Plasma-Engineering of Oxygen Vacancies on NiCo2O4 Nanowires with Enhanced Bifunctional Electrocatalytic Performance for Rechargeable Zinc-air Battery.

Designing an efficient, durable, and inexpensive bifunctional electrocatalyst toward oxygen evolution reactions (OER) and oxygen reduction reactions (ORR) remains a significant challenge for the development of rechargeable zinc-air batteries (ZABs). The generation of oxygen vacancies plays a vital role in modifying the surface properties of transition-metal-oxides (TMOs) and thus optimizing their electrocatalytic performances. Herein, a H2/Ar plasma is employed to generate abundant oxygen vacancies at the surfaces of NiCo2O4 nanowires. Compared with the Ar plasma, the H2/Ar plasma generated more oxygen vacancies at the catalyst surface owing to the synergic effect of the Ar-related ions and H-radicals in the plasma. As a result, the NiCo2O4 catalyst treated for 7.5 min in H2/Ar plasma exhibited the best bifunctional electrocatalytic activities and its gap potential between Ej = 10 for OER and E1/2 for ORR is even smaller than that of the noble-metal-based catalyst. In situ electrochemical experiments are also conducted to reveal the proposed mechanisms for the enhanced electrocatalytic performance. The rechargeable ZABs, when equipped with cathodes utilizing the aforementioned catalyst, achieved an outstanding charge-discharge gap, as well as superior cycling stability, outperforming batteries employing noble-metal catalyst counterparts.

Mechanochemical treatment for degradation of ciprofloxacin (CIP) in solutions.

Ciprofloxacin (CIP) is a kind of widely used fluoroquinolone antibiotic, and the widespread presence of CIP in aquatic environment has become a serious issue. Mechanochemical treatment (MCT), as an effective approach to degrade persistent organic pollutants, has many advantages of low cost, simplicity, and being environmentally innocuous. However, little attention has been paid to employing MCT to treat effluents containing CIP. In this study, MCT was introduced to degrade CIP in aquatic solutions. A series of CIP degradation experiments were conducted by a planetary ball mill, and the influences of main parameters on CIP degradation efficiency were investigated. Furthermore, an optimum combination was selected through orthogonal experiments, and CIP degradation efficiency could reach as high as 99% in certain conditions. Besides, the biotoxicity of CIP solution was also studied. MCT exhibits satisfying performance for degrading CIP in solutions, which makes MCT a promising approach to CIP elimination and also encourages further applications in treating effluents containing other organic pollutants.

Au nanobowtie on a SiO2 microsphere for optoplasmonic trapping.

The combination of photonic and plasmonic elements with complementary optical properties has stimulated the development of optoplasmonic hybrid systems, in which photonic and plasmonic elements can interact synergistically, breaking through the limitations of traditional structures. In this paper, a new optoplasmonic tweezer is theoretically proposed by using the Au nanobowtie and SiO2 microsphere. The finite-difference time-domain simulation is used to study the influence of the size of the SiO2 microsphere and the SiO2 hemisphere in polydimethylsiloxane on the optical potential well. The simulation results show that the electric field intensity of the structure is increased by 6 times compared with the Au nanobowtie structure, and the gradient force and the trapping potential are also significantly improved.

Piezo tube stacked scanning tunneling microscope for use in extreme and confined environments.

Scanning Tunneling Microscopy (STM) is widely used for observing atomic structures due to its ultra-high spatial resolution. As the core units of STM, the coarse stepper motor and imaging unit, have conflicting size requirements for piezo tubes. Longer piezo tubes yield greater output force and easier movement for the motor, while shorter tubes enhance imaging precision and stability for the scanner. Traditional STMs typically employ a large piezo tube for coarse stepping and a smaller one for independent imaging to address this issue. Here, we present the new design of a piezo tube stacked STM, in which two independent piezo tubes act together during tip-sample approach process and only one shorter tube works during scanning imaging. Both tubes are fixed to the framework, ensuring high rigidity and compactness. The new design enables us to achieve both coarse stepping and imaging functions with a total length of only 25 mm for the two tubes, effectively reducing the length of whole STM, facilitating its integration into narrow low-temperature spaces for imaging applications. Using this device, we obtained high-quality atomic images of graphite sample surfaces at room temperature. Continuous scanning imaging of the same area on Au film at 300 K demonstrates the STM's high stability in both X-Y and Z directions. Atomic images, I-V spectra, and di/dv spectra obtained at 2 K on graphite surface illustrate the excellent application potential of this device in low-temperature environments. Finally, atomic images obtained of graphite in sweeping the magnetic fields from 0 T to 11 T in a huge vibrational dry magnet prove the new STM's excellent performance in extreme conditions.

