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For the first time, a series of MXene (Ti3C2Tx)/Bi2WO6 Schottky junction piezocatalysts were constructed, and the piezocatalytic hydrogen evolution activity was explored. Optimal Ti3C2Tx/Bi2WO6 exhibits the highest piezocatalytic hydrogen evolution rate of 764.4 µmol g-1 h-1, which is nearly 8 times higher than that of pure Ti3C2Tx and twice as high as that of Bi2WO6. This value also surpasses that of most recently reported typical piezocatalysts. Moreover, related experimental results and density functional theory calculations reveal that Ti3C2Tx/Bi2WO6 can provide unique channels for efficient electron transfer, enhance piezoelectric properties, optimize the adsorption Gibbs free energy of water, reduce activation energy for hydrogen atoms, endow robust separation capacity of charge carrier, and restrict the electron-hole recombination rate, thus significantly promoting the efficiency of hydrogen evolution reaction. Ultimately, we have unraveled an innovative piezocatalytic mechanism. This work broadens the scope of MXene materials in a sustainable energy piezocatalysis application.
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The weak electronic interaction at metal-photocatalyst heterointerfaces often compromises solar-to-fuel performance. Here, a trifunctional Schottky junction, involving chemically stabilized ultrafine platinum nanoparticles (Pt NPs, ≈3 nm in diameter) on graphitic carbon nitride nanosheets (CNs) is proposed. The Pt-CN electronic interaction induces a 1.5% lattice compressive strain in Pt NPs and maintains their ultrafine size, effectively preventing their aggregation during photocatalytic reactions. Density functional theory calculations further demonstrate a significant reduction in the Schottky barrier at the chemically bonded CN-Pt heterointerface, facilitating efficient interfacial electron transfer, as supported by femtosecond transient absorption spectra (fs-TAS) measurements. The combined effects of lattice strain, stabilized Pt NPs, and efficient interfacial charge transport collaboratively enhance the photocatalytic performance, leading to over an 11-fold enhancement in visible light H2 production (8.52 mmol g-1 h-1) compared to the CN nanosheets with the in situ photo-deposited Pt NPs (0.76 mmol g-1 h-1). This study highlights the effectiveness of strong metal-semiconductor electronic interactions and underscores the potential for developing high-efficiency photocatalysts.
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The prodigious employment of fossil fuels to conquer the global energy demand is becoming a dreadful threat to the human society. This predicament is appealing for a potent photocatalyst that can generate alternate energy sources via solar to chemical energy conversion. With this interest, we have fabricated a ternary heterostructure of Ti3C2 nanosheet modified g-C3N4/Bi2O3 (MCNRBO) Z-scheme photocatalyst through self-assembly process. The morphological analysis clearly evidenced the close interfacial interaction between g-C3N4 nanorod, Bi2O3 and Ti3C2 nanosheets. The oxygen vacancy created on Bi2O3 surface, as suggested by XPS and EPR analysis, supported the Z-scheme heterojunction formation between g-C3N4 nanorod and Bi2O3 nanosheets. The collaborative effect of Z-scheme and Schottky junction significantly reduced charge transfer resistance promoting separation efficiency of excitons as indicated from PL and EIS analysis. The potential of MCNRBO towards photocatalytic application was investigated by H2O2 and H2 evolution reaction. A superior photocatalytic H2O2 and H2 production rate for MCNRBO is observed, which are respectively around 5 and 18 folds higher as compared to pristine CNR nanorod. The present work encourages for the development of a noble, eco-benign and immensely efficient dual heterojunction based photocatalyst, which can acts as saviour of human society from energy crisis.
