In Situ Tracking of Water Oxidation Generated Nanoscale Dynamics in Layered Double Hydroxides Nanosheets.

Layered double hydroxides (LDHs) are potential catalysts for water oxidation, and it is recognized that they undergo dynamic evolution during the operation. However, little is known about the interfacial behaviors at the nanoscale under working conditions nor the underlying effects on electrocatalytic performance. Herein, using electrochemical atomic force microscopy, we in situ visualize the heterogeneous evolution of LDH nanosheets during oxygen evolution reaction (OER). By further combining density functional theory calculations, we elucidate the origin of the heterogeneous dynamics and their impact on the OER efficiency. Our findings demonstrate that NiCo LDHs transform to the catalytically active NiCoOx(OH)2-x phase during OER, and the redox transition between is accompanied by compressive and tensile strain, leading to in-plane contraction and reversible expansion of the nanosheets. Nonisotropic strain and out-of-plane strain relaxation due to defects and interparticle interactions result in cracking and wrinkling in the nanostructure, which is responsible for the partial activation and long-term deterioration of LDH electrocatalysts toward the OER. With this knowledge, we suggest and validate that engineering defects can precisely tune these dynamic behaviors, improving the OER activity and stability among LDH-based electrocatalysts.

Waterproof molecular monolayers stabilize 2D materials.

Two-dimensional van der Waals materials have rich and unique functional properties, but many are susceptible to corrosion under ambient conditions. Here we show that linear alkylamines n-C m H2m+1NH2, with m = 4 through 11, are highly effective in protecting the optoelectronic properties of these materials, such as black phosphorus (BP) and transition-metal dichalcogenides (TMDs: WS2, 1T'-MoTe2, WTe2, WSe2, TaS2, and NbSe2). As a representative example, n-hexylamine (m = 6) can be applied in the form of thin molecular monolayers on BP flakes with less than 2-nm thickness and can prolong BP's lifetime from a few hours to several weeks and even months in ambient environments. Characterizations combined with our theoretical analysis show that the thin monolayers selectively sift out water molecules, forming a drying layer to achieve the passivation of the protected 2D materials. The monolayer coating is also stable in air, H2 annealing, and organic solvents, but can be removed by certain organic acids.

In Situ Resistive Switching Effect Scrutinization on Co-Designed Graphene Sensor.

Resistive switching (RS), an electric property based on the forming and rupture of conductive filaments in metal-insulator-metal structures, has attracted intensive attention due to its potential application in next generation energy-efficient and area-efficient memory devices. In situ studies of the RS effect are urgently needed for its mechanism understanding and memristive performance improvement. Here investigations of both the RS effect as well as the gate tunable conductance quantization effect are realized by co-designing an Ag/SiO2 based memory structure on a graphene local sensor. This design enables self-monitoring of the working states of the memristor in real-time by virtue of the graphene sensor. These findings pave the way for further investigations of on-chip electronics and quantum physics.

Electronic Modulation of Hierarchical Spongy Nanosheets toward Efficient and Stable Water Electrolysis.

The energy conversion efficiency of water electrolysis is determined by the activity of selected catalysts. Ideal catalysts should possess not only porous architecture for high-density assembly of active sites but also a subtle electronic configuration for the optimized activity at each site. In this context, the development of stable porous hosting materials that allow the incorporation of various metal elements is highly desirable for both experimental optimization and theoretical comparison/prediction. Herein, MOF-derived spongy nanosheet arrays constructed by assembly of carbon encapsulated hetero-metal doped Ni2 P nanoparticles is presented as a superior bifunctional electrocatalyst for water splitting. This hierarchical structure can be stably retained when secondary metal dopants are introduced, providing a flexible platform for electronic modulation. The catalytic origin of activity enhancement via metal (Fe, Cr, and Mn) doping is deciphered through experimental and theoretical investigations. Combining the advantages in both morphological and electronic structures, the optimized catalyst NiMn-P exhibits remarkable activity in both hydrogen and oxygen evolution in the alkaline media, with an ultrasmall cell voltage of 1.49 V (at 10 mA cm-2 ) and high durability for at least 240 h.

In Situ Construction of Mo2 C Quantum Dots-Decorated CNT Networks as a Multifunctional Electrocatalyst for Advanced Lithium-Sulfur Batteries.