Support effect on Ni-based mono- and bimetallic catalysts in CO2 hydrogenation.

Aiming at a comprehensive understanding of support effects on Ni-based bimetallic catalyst for CO2 hydrogenation, spectroscopy (DRIFTS) with CO as a probe molecule and temperature-programmed techniques were used to investigate the impact of different supports (MgO, CeO2, ZrO2) on Ni- and Ni,Fe catalysts. Kinetic parameters revealed that the higher selectivity to methanation for Ni and Ni,Fe supported on the reducible oxides (CeO2, ZrO2) is due to the inhibition of reverse water-gas shift reaction (RWGS) by hydrogen. A promoting effect of Fe on Ni was only observed on MgO-supported catalysts. In situ DRIFTS with CO adsorption showed different electronic properties of Ni sites with partially reduced oxide (i.e. ZrO2 and CeO2). H2-TPR and CO2-TPD confirmed the significant role of metal-support interaction (MSI) in CeO2-supported catalysts for CO2 activation. The MSI between Ni/Ni,Fe and reducible supports are crucial for catalytic performance, ultimately leading to the higher activity and stability in CO2 hydrogenation.

Case report: Successful treatment of a rare HER2-positive advanced breast squamous cell carcinoma.

Background: Breast squamous cell carcinoma (SCC) is an uncommon and highly aggressive variant of metaplastic breast cancer. Despite its rarity, there is currently no consensus on treatment guidelines for this specific subtype. Previous studies have demonstrated that chemotherapy alone has limited efficacy in treating breast SCC. However, the potential for targeted therapy in combination with chemotherapy holds promise for future treatment options. Case presentation: In this case report, we present a patient with advanced HER2-positive breast SCC, exhibiting a prominent breast mass, localized ulcers, and metastases in the lungs and brain. Our treatment approach involved the administration of HER2-targeted drugs in conjunction with paclitaxel, resulting in a sustained control of tumor growth. Conclusion: This case represents a rare occurrence of HER2-positive breast SCC, with limited available data on the efficacy of previous HER2-targeted drugs in treating such patients. Our study presents the first application of HER2-targeted drugs in this particular case, offering novel therapeutic insights for future considerations. Additionally, it is imperative to conduct further investigations to assess the feasibility of treatment options in a larger cohort of patients.

Unveiling the Structure-Property Relationship of MgO-Supported Ni Ammonia Decomposition Catalysts from Bulk to Atomic Structure by In Situ/Operando Studies.

Ammonia is currently being studied intensively as a hydrogen carrier in the context of the energy transition. The endothermic decomposition reaction requires the use of suitable catalysts. In this study, transition metal Ni on MgO as a support is investigated with respect to its catalytic properties. The synthesis method and the type of activation process contribute significantly to the catalytic properties. Both methods, coprecipitation (CP) and wet impregnation (WI), lead to the formation of Mg1-xNixO solid solutions as catalyst precursors. X-ray absorption studies reveal that CP leads to a more homogeneous distribution of Ni2+ cations in the solid solution, which is advantageous for a homogeneous distribution of active Ni catalysts on the MgO support. Activation in hydrogen at 900 °C reduces nickel, which migrates to the support surface and forms metal nanoparticles between 6 nm (CP) and 9 nm (WI), as shown by ex situ STEM. Due to the homogeneously distributed Ni2+ cations in the solid solution structure, CP samples are more difficult to activate and require harsher conditions to reduce the Ni. The combination of in situ X-ray diffraction (XRD) and operando total scattering experiments allows a structure-property investigation of the bulk down to the atomic level during the catalytic reaction. Activation in H2 at 900 °C for 2 h leads to the formation of large Ni particles (20-30 nm) for the samples synthesized by the WI method, whereas Ni stays significantly smaller for the CP samples (10-20 nm). Sintering has a negative influence on the catalytic conversion of the WI samples, which is significantly lower compared to the conversion observed for the CP samples. Interestingly, metallic Ni redisperses during cooling and becomes invisible for conventional XRD but can still be detected by total scattering methods. The conditions of activation in NH3 at 650 °C are not suitable to form enough reduced Ni nanoparticles from the solid solution and are, therefore, not a suitable activation procedure. The activity steadily increases in the samples activated at 650 °C in NH3 (Group 1) compared to the samples activated at 650 °C in H2 and then reaches the best activity in the samples activated at 900 °C in H2. Only the combination of complementary in situ and ex situ characterization methods provides enough information to identify important structure-property relationships among these promising ammonia decomposition catalysts.