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BACKGROUND: Most bone defects caused by bone disease or trauma are accompanied by infection, and there is a high risk of infection spread and defect expansion. Traditional clinical treatment plans often fail due to issues like antibiotic resistance and non-union of bones. Therefore, the treatment of infected bone defects requires a strategy that simultaneously achieves high antibacterial efficiency and promotes bone regeneration. RESULTS: In this study, an ultrasound responsive vanadium tetrasulfide-loaded MXene (VSM) Schottky junction is constructed for rapid methicillin-resistant staphylococcus aureus (MRSA) clearance and bone regeneration. Due to the peroxidase (POD)-like activity of VS4 and the abundant Schottky junctions, VSM has high electron-hole separation efficiency and a decreased band gap, exhibiting a strong chemodynamic and sonodynamic antibacterial efficiency of 94.03%. Under the stimulation of medical dose ultrasound, the steady release of vanadium element promotes the osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs). The in vivo application of VSM in infected tibial plateau bone defects of rats also has a great therapeutic effect, eliminating MRSA infection, then inhibiting inflammation and improving bone regeneration. CONCLUSION: The present work successfully develops an ultrasound responsive VS4-based versatile sonosensitizer for robust effective antibacterial and osteogenic therapy of infected bone defects.
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Staphylococcus aureus Resistente a Meticilina , Osteogénesis , Humanos , Ratas , Animales , Vanadio/farmacología , Regeneración Ósea , Antibacterianos/farmacologíaRESUMEN
Defect engineering in perovskite thin films has attracted extensive attention recently due to the films' atomic-scale modification, allowing for remarkable flexibility to design novel nanostructures for next generation nanodevices. However, the defect-assisted three-dimensional nanostructures in thin film matrices usually has large misfit strain and thus causes unstable thin film structures. In contrast, defect-assisted one- or two-dimensional nanostructures embedded in thin films can sustain large misfit strains without relaxation, which make them suitable for defect engineering in perovskite thin films. Here, we reported the fabrication and characterization of edge-type misfit dislocation-assisted two-dimensional BiMnOx nanochannels embedded in SrTiO3/La0.7Sr0.3MnO3/TbScO3 perovskite thin films. The nanochannels are epitaxially grown from the surrounding films without noticeable misfit strain. Diode-like current rectification was spatially observed at nanochannels due to the formation of Schottky junctions between BiMnOx nanochannels and conducting La0.7Sr0.3MnO3 thin films. Such atomically scaled heterostructures constitute more flexible ultimate functional units for nanoscale electronic devices.
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An oxygen vacancy-tailored Schottky heterostructure composed of polyvinylpyrrolidone-assisted Bi2 Sn2 O7 (PVPBSO) nanocrystals and moderate work function graphene (mWFG, WF = 4.36 eV) is designed, which in turn intensifies the built-in voltage and interface dipole across the space charge region (SCR), leading to the inversion of majority carriers for facilitating K+ transport/diffusion behaviors. Thorough band-alignment experiments and interface simulations reveal the dynamics between deficient BSO and mWFG, and how charge redistribution within the SCR leads to carrier inversion, demonstrating the impact of different defect engineering degrees on the amplification of Schottky junctions. The ordered transport of bipolar carriers can boost electrons and K ions easily passing through the inner and outer surfaces of the heterostructure. With high activity and low resistance in electrochemical reactions, the PVPBSO/mWFG exhibits an attractive capacity of 430 mA h g-1 and a rate capability exceeding 2000 mA g-1 , accompanied by minimal polarization and efficient utilization of conversion-alloying reactions. The substantial cell capacity and high-redox plateau of PVPBSO/mWFG//PB contribute to the practical feasibility of high-energy full batteries, offering long-cycle retention and high-voltage output. This study emphasizes the direct importance of interface and junction engineering in improving the efficiency of diverse electrochemical kinetic and diffusion processes for potassium-ion batteries.
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High operating temperature (HOT) broadband photodetectors are urgently necessary for extreme condition applications in infrared-guided missiles, infrared night vision, fire safety imaging, and space exploration sensing. However, conventional photodetectors show dramatic carrier mobility decreases and carrier losses with low photoresponsivity at HOT due to the increased carrier scattering in channels at high temperatures. Herein, the HOT broadband photodetectors from room temperature to 470 K are developed for the first time by large-area black phosphorus (BP)/PtSe2 films device arrays via a depletion-enhanced photocarrier dynamics strategy. Attributed to the 2D Schottky junction at BP/PtSe2 interface and resulting in full depleted working channels, the BP/PtSe2 photodetector arrays exhibit high tolerance to carrier mobility decrease during the increasing operating temperature in a wide wavelength range from 532 to 2200 nm. Thus, the photodetector shows a state-of-the-art operating temperature at 470 K with the photo-responsivity (R) and specific detectivity (D*) of 25 A W-1 and 6.4 × 1011 Jones under 1850 nm illumination, respectively. Moreover, BP/PtSe2 photodetector arrays show high-uniformity photo-response in a large area. This work provides new strategies for high-performance broadband photodetector arrays with HOT by Schottky junction of large-area BP/PtSe2 films.