The slow redox kinetics during cycling process and the serious shuttle effect caused by the solubility of lithium polysulfides (LiPSs) dramatically hinder the practical application of Li-S batteries. Herein, a facile and scalable spray-drying strategy is presented to construct conductive polar Mo2 C quantum dots-decorated carbon nanotube (CNT) networks (MCN) as an efficient absorbent and electrocatalyst for Li-S batteries. The results reveal that the MCN/S electrode exhibits a high specific capacity of 1303.3 mAh g-1 at 0.2 C, and ultrastable cycling stability with decay of 0.019% per cycle even at 1 C. Theoretical simulation uncovers that Mo2 C exhibits much stronger binding energies for S8 and Li2 Sn . The energy barrier for the conversion between Li2 S4 and Li2 S2 decreases from 1.02 to 0.72 eV when hybriding with Mo2 C. Furthermore, in situ discharge/charge-dependent Raman spectroscopy shows that long-chain Li2 S8 configuration is generated via S8 ring opening near the first plateaus at ≈2.36 V versus Li/Li+ and the S6 2- configuration in CNT/S electrode is maintained below the potential of ≈2.30 V versus Li/Li+ , indicating that the shuttle of soluble LiPSs happens during the whole discharge process. This work provides deep insights into the polar nanoarchitecture design and scalable fabrication for advanced Li-S batteries.

Recent progress in Van der Waals 2D PtSe2.

As a new member in two-dimensional (2D) transition metal dichalcogenides (TMDCs) family, platinum diselenium (PtSe2) has many excellent properties, such as the layer-dependent band gap, high carrier mobility, high photoelectrical coupling, broadband response, etc, thus it shows good promising application in room temperature photodetectors, broadband photodetectors, transistors and other fields. Furthermore, compared with other TMDCs, PtSe2is chemical inert in ambient, showing nano-devices potential with higher performance and stability. However, up to now, the synthesis and its device applications are in its early stage. This review systematically summarized the state of the art of PtSe2from its structure, property, synthesis and potential application. Finally, the current challenges and future perspectives are outlined for the applications of 2D PtSe2.

In vitro single-cell dissection revealing the interior structure of cable bacteria.

Filamentous Desulfobulbaceae bacteria were recently discovered as long-range transporters of electrons from sulfide to oxygen in marine sediments. The long-range electron transfer through these cable bacteria has created considerable interests, but it has also raised many questions, such as what structural basis will be required to enable micrometer-sized cells to build into centimeter-long continuous filaments? Here we dissected cable bacteria cells in vitro by atomic force microscopy and further explored the interior, which is normally hidden behind the outer membrane. Using nanoscale topographical and mechanical maps, different types of bacterial cell-cell junctions and strings along the cable length were identified. More important, these strings were found to be continuous along the bacterial cells passing through the cell-cell junctions. This indicates that the strings serve an important function in maintaining integrity of individual cable bacteria cells as a united filament. Furthermore, ridges in the outer membrane are found to envelop the individual strings at cell-cell junctions, and they are proposed to strengthen the junctions. Finally, we propose a model for the division and growth of the cable bacteria, which illustrate the possible structural requirements for the formation of centimeter-length filaments in the recently discovered cable bacteria.

Engineering a Genetically Encoded Magnetic Protein Crystal.

Magnetogenetics is a new field that leverages genetically encoded proteins and protein assemblies that are sensitive to magnetic fields to study and manipulate cell behavior. Theoretical studies show that many proposed magnetogenetic proteins do not contain enough iron to generate substantial magnetic forces. Here, we have engineered a genetically encoded ferritin-containing protein crystal that grows inside mammalian cells. Each of these crystals contains more than 10 million ferritin subunits and is capable of mineralizing substantial amounts of iron. When isolated from cells and loaded with iron in vitro, these crystals generate magnetic forces that are 9 orders of magnitude larger than the forces from the single ferritin cages used in previous studies. These protein crystals are attracted to an applied magnetic field and move toward magnets even when internalized into cells. While additional studies are needed to realize the full potential of magnetogenetics, these results demonstrate the feasibility of engineering protein assemblies for magnetic sensing.

Hierarchically Porous W-Doped CoP Nanoflake Arrays as Highly Efficient and Stable Electrocatalyst for pH-Universal Hydrogen Evolution.