A rigid and compact piezoelectric motor with high output efficiency.

We introduce a novel piezoelectric stepper motor featuring high compactness, rigidity, and any direction operability. Here, not only is the structure of high novelty but also the working principle very simple. The piezo stacks unit is sandwiched between two spring finger pieces, with almost equal clamping forces applied between the top of the piezo stacks' unit and the spring finger piece. Applying individual driving signals to each of the five piezo stack pairs, causing deformation one by one in the same direction, followed by simultaneous recovery in the reverse direction, enables movement of the frame part. The optimized clamping force of the piezoelectric stack units and spring fingers ensures maximum output force. The motor's operational capability at low threshold voltages, specifically 8 V for downward movement and 10 V for upward movement, confirmed its efficacy in both vertical and horizontal directions. The motor's operational capability at a low threshold voltage of 10 V confirmed its efficacy in both vertical and horizontal directions. At room temperature, step size ranges from 0.3 to 7.4 µm at 20 Hz frequency and varying driving voltage from 10 to 180 V. It has a maximum travel range of about 5 mm and can lift a maximum load of 220 g in an upward direction, so the maximum output force generated by this motor is 2.2 N. The compact and rigid design is capable of building an atomically resolved scanning probe microscope, and its working ability has the potential to use the cleavage of different types of samples in limited space environments, such as the small-bore superconducting magnet and low temperature.

A novel STM for quality atomic resolution with piezoelectric motor of high compactness and simplicity.

Scanning tunneling microscope (STM) is a renowned scientific tool for obtaining high-resolution atomic images of materials. Herein, we present an innovative design of the scanning unit with a compact yet powerful inertial piezoelectric motor inspired by the Spider Drive motor principle. The scanning unit mainly consists of a small 9 mm long piezoelectric tube scanner (PTS), one end of which is coaxially connected to the main sapphire body of the STM. Of particular emphasis in this design is the piezoelectric shaft (PS), constructed from piezoelectric material instead of conventional metallic or zirconium materials. The PS is a rectangular piezoelectric stack composed of two piezoelectric plates, which are elastically clamped on the inner wall of the PTS via a spring strip. The PTS and PS expand and contract independently with each other to improve the inertial force and reduce the threshold voltage. To ensure the stability of the PS and balance the stepping performance of the inertial motor, a counterweight, and a matching conical spring are fixed at the tail of the PS. This innovative design allows for the assessment of scanning unit performance by applying a driving signal, threshold voltage is 50 V at room temperature. Step sizes vary from 0.1 to 1 µm by changing the driving signal at room temperature. Furthermore, we successfully obtained atomic-resolution images of a highly oriented pyrolytic graphite (HOPG) sample and low drift rates of 23.4 pm/min and 34.6 pm/min in X-Y plane and Z direction, respectively, under ambient conditions. This small, compact STM unit has the potential for the development of a rotatable STM for use in cryogen-free magnets, and superconducting magnets.

Glovebox-assisted magnetic force microscope for studying air-sensitive samples in a cryogen-free magnet.