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Regulating electronic structures of the active site by manipulating the local coordination is one of the advantageous means to improve photocatalytic hydrogen evolution (PHE) kinetics. Herein, the ZnIn2 S4 /Mo2 TiC2 Schottky junctions are designed to be constructed through the interfacial local coordination of In3+ with the electronegative O terminal group on Mo2 TiC2 based on the different work functions. Kelvin probe force microscopy and charge density difference reveal that an electronic unidirectional transport channel across the Schottky interface from ZnIn2 S4 to Mo2 TiC2 is established by the formed local nucleophilic/electrophilic region. The increased local electron density of Mo2 TiC2 inhibits the backflow of electrons, boosts the charge transfer and separation, and optimizes the hydrogen adsorption energy. Therefore, the ZnIn2 S4 /Mo2 TiC2 photocatalyst exhibits a superior PHE rate of 3.12 mmol g-1 h-1 under visible light, reaching 3.03 times that of the pristine ZnIn2 S4 . This work provides some insights and inspiration for preparing MXene-based Schottky catalysts to accelerate PHE kinetics.
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Selective oxidation of biomass-based molecules to high-value chemicals in conjunction with hydrogen evolution reaction (HER) is an innovative photocatalysis strategy. The key challenge is to design bifunctional photocatalysts with suitable band structures, which can achieve highly efficient generation of high-value chemicals and hydrogen. Herein, NiS/Cd0.6 Zn0.4 S Schottky junction bifunctional catalysts are constructed for sunlight-driven catalytic vanillyl alcohol (VAL) selective oxidation towards vanillin (VN) coupling HER. At optimal conditions, the 8% NiS/Cd0.6 Zn0.4 S photocatalyst achieves high activity of VN production (3.75 mmol g-1 h-1 ) and HER (3.84 mmol g-1 h-1 ). It also exhibits remarkable VAL conversion (66.9%), VN yield (52.1%), and selectivity (77.8%). The photocatalytic oxidation of VAL proceeds a carbon-centered radical mechanism via the cleavage of αC-H bond. Experimental results and theoretical calculations show that NiS with metallic properties enhances the electron transfer capability. Importantly, a Ni-S-Cd "electron bridge" formed at the interface of NiS/Cd0.6 Zn0.4 S further improves the separation/transfer of electrone/h+ pairs and also furnishes HER active sites due to its smaller the |ΔGH* | value, thereby resulting in a remarkably HER activity. This work sheds new light on the selective catalytic oxidation VAL to VN coupling HER, with a new pathway towards achieving its efficient HER efficiency.
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We present a straightforward approach to develop a high-detectivity silicon (Si) sub-bandgap near-infrared (NIR) photodetector (PD) based on textured Si/Au nanoparticle (NP) Schottky junctions coated with graphene film. This is a photovoltaic-type PD that operates at 0 V bias. The texturing of Si is to trap light for NIR absorption enhancement, and Schottky junctions facilitate sub-bandgap NIR absorption and internal photoemission. Both Au NPs and the texturing of Si were made in self-organized processes. Graphene offers additional pathways for hot electron transport and to increase photocurrent. Under 1319 nm illumination at room temperature, a responsivity of 3.9 mA/W and detectivity of 7.2 × 1010 cm × (Hz)1/2/W were obtained. Additionally, at -60 °C, the detectivity increased to 1.5 × 1011 cm × (Hz)1/2/W, with the dark current density reduced and responsivity unchanged. The result of this work demonstrates a facile method to create high-performance Si sub-bandgap NIR PDs for promising applications at ambient temperatures.