It is still challenging to develop high-efficiency and low-cost non-noble metal-based electrocatalysts for hydrogen evolution reaction (HER) in pH-universal electrolytes. Herein, hierarchically porous W-doped CoP nanoflake arrays on carbon cloth (W-CoP NAs/CC) are synthesized via facile liquid-phase reactions and a subsequent phosphorization process. The W-CoP NAs/CC hybrid can be directly employed as a binder-free electrocatalyst and delivers superior HER performance in pH-universal electrolytes. Especially, it delivers very low overpotentials of 89, 94, and 102 mV to reach a current density of 10 mA cm-2 in acidic, alkaline, and neutral electrolytes, respectively. Furthermore, it shows a nearly 100% Faradaic efficiency as well as superior long-term stability with no decreasing up to 36 h in pH-universal electrolytes. The outstanding electrocatalytic performance of W-CoP NAs/CC can be mainly attributed to the porous W-doped nanoflake arrays, which not only afford rich exposed active sites, but also accelerate the access of electrolytes and the diffusion of H2 bubbles, thus efficiently promoting the HER performance. This work provides a new horizon to rationally design and synthesize highly effective and stable non-noble metal phosphide-based pH-universal electrocatalysts for HER.

Recent advances in synthesis and biosensors of two-dimensional MoS2.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted tremendous research interests due to their exciting optical properties, large surface area, intercalatable morphologies and excellent electrochemically catalytic activity. Acting as the most typical member in TMDCs family, layer-dependent molybdenum disulfide (MoS2) with particular direct bandgap of 1.8 eV in monolayer has been widely applied in various biosensors with high sensitivity and selectivity. In this review, the preparation methods of MoS2, together with MoS2-based biosensors for detecting cells and biomolecules (such as glucose, DNA and antigens) would be summarized. In addition, the current challenges and future perspectives are outlined for the applications of biosensors based on 2D MoS2.

Graphene-coated microfiber Bragg grating for high-sensitivity gas sensing.

A graphene coated microfiber Bragg grating (GMFBG) for gas sensing is reported in this Letter. Taking advantage of the surface field enhancement and gas absorption of a GMFBG, we demonstrate an ultrasensitive approach to detect the concentration of chemical gas. The obtained sensitivities are 0.2 and 0.5 ppm for NH3 and xylene gas, respectively, which are tens of times higher than that of a GMFBG without graphene for tiny gas concentration change detection. Experimental results indicate that the GMFBG-based NH3 gas sensor has fast response due to its highly compact structure. Such a miniature fiber-optic element may find applications in high sensitivity gas sensing and trace analysis.

Shape-Preserved CoFeNi-MOF/NF Exhibiting Superior Performance for Overall Water Splitting across Alkaline and Neutral Conditions.

This study reported a multi-functional Co0.45Fe0.45Ni0.9-MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape-preserving two-step hydrothermal method. The resulting bowknot flake structure on NF enhanced the exposure of active sites, fostering a superior electrocatalytic surface, and the synergistic effect between Co, Fe, and Ni enhanced the catalytic activity of the active site. In an alkaline environment, the catalyst exhibited impressive overpotentials of 244 mV and 287 mV at current densities of 50 mA cm-2 and 100 mA cm-2, respectively. Transitioning to a neutral environment, an overpotential of 505 mV at a current density of 10 mA cm-2 was achieved with the same catalyst, showing a superior property compared to similar catalysts. Furthermore, it was demonstrated that Co0.45Fe0.45Ni0.9-MOF/NF shows versatility as a bifunctional catalyst, excelling in both OER and HER, as well as overall water splitting. The innovative shape-preserving synthesis method presented in this study offers a facile method to develop an efficient electrocatalyst for OER under both alkaline and neutral conditions, which makes it a promising catalyst for hydrogen production by water splitting.

Electrically tunable interlayer recombination and tunneling behavior in WSe2/MoS2 heterostructure for broadband photodetector.

Electrically tunable band structure and light-matter interaction are of great importance in designing novel devices and constructing high-integrated and high-performance photodetector systems in the future. However, tunable mechanisms on the layered semiconductor, especially the heterojunction, are still unclear. Herein, the WSe2/MoS2 phototransistor with dual-gated configuration is fabricated, and its electrical and photoelectrical conversion has been studied to show large tunability. It was found that conduction and rectification characteristics can be tuned by dual gates showing four states, p-i, p-n, i-n, and n-n, as a result of the charging and depletion of WSe2 and MoS2. The rectifying ratio can be modulated across a large range from 102.5 to 10-3.2. Its photoelectronic characteristics were observed to exhibit bipolar and wavelength-dependent behaviors. The interlayer recombination of charge carriers dominates the photoresponse of the device under the illumination of visible light, while it is dominated by interlayer tunneling under the illumination of near-infrared wavelengths. This bipolar photoresponse is associated with different states of band alignment, which can be switched by dual-gating modulation. Finally, by tuning the gate voltage, responsivities reach 27 445 A W-1 and 2827 A W-1 at wavelengths of 400 and 1010 nm at room temperature, respectively, which directly extends the response region from visible light to near-infrared.