Most known two-dimensional magnets exhibit a high sensitivity to air, making direct characterization of their domain textures technically challenging. Herein, we report on the construction and performance of a glovebox-assisted magnetic force microscope (MFM) operating in a cryogen-free magnet, realizing imaging of the intrinsic magnetic structure of water and oxygen-sensitive materials. It features a compact tubular probe for a 50 mm-diameter variable temperature insert installed in a 12 T cryogen-free magnet. A detachable sealing chamber can be electrically connected to the tail of the probe, and its pump port can be opened and closed by a vacuum manipulator located on the top of the probe. This sealing chamber enables sample loading and positioning in the glove box and MFM transfer to the magnet maintained in an inert gas atmosphere (in this case, argon and helium gas). The performance of the MFM is demonstrated by directly imaging the surface (using no buffer layer, such as h-BN) of very air-sensitive van der Waals magnetic material chromium triiodide (CrI3) samples at low temperatures as low as 5 K and high magnetic fields up to 11.9 T. The system's adaptability permits replacing the MFM unit with a scanning tunneling microscope unit, enabling high-resolution atomic imaging of air-sensitive surface samples.

Isolated scan unit and scanning tunneling microscope for stable imaging in ultra-high magnetic fields.

The high resolution of a scanning tunneling microscope (STM) relies on the stability of its scan unit. In this study, we present an isolated scan unit featuring non-magnetic design and ultra-high stability, as well as bidirectional movement capability. Different types of piezoelectric motors can be incorporated into the scan unit to create a highly stable STM. The standalone structure of scan unit ensures a stable atomic imaging process by decreasing noise generated by motor. The non-magnetic design makes the scan unit work stable in high magnetic field conditions. Moreover, we have successfully constructed a novel STM based on the isolated scan unit, in which two inertial piezoelectric motors act as the coarse approach actuators. The exceptional performance of homebuilt STM is proved by the high-resolution atomic images and dI/dV spectrums on NbSe2 surface at varying temperatures, as well as the raw-data images of graphite obtained at ultra-high magnetic fields of 23 T. According to the literature research, no STM has previously reported the atomic image at extreme conditions of 2 K low temperature and 23 T ultra-high magnetic field. Additionally, we present the ultra-low drift rates between the tip and sample at varying temperatures, as well as when raising the magnetic fields from 0 T to 23 T, indicating the ultra-high stability of the STM in high magnetic field conditions. The outstanding performance of our stable STM hold great potential for investigating the materials in ultra-high magnetic fields.

An ultracompact scanning tunneling microscope within a Φ 10 piezo tube in a 20 T superconducting magnet.

Low-temperature scanning tunneling microscopy and spectroscopy (STM/S) help to better understand the fundamental physics of condensed matter. We present an ultracompact STM within a Φ 10 piezo tube in a 20 T superconducting magnet. The carefully cut piezo tube contains the STM's coarse-positioning assembly. Loading an STM tip-sample mechanical loop into the piezo tube with special cut openings enables an ultracompact pencil-size dimension down to Φ 10 mm, in which fine-machined nonmagnetic parts are assembled to enable slide-stick motion and xyz-scanning procedures. The small size leads to a higher resonant frequency, a typical feature of a rigid STM instrument, increasing its vibration immunity. Scanning by moving the sample while keeping the tip stationary improves the stability of the tip-sample junction compared to moving the tip. Taking advantage of its high-field compatibility and rigid design, our STM captures the atomically resolved topography of highly oriented pyrolytic graphite (HOPG) at 1.5 K and in magnetic fields up to 17 T. The topography of graphene lattice and graphite is simultaneously recorded on an atomic terrace of HOPG, unveiling a modified local charge density at a surface defect. The superconducting energy gaps of layered type-II superconductors NbSe2 and PdBi2 are well resolved through dI/dV tunneling spectra at sub-2 K. Our unique STM is highly suitable for potential STM/S applications in world-class high-field facilities where the strong magnetic field can exceed 30 T.

Real-Space Imaging of Intrinsic Symmetry-Breaking Spin Textures in a Kagome Lattice.