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Grafito , Nanopartículas del Metal , Oro , Silicio , Películas CinematográficasRESUMEN
Photocatalytic valorization and selective transformation of biomass-derived platform compounds offer great opportunities for efficient utilization of renewable resources under mild conditions. Here, the novel three-dimensional hierarchical flower-like CdS/Ti3 C2 Schottky junction (MCdS) composed of surface-controlled CdS and pretreated Ti3 C2 MXene is created for photocatalytic dehydrogenation-reductive amination of biomass-derived amino acid production under ambient temperature with unprecedented activity and selectivity. Schottky junction efficiently promotes photoexcited charge migration and separation and inhibits photogenerated electron-hole recombination, which results in a super-high activity. Meanwhile, CdS with the reduced surface energy supplies sufficient hydrogen sources for imine reduction and induces the preferential orientation of alanine, thus contributing superior selectivity. Moreover, a wide range of hydroxyl acids are successfully converted into corresponding amino acids and even one-pot conversion of glucose to alanine is easily achieved over MCdS. This work illustrates the mechanism of crystal orientation control and heterojunction construction in controlling catalytic behavior of photocatalytic nanoreactor, providing a paradigm for construction of MXene-based heterostructure.
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Photocatalysis presents a feasible option to control low-concentration NO emissions from industrial burning facilities, and increasing excitons in quantity and improving surface activity are the crucial issues to be solved. Plasmonic silver with the orientation of the (111) plane is uniformly distributed on the Ti-O termination of the SrTiO3 (STO) (100) plane (major). The NO conversion rate has a sixfold increment compared to pristine STO. Meanwhile, the toxic NO2 had a significant decline in the absence of water. This high performance could be attributed to the unique property of the localized surface plasmonic resonance of silver particles, which increases the optical response range of the catalyst. Meanwhile, the formation of a Schottky junction could promote the charge separation and enhance the lifetime of excitons via the electron transfer from silver particles to STO. More importantly, the Ag-O bond of the heterojunction increases the charge density of adjacent Ti, preferring to bond with the antibonding orbital electron of adsorbed molecules, which offers a favorable channel for the NO adsorption and activation of reactive oxidation species.
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Photoelectrochemical (PEC) detection as a potential development strategy for Cu2+ ion sensor has arisen extensive attention. Herein, CdS/Ti3C2 heterostructure was synthesized by electrostatically driven assembly and hydrothermal method. On the basis of a CdS/Ti3C2 heterostructure, a novel anodic PEC sensing platform was constructed for highly sensitive detection of trace amount of Cu2+. Carrier transport at the interface of CdS/Ti3C2 heterostructure was tremendously improved, due to the generation of effective Schottky junctions. Under visible light irradiation, the CdS/Ti3C2 heterostructure-modified PEC platform exhibits great anode photocurrent signal, and the formation of CuxS reduces the PEC response with the presence of Cu2+ as a representative analyte. Thus, the linear response of Cu2+ ranges from 0.1 nM to 10 µM and the limits of detection (LOD, 0.05 nM) are obtained, which is lower than that of WHO's Guidelines for Drinking-water Quality (30 µM). This idea of component reconstitution provides a new paradigm for the design of advanced PEC sensors.
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Técnicas Biosensibles , Técnicas Electroquímicas , Técnicas Biosensibles/métodos , Electrodos , Luz , Límite de Detección , Titanio/químicaRESUMEN
To meet the fast-growing need for broad applications in remote sensing, novel optoelectronic devices with high detectivity in full bands and room temperature operation are urgently desired. This paper reports our progress in developing a specially designed photovoltaic detector by integrating a monolayer graphene onto a silicon-based nanopillar array standing on a p-n junction. Optoelectronic measurements of the fabricated detectors show that the monolayer graphene plays a critical role in device performance. Compared with the one without the graphene covering, the new device demonstrates significant improvements in the specific detectivity of 1.43 × 1013 Jones and the responsivity exceeding â¼106 V/W with a reduced leakage current corresponding to a quantum efficiency of 74.8% at 860 nm wavelength. Moreover, such sensing performance remained unaffected over the entire band from 450 to 1100 nm at room temperature, which is suitable for broadband imaging applications.