Sm and Gd Contacts in 2D Semiconductors for High-Performance Electronics and Spintronics.

Two-dimensional (2D) semiconductors have attracted great attention due to their rich electronic properties and even been considered to have the potential to extend Moore's Law. However, the Schottky barrier between the metal and 2D semiconductor is formed due to the metal-induced gap states (MIGS), which greatly hinder the development of 2D semiconductor transistors in large-scale integrated circuits. Meanwhile, most air-stable 2D semiconductors are nonmagnetic, limiting the possibility of spintronic application. Here, we report a new strategy to suppress the MIGS and reduce the Schottky barrier height on 2D semiconductors (MoS2, WS2, and WSe2) by using lanthanide metal (Sm and Gd) contacts. It was found the lanthanide contacts exhibit a good Ohmic property with a near-zero Schottky barrier. As a result, the carrier mobility of MoS2 transistors reaches 118 cm2/(V s). Furthermore, Gd-contact MoS2 transistors show the typical magnetic property where the magnetoresistance reaches 2.7% at 5 K. By studying its spin valve effect, it was demonstrated that the nonlocal magnetoresistance is 4.1% and spin polarization is 3.25%. This study provides a promising pathway for high-performance 2D electronic and spintronics, which may open a new strategy for future computing-in-memory architecture.

Flexible Ag2Se Thermoelectric Films Enable the Multifunctional Thermal Perception in Electronic Skins.

Skin is critical for shaping our interactions with the environment. The electronic skin (E-skin) has emerged as a promising interface for medical devices to replicate the functions of damaged skin. However, exploration of thermal perception, which is crucial for physiological sensing, has been limited. In this work, a multifunctional E-skin based on flexible thermoelectric Ag2Se films is proposed, which utilizes the Seebeck effect to replicate the sensory functions of natural skin. The E-skin can enable capabilities including temperature perception, tactile perception, contactless perception, and material recognition by analyzing the thermal conduction behaviors of various materials. To further validate the capabilities of constructed E-skins, a wearable device with multiple sensory channels was fabricated and tested for gesture recognition. This work highlights the potential for using flexible thermoelectric materials in advanced biomedical applications including health monitoring and smart prosthetics.

Demonstration of complex refractive index of graphene waveguide by microfiber-based Mach-Zehnder interferometer.

The complex refractive index (CRI) of graphene waveguide (GW) is of great importance for modeling and developing graphene-based photonic or optoelectronic devices. In this paper, the CRI of the GW is investigated theoretically and experimentally, it is found that the CRI of the GW will modulate the intensity and phase of transmitting light. The phase alterations are obtained spectrally by a Microfiber-based Mach-Zehnder interferometer (MMZI), experimental results demonstrate that the CRIs of the GW vary from 2.91-i13.92 to 3.81-i14.64 for transmitting wavelengths ranging from 1510 to 1590 nm. This method cannot only be used to determine the CRI of the GW optically and provide one of the fundamental parameters for designing graphene-based optic devices for communication and sensing applications, but also is adoptable in graphene-based transformation optics for determination of the CRI of the GW at other wavelengths.

Strong Anisotropic Two-Dimensional In2Se3 for Light Intensity and Polarization Dual-Mode High-Performance Detection.

Detecting the light from different freedom is of great significance to gain more information. Two-dimensional (2D) materials with low intrinsic carrier concentration and highly tunable electronic structure have been considered as the promising candidate for future room-temperature multi-functional photodetectors. However, current investigations mainly focus on intensity-sensitive detection; the multi-dimensional photodetection such as polarization-sensitive photodetection is still in its early stage. Herein, the intensity- and polarization-sensitive photodetection based on α-In2Se3 is studied. By using angle-resolved polarized Raman spectroscopy, it is demonstrated that α-In2Se3 shows an anisotropic phonon vibration property indicating its asymmetric structure. The α-In2Se3-based photodetector has a photoelectric performance with a responsivity of 1936 A/W and a specific detectivity of 2.1 × 1013 Jones under 0.2 mW/cm2 power density at 400 nm. Moreover, by studying the polarized angle-resolved photoelectrical effect, it is found that the ratio of maximum and minimum photocurrent (dichroic ratio) reaches 1.47 at 650 nm suggesting good polarization-sensitive detection. After post-annealing, α-In2Se3 in situ converts to ß-In2Se3 which has similar in-plane anisotropic crystallinity and exhibits a dichroic ratio of 1.41. It is found that the responsivity of ß-In2Se3 is 6 A/W, much lower than that of α-In2Se3. The high-performance light intensity- and polarization-detection of α-In2Se3 enlarges the 2D anisotropic materials family and provides new opportunities for future dual-mode photodetection.