The electronic orders in kagome materials have emerged as a fertile platform for studying exotic quantum states, and their intertwining with the unique kagome lattice geometry remains elusive. While various unconventional charge orders with broken symmetry is observed, the influence of kagome symmetry on magnetic order has so far not been directly observed. Here, using a high-resolution magnetic force microscopy, it is, for the first time, observed a new lattice form of noncollinear spin textures in the kagome ferromagnet in zero magnetic field. Under the influence of the sixfold rotational symmetry of the kagome lattice, the spin textures are hexagonal in shape and can further form a honeycomb lattice structure. Subsequent thermal cycling measurements reveal that these spin textures transform into a non-uniform in-plane ferromagnetic ground state at low temperatures and can fully rebuild at elevated temperatures, showing a strong second-order phase transition feature. Moreover, some out-of-plane magnetic moments persist at low temperatures, supporting the Kane-Mele scenario in explaining the emergence of the Dirac gap. The observations establish that the electronic properties, including both charge and spin orders, are strongly coupled with the kagome lattices.

Highly loaded bimetallic iron-cobalt catalysts for hydrogen release from ammonia.

Ammonia is a storage molecule for hydrogen, which can be released by catalytic decomposition. Inexpensive iron catalysts suffer from a low activity due to a too strong iron-nitrogen binding energy compared to more active metals such as ruthenium. Here, we show that this limitation can be overcome by combining iron with cobalt resulting in a Fe-Co bimetallic catalyst. Theoretical calculations confirm a lower metal-nitrogen binding energy for the bimetallic catalyst resulting in higher activity. Operando spectroscopy reveals that the role of cobalt in the bimetallic catalyst is to suppress the bulk-nitridation of iron and to stabilize this active state. Such catalysts are obtained from Mg(Fe,Co)2O4 spinel pre-catalysts with variable Fe:Co ratios by facile co-precipitation, calcination and reduction. The resulting Fe-Co/MgO catalysts, characterized by an extraordinary high metal loading reaching 74 wt.%, combine the advantages of a ruthenium-like electronic structure with a bulk catalyst-like microstructure typical for base metal catalysts.

Atomic imaging with a 12 T magnetic field perpendicular or parallel to the sample surface by an ultra-stable scanning tunneling microscope.

We present the first nonmetallic scanning tunneling microscope (STM) featuring an ultra-stable tip-sample mechanical loop and capable of atomic-resolution imaging within a 12 T magnetic field that could be either perpendicular or parallel to the sample surface. This is also the first STM with an ultra-stable tip-sample mechanical loop but without a standalone scanner. The STM head is constructed only with two parts: an improved spider-drive motor and a zirconia tip holder. The motor performs both the coarse approach and atomic imaging. A supporting spring is set at the fixed end of the motor tube to decrease the tip-sample mechanical loop. The zirconia tip holder performs as the frame of the whole STM head. With the novel design, the STM head in three dimensions can be as small as 7.9 mm × 7.9 mm × 26.5 mm. The device's excellent performance is demonstrated by atomic-resolution images of graphite and NbSe2 obtained at 300 K and 2 K, as well as the high-resolution dI/dV spectrums of NbSe2 at variable temperatures. Low drift rates in the X-Y plane and Z direction further prove the imaging stability of our new STM. High-quality imaging of the Charge Density Wave (CDW) structure on a TaS2 surface shows the STM's good application capability. Continuous atomic images obtained in magnetic fields rangs from 0 T to 12 T with the direction of the magnetic field perpendicular or parallel to the sample surface show the STM's good immunity to high magnetic fields. Our results illustrate the new STM's broad application ability in extreme conditions of low temperature and high magnetic field.

Positioning and atomic imaging of micron-size graphene sheets by a scanning tunneling microscope.

We present a mechanism for directly positioning the tip over a micron-size sample by tracking the trajectory of the tip and tip shadow. A bilayer graphene sheet identified by Raman spectroscopy with a lateral size of 20 µm × 50 µm was transferred on the surface of shaped gold electrodes, on which it will be rapidly captured by a homebuilt scanning tunneling microscopy (STM) with the help of an optical microscope. Using the improved line-based imaging mode, atomic-resolution images featuring a hexagonal lattice structure on the bilayer graphene sheet were obtained by our positioning-capable STM. We have also observed a unique O-ring superstructure on graphene surface that caused by the collective interference near the boundaries or defects. Furthermore, we successfully captured a graphene sheet of size as small as 1.3 nm by a rapid and large-area searching operation; this is the first time that such a small graphene sheet has been observed with atomic resolution. The STM images of a micron-size graphene sheet illustrate the significant positioning ability and imaging precision of our homebuilt STM. Our results contribute to further STM studies on samples with ultra-small size.