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We report on the evidence of negative capacitance values in a system consisting of metal-semiconductor-metal (MSM) structures, with Schottky junctions made of zinc oxide thin films deposited by Atomic Layer Deposition (ALD) on top of platinum interdigitated electrodes (IDE). The MSM structures were studied over a wide frequency range, between 20 Hz and 1 MHz. Light and mechanical strain applied to the device modulate positive or negative capacitance and conductance characteristics by tuning the flow of electrons involved in the conduction mechanisms. A complete study was carried out by measuring the capacitance and conductance characteristics under the influence of both dark and light conditions, over an extended range of applied bias voltage and frequency. An impact-loss process linked to the injection of hot electrons at the interface trap states of the metal-semiconductor junction is proposed to be at the origin of the apparition of the negative capacitance values. These negative values are preceded by a local increase of the capacitance associated with the accumulation of trapped electrons at the interface trap states. Thus, we propose a simple device where the capacitance values can be modulated over a wide frequency range via the action of light and strain, while using cleanroom-compatible materials for fabrication. These results open up new perspectives and applications for the miniaturization of highly sensitive and low power consumption environmental sensors, as well as for broadband impedance matching in radio frequency applications.
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Hall-effect in semiconductors has wide applications for magnetic field sensing. Yet, a standard Hall sensor retains two problems: its linearity is affected by the non-uniformity of the current distribution; the sensitivity is bias-dependent, with linearity decreasing with increasing bias current. In order to improve the performance, we here propose a novel structure which realizes bias-free, photo-induced Hall sensors. The system consists of a semi-transparent metal Pt and a semiconductor Si or GaAs to form a Schottky contact. We systematically compared the photo-induced Schottky behaviors and Hall effects without net current flowing, depending on various magnetic fields, light intensities and wavelengths of Pt/GaAs and Pt/Si junctions. The electrical characteristics of the Schottky photo-diodes were fitted to obtain the barrier height as a function of light intensity. We show that the open-circuit Hall voltage of Pt/GaAs junction is orders of magnitude lower than that of Pt/Si, and the barrier height of GaAs is smaller. It should be attributed to the surface states in GaAs which block the carrier drifting. This work not only realizes the physical investigations of photo-induced Hall effects in Pt/GaAs and Pt/Si Schottky junctions, but also opens a new pathway for bias-free magnetic sensing with high linearity and sensitivity comparing to commercial Hall-sensors.
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Although photocatalysis is one of the most promising technologies for environmental and energy issues, the irreconcilable contradiction between the absorption of the visible light and the strong redox capability of the photocatalyst and the low photocatalytic reaction kinetics result in the poor efficiency. Here, a composite photocatalyst is reported with high redox capability and accelerated reaction kinetics synergistically utilizing 2D semiconducting structural advantages and the noble-metal-free Schottky junction effect. The 2D structure can not only increase the bandgap of the photocatalyst but also improve the transfer and separation of the photogenerated charge carriers. Furthermore, the introduction of the noble-metal-free Schottky junction effect accelerates the photocatalytic reaction kinetics. The Schottky barrier can also prevent the photogenerated charges trapped by the electron acceptor from flowing back to the semiconductor, which can further boost the photocatalytic performance. The transfer process of the photogenerated charge carriers is also researched in detail by the comprehensive characterization methods, which enable the photocatalytic mechanism to be revealed.