Emerging MoS2 Wafer-Scale Technique for Integrated Circuits.

As an outstanding representative of layered materials, molybdenum disulfide (MoS2) has excellent physical properties, such as high carrier mobility, stability, and abundance on earth. Moreover, its reasonable band gap and microelectronic compatible fabrication characteristics makes it the most promising candidate in future advanced integrated circuits such as logical electronics, flexible electronics, and focal-plane photodetector. However, to realize the all-aspects application of MoS2, the research on obtaining high-quality and large-area films need to be continuously explored to promote its industrialization. Although the MoS2 grain size has already improved from several micrometers to sub-millimeters, the high-quality growth of wafer-scale MoS2 is still of great challenge. Herein, this review mainly focuses on the evolution of MoS2 by including chemical vapor deposition, metal-organic chemical vapor deposition, physical vapor deposition, and thermal conversion technology methods. The state-of-the-art research on the growth and optimization mechanism, including nucleation, orientation, grain, and defect engineering, is systematically summarized. Then, this review summarizes the wafer-scale application of MoS2 in a transistor, inverter, electronics, and photodetectors. Finally, the current challenges and future perspectives are outlined for the wafer-scale growth and application of MoS2.

Highly Tunable, Broadband, and Negative Photoresponse MoS2 Photodetector Driven by Ion-Gel Gate Dielectrics.

Revealing the light-matter interaction of molybdenum disulfide (MoS2) and further improving its tunability facilitate the construction of highly integrated optoelectronics in communication and wearable healthcare, but it still remains a significant challenge. Herein, polyvinylidene fluoride and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PVDF-EMIM-TFSI) ion-gel are employed to replace the oxide to fabricate a MoS2-based phototransistor. The high capacitance enables a large tunability of the carrier concentration that results in ambipolar transport of MoS2. It is found that the photoelectrical effect of the MoS2 ion-gel phototransistor can be greatly tuned by the gate voltage including its photoresponsivity, detectivity, and response wavelength. An abnormal negative photoelectrical effect in both the electron branch and the hole branch is observed which is due to the adsorption/desorption of the C2F6NO4S2- ion. By tuning the carrier concentration, the photoresponse can be extended from the visible region to the short infrared region. At 1200 nm, the photoresponse and detectivity can be tuned as large as 0.90 A/W and 1.88 × 1011 Jones, respectively. Ultimately, by combining the tunability of gate voltage and wavelength, it is demonstrated that the photoelectrical effect is dominated by the photogating effect in the hole carrier, while it is coregulated by a photogating and photothermal effect in electron carrier. This study provides new insights for developing a highly tunable broadband photodetector with low consumption.

Si/SnSe-Nanorod Heterojunction with Ultrafast Infrared Detection Enabled by Manipulating Photo-Induced Thermoelectric Behavior.

Photothermal detectors have attracted tremendous research interest in uncooled infrared imaging technology but with a relatively slow response. Here, Si/SnSe-nanorod (Si/SnSe-NR) heterojunctions are fabricated as a photothermal detector to realize high-performance infrared response beyond the bandgap limitation. Vertically standing SnSe-NR arrays are deposited on Si by a sputtering method. Through manipulating the photoinduced thermoelectric (PTE) behavior along the c-axis, the Si/SnSe-NRs heterojunction exhibits a unique four-stage photoresponse with a high photoresponsivity of 106.3 V W-1 and high optical detectivity of 1.9 × 1010 cm Hz1/2 W-1 under 1342 nm illumination. Importantly, an ultrafast infrared photothermal response is achieved with the rise/fall time of 11.3/258.7 µs. Moreover, the coupling effect between the PTE behavior and external thermal excitation enables an improved response by 288.4%. The work not only offers a new strategy to develop high-speed photothermal detectors but also performs a deep understanding of the PTE behavior in a heterojunction system.