Impedance Spectroscopy on Hafnium Oxide‐Based Memristive Devices

Ag-dispersive chalcogenide media for readily activated electronic memristor

ABSTRACTMolybdenum disulfide (MoS2), one of the transition-metal dichalcogenides, is a 2-dimensional semiconducting material that has a layered structure. Owing to excellent optical and electronic properties, the ultra-thin MoS2 film is expected to be used for various devices, such as transistors and flexible displays. In this study, we investigated the physical and chemical properties of sputtered-MoS2 film in the sub-10-nm region by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). As the results of Raman spectroscopy investigations, we observed two Raman modes, E12g and A1g, in the 2-dimensional MoS2 films. As the thickness of the MoS2 film decreased, the peak frequency difference between E12g and A1g modes increased. From the XPS investigations, we confirmed sulfur reductions from the 2-dimensional MoS2 films. Therefore, we considered that the sulfur vacancies in the MoS2 film affected the Raman peak positions. Moreover, we performed the additional sulfurization of sputtered-MoS2 films. From the XPS and Raman investigations, the quality of the sputtered-MoS2 films was improved by the additional sulfurization.

Redox-based memristive devices (ReRAM) are considered for future energy-efficient non-volatile memory. Memristive cells enable high speed data access, low power consumption and high scalability, which is a key requirement for their use as artificial synapses in neuromorphic computing. Applications in networks of up to 106 devices require a scaling of the cell volume to about 103 nm3. For a typical valence-change-mechanism (VCM)-type switching cell with a metal oxide, like HfO2, sandwiched between two metal electrodes of different oxidation enthalpy, this means that the individual layer thickness is in the range of a few nanometers. Therefore, a control of the device properties demands for a control of interfacial reactions during device fabrication. Here, we are going to present a careful analysis of the oxidation of an Hf electrode layer during atomic layer deposition (ALD) of different metal oxides, these are Al2O3, TiO2, and HfO2. The in-situ encapsulation of a reactive metal electrode by means of an ALD metal oxide layer enables a better process control compared to stack structures formed by breaking the vacuum conditions.In this study, plasma and thermal ALD processes were used to grow ultrathin layers of Al2O3, TiO2, and HfO2 on top of Hf metal films, after transfer under UHV conditions. The growth of homogeneous metal oxide films of a few nanometer in thickness enabled a systematic analysis of the HfO2 formation at the Hf/metal oxide interface by means of angle dependent X-ray photoelectron spectroscopy (XPS). The results show that the properties of the interfacial HfO2 layer can be controlled by the metal oxide deposited on top as well as by the process chemistry and deposition temperature. In contrast to the TiO2 film, the Al2O3 layer clearly serves as oxidation barrier. In addition, the chemistry and structure of the HfO2 interfacial layer were analyzed from XPS and transmission electron microscopy analysis.Memristive device were fabricated from the Hf/HfO2/MOx stacks by depositing Pt top electrodes. The initial current of the devices scales with the pad size indicating the high quality of the insulating oxide layers. Consistent with VCM-type memristive devices the cells required an electroforming voltage to enable bipolar-type resistive switching. In this presentation, the trade-off between the two functionalities of oxidation protection versus enabling of a low electroforming voltage will be discussed.

XPS, TEM and SAD investigations of nanosized CoxByHz particles obtained by two different borohydride methods

Conduction and switching behavior of e-beam deposited polycrystalline Nb2O5 based nano-ionic memristor for non-volatile memory applications

Flexible electronic devices have generated large research interest in recent years. Herein, we demonstrate a resistive random access memory (ReRAM) device fabricated on a flexible polyethylene terepthalate (PET) substrate using a bilayer of graphene oxide (GO) and HfOx films. The physical properties of GO and HfOx were characterized by a number of techniques such as X-ray diffraction (XRD), UV–Visible absorption spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The GO/HfOx-bilayered ReRAM devices exhibited good switching behavior at low SET/RESET voltages and showed improved cell-to-cell uniformity of switching parameters compared to the devices without HfOx layer, due to the oxygen vacancies within the HfOx film as confirmed by XPS. The switching mechanism was explained by the formation/rupture of the conductive filament through the migration-induced oxidation/reduction reaction of the oxygen vacancies at the interface of GO/HfOx. From the I–V curve fitting, the conduction in low resistance state (LRS) was found to be governed by the Ohmic mechanism and the trap-controlled space charge limited current (SCLC) in high resistance state (HRS) was observed for both the cycles.