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Understanding the electronic structure and charge carrier dynamics of supported clusters is important due to their many potential applications in photochemistry and catalysis. In this investigation, photoemission spectroscopy, in conjunction with femtosecond extreme ultraviolet (XUV) laser pulses, is used to investigate the electronic structure and ultrafast charge carrier dynamics at a Si(100) surface decorated with Zn clusters. Static photoemission spectroscopy is used to investigate the changes in the electronic structure as the dimensionality of the Zn is increased from small clusters composed of a very few atoms to metallic Zn particles. Furthermore, femtosecond optical-pump XUV-probe photoemission spectroscopy is employed to induce a charge transfer from the p-Si(100) substrate to the Zn clusters and to measure in real time the charge trapping at the Zn cluster as well as the subsequent charge relaxation. The ultrafast charge carrier dynamics are also investigated for small clusters and metallic Zn particles. Significant transient charging of the Zn clusters after excitation of the Si(100) substrate by 800 nm light is observed for Zn coverages greater than 0.12 ML Zn, which coincides with the formation of a Schottky barrier at the interface between the Zn particle and the p-Si(100) substrate. The transient signals show that the charge trapping time at the Zn cluster varies with the cluster size, which is rationalized based on the electronic structure of the cluster as well as the band energy alignment at the Zn cluster-Si(100) junction.
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Nano-size photocatalysts exhibit multifunctional properties that opened the door for improved efficiency in energy, environment, and health care applications. Among the diversity of catalyst Quantum dots are a class of nanomaterials having a particle size between 2 and 10â¯nm, showing unique optoelectrical properties that are limited to some of the metal, metal oxide, metal chalcogenides, and carbon-based nanostructures. These unique characteristics arise from either pristine or binary/ternary composites where noble metal/metal oxide/metal chalcogenide/carbon quantum dots are anchored on the surface of semiconductor photocatalyst. It emphasized that properties, as well as performance of photocatalytic materials, are greatly influenced by the choice of synthesis methods and experimental conditions. Among the chemical methods, photo-deposition, precipitation, and chemical reduction, are the three most influential synthesis approaches. Further, two types of quantum dots namely metal based and carbon-based materials have been highlighted. Based on the optical, electrical and surface properties, quantum dots based photocatalysts have been divided into three categories namely (a) photocatalyst (b) co-catalyst and (c) photo-sensitizer. They showed enhanced photocatalytic performance for hydrogen production under visible/UV-visible light irradiation. Often, pristine metal chalcogenides as well as metal/metal oxide/carbon quantum dots attached to a semiconductor particle exhibit enhanced the photocatalytic activity for hydrogen production through absorption of visible light. Alternatively, noble metal quantum dots, which provide plenty of defects/active sites facilitate continuous hydrogen production. For instance, production of hydrogen in the presence of sacrificial agents using metal chalcogenides, metal oxides, and coinage metals based catalysts such as CdS/MoS2 (99,000⯵molâ¯h-1g-1) TiO2-Ni(OH)2 (47,195⯵molâ¯h-1g-1) and Cu/Ag-TiO2 nanotubes (56,167⯵molâ¯h-1g-1) have been reported. Among the carbon-based nanostructures, graphitic C3N4 and carbon quantum dots composites displayed enhanced hydrogen gas (116.1⯵molâ¯h-1) production via overall water splitting. This review accounts recent findings on various chemical approaches used for quantum dots synthesis and their improved materials properties leading to enhanced hydrogen production particularly under visible light irradiation. Finally, the avenue to improve quantum efficiency further is proposed.
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Grafito , Puntos Cuánticos , Catálisis , Hidrógeno , SemiconductoresRESUMEN
The Schottky junction is an important unit in electronics and optoelectronics. However, its properties greatly degrade with device miniaturization. The fast development of circuits has fueled a rapid growth in the study of two-dimensional (2D) crystals, which may lead to breakthroughs in the semiconductor industry. Here we report a floating-gate manipulated nonvolatile ambipolar Schottky junction memory from stacked all-2D layers of graphene-BP/h-BN/graphene (BP, black phosphorus; h-BN, hexagonal boron nitride) in a designed floating-gate field-effect Schottky barrier transistor configuration. By manipulating the voltage pulse applied to the control gate, the device exhibits ambipolar characteristics and can be tuned to act as graphene-p-BP or graphene-n-BP junctions with reverse rectification behavior. Moreover, the junction exhibits good storability properties of more than 10 years and is also programmable. On the basis of these characteristics, we further demonstrate the application of the device to dual-mode nonvolatile Schottky junction memories, memory inverter circuits, and logic rectifiers.