Atomic-Resolution Imaging of Micron-Sized Samples Realized by High Magnetic Field Scanning Tunneling Microscopy.

Scanning tunneling microscopy (STM) can image material surfaces with atomic resolution, making it a useful tool in the areas of physics and materials. Many materials are synthesized at micron size, especially few-layer materials. Limited by their complex structure, very few STMs are capable of directly positioning and imaging a micron-sized sample with atomic resolution. Traditional STMs are designed to study the material behavior induced by temperature variation, while the physical properties induced by magnetic fields are rarely studied. In this paper, we present the design and construction of an atomic-resolution STM that can operate in a 9 T high magnetic field. More importantly, the homebuilt STM is capable of imaging micron-sized samples. The performance of the STM is demonstrated by high-quality atomic images obtained on a graphite surface, with low drift rates in the X-Y plane and Z direction. The atomic-resolution image obtained on a 32-µm graphite flake illustrates the new STM's ability of positioning and imaging micron-sized samples. Finally, we present atomic resolution images at a magnetic field range from 0 T to 9 T. The above advantages make our STM a promising tool for investigating the quantum hall effect of micron-sized layered materials.

A Novel Atomically Resolved Scanning Tunneling Microscope Capable of Working in Cryogen-Free Superconducting Magnet.

We present a novel homebuilt scanning tunneling microscope (STM) with atomic resolution integrated into a cryogen-free superconducting magnet system with a variable temperature insert. The STM head is designed as a nested structure of double piezoelectric tubes (PTs), which are connected coaxially through a sapphire frame whose top has a sample stage. A single shaft made of tantalum, with the STM tip on top, is held firmly by a spring strip inside the internal PT. The external PT drives the shaft to the tip-sample junction based on the SpiderDrive principle, and the internal PT completes the subsequent scanning and imaging work. The STM head is simple, compact, and easy to assemble. The excellent performance of the device was demonstrated by obtaining atomic-resolution images of graphite and low drift rates of 30.2 pm/min and 41.4 pm/min in the X-Y plane and Z direction, respectively, at 300K. In addition, we cooled the sample to 1.6 K and took atomic-resolution images of graphite and NbSe2. Finally, we performed a magnetic field sweep test from 0 T to 9 T at 70 K, obtaining distinct graphite images with atomic resolution under varying magnetic fields. These experiments show our newly developed STM's high stability, vibration resistance, and immunity to high magnetic fields.

A cryogen-free superconducting magnet based scanning tunneling microscope for liquid phase measurement.

Scanning tunneling microscopes (STMs) that work in ultra-high vacuum and low temperatures are commonly used in condensed matter physics, but an STM that works in a high magnetic field to image chemical molecules and active biomolecules in solution has never been reported. Here, we present a liquid-phase STM for use in a 10 T cryogen-free superconducting magnet. The STM head is mainly constructed with two piezoelectric tubes. A large piezoelectric tube is fixed at the bottom of a tantalum frame to perform large-area imaging. A small piezoelectric tube mounted at the free end of the large one performs high-precision imaging. The imaging area of the large piezoelectric tube is four times that of the small one. The high compactness and rigidity of the STM head make it functional in a cryogen-free superconducting magnet with huge vibrations. The performance of our homebuilt STM was demonstrated by the high-quality, atomic-resolution images of a graphite surface, as well as the low drift rates in the X-Y plane and Z direction. Furthermore, we successfully obtained atomic-resolution images of graphite in solution conditions while sweeping the field from 0 to 10 T, illustrating the new STM's immunity to magnetic fields. The sub-molecular images of active antibodies and plasmid DNA in solution conditions show the device's capability of imaging biomolecules. Our STM is suitable for studying chemical molecules and active biomolecules in high magnetic fields.