn0.1O2 (NCM811) Electrode/Electrolyte Interface of a Graphite/NCM811 Li-Ion Cell.

Adiponitrile (ADN) is studied as an additive of commercial carbonate electrolyte for a graphite/NCM811 Li-ion cell in this work. Compared with the cell using a baseline electrolyte, the cycling stability of the cells using 0.2, 0.5, 1, and 2 wt % ADN-added electrolytes is significantly improved. Among them, the effect is most prominent when the ADN content is 0.5 wt %, and the capacity retention rate of the cell after 200 cycles at 0.3 C is increased by 17.6%. Scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses confirm that ADN can make the coating layer formed on the cathode and anode surfaces of the cell denser and uniform. The formation of the cathodic coating layer does not obey the usual mechanism of adsorption between the nitrile group and metal ions, but it may be due to the polymerization of ADN initiated by carbocations from the oxidation of solvent molecules (ethylene carbonate/ethyl methyl carbonate) in the electrolyte. The cathodic coating layer greatly decreases the oxidation of the electrolyte so that a stable coating layer (also called solid electrolyte interface/SEI) can be formed on the anode, which is the reason for improvement of the cycling performance of the cell. However, the formation of the anode SEI layer is almost independent of ADN, and it still depends on the common reduction reaction of the electrolyte.

Covalent Organic Framework Based Functional Materials: Important Catalysts for Efficient CO2 Utilization.

As hot topics in the chemical conversion of CO2 , the photo-/electrocatalytic reduction of CO2 and use of CO2 as a supporter for energy storage have shown great potential for the utilization of CO2 . However, many obstacles still exist on the road to realizing highly efficient chemical CO2 conversion, such as inefficient uptake/activation of CO2 and mass transport in catalysts. Covalent organic frameworks (COFs), as a kind of porous material, have been widely explored as catalysts for the chemical conversion of CO2 owing to their unique features. In particular, COF-based functional materials containing diverse active sites (such as single metal sites, metal nanoparticles, and metal oxides) offer great potential for realizing CO2 conversion and energy storage. This Minireview discusses recent breakthroughs in the basic knowledge, mechanisms, and pathways of chemical CO2 conversion strategies that use COF-based functional catalysts. In addition, the challenges and prospects of COF-based functional catalysts for the efficient utilization of CO2 are also introduced.