In a memristor or a so-called memristive device, the resistance state depends on the previous charge flow through the device. The new resistance state is stored and classifies a memristor as a non-volatile memory device. This likewise unique and simple feature qualifies memristive devices as attractive compartments with regard to the development of a universal memory and beyond von Neumann computing architectures, including in-memory computing and neuromorphic circuits. In this chapter, we present studies on two kinds of bi-layer metal oxide memristive devices with the layer sequences Nb/NbO$$_{\textrm{z}}$$ z /Al$$_2$$ 2 O$$_3$$ 3 /Nb$$_{\textrm{x}}$$ x O$$_{\textrm{y}}$$ y /Au and TiN/TiO$$_\textrm{x}$$ x /HfO$$_\textrm{x}$$ x /Au, either prepared by reactive DC-magnetron sputtering, etching and optical lithography. It is shown that the memristive properties of such devices can be engineered, which enables tailoring of the memristive devices for particular applications.

Developing novel memristive systems aims to implement key principles of biological neuron assemblies – plasticity, adaptivity, and self‐organization – into artificial devices for parallel, energy‐efficient computing. Solid‐state memristive devices, such as crossbar arrays and percolated nanoparticle (NP) networks, already demonstrate these properties. However, closer similarity to neural networks is expected from liquid‐state systems, including polymer melts, which remain largely unexplored. Here, the resistive switching in silver/poly(ethylene glycol) (Ag/PEG) nanofluids, prepared by depositing gas‐aggregated Ag NPs into PEGs of varying molecular mass, is investigated. These systems form long‐range conductive NP bridges with reconfigurable resistance states in response to an electric field. The zeta‐potential of Ag NPs and molecular mobility of PEG determine the prevalence of low resistance (ohmic) state, high resistance states (poor conductance) or intermediate transition states governed by space‐charge‐limited conduction or electron tunneling. The occurrence of these states is given by the interparticle gaps, which are determined by the conformation of PEG molecules adsorbed on the NPs. It is presented, for the first time, an equivalent circuit model for the Ag/PEG system. These findings pave the way to adopt polymer melts as matrices for neuromorphic engineering and bio‐inspired electronics.

Memristive devices have attracted considerable attention as a promising candidate for the next generation nonvolatile random access memory and unconventional computing. One obstacle for wide applications of these devices is their performance variation from device to device and from cycle to cycle. Here, the authors report that by introducing a thin HfO2 layer into the Pt/TiO2/Pt device geometry, the cycle-to-cycle uniformity of the programing voltages and the resistance states are greatly improved. The programing voltages are distributed in much narrower ranges. The uniformities of low-resistance state resistance and high-resistance state resistance were improved by 25 and 20 times, respectively. It is believed that the extra layer of HfO2 has led to fewer potential conducting filaments in the bilayer devices, contributing to the significant improvement in switching uniformity.

Open AccessCCS ChemistryRESEARCH ARTICLE1 May 2022Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures Yanliang Zhou†, Congying Wang†, Xuanbei Peng†, Tianhua Zhang, Xiuyun Wang, Yafei Jiang, Haifeng Qi, Lirong Zheng, Jianxin Lin and Lilong Jiang Yanliang Zhou† National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 , Congying Wang† National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 , Xuanbei Peng† National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 , Tianhua Zhang National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 , Xiuyun Wang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 , Yafei Jiang Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055 , Haifeng Qi Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 , Lirong Zheng Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 , Jianxin Lin National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 and Lilong Jiang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002 https://doi.org/10.31635/ccschem.021.202100912 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Ammonia (NH3) synthesis at mild conditions is of great significance, while the significant bottleneck of this process is the activation of N2 to realize the desired NH3 synthesis performance, which requires deep insight and rational design of active sites at the atomic level. Here, were synthesized atomically dispersed Co-based catalysts with different Co-N coordination numbers (CNs) to explore the coordination-sensitive NH3 synthesis reaction for the first time. Our studies showed that Co-based catalysts increased the NH3 synthesis rate gradually with a decrease in CN. The Co-N2 catalyst exhibited the highest NH3 synthesis rate of 85.3 mmol gCo−1 h−1 at 300 °C and 1 MPa, which outperformed most of the previously reported Co-based catalysts. Various characterizations and theoretical calculations demonstrated that atomically dispersed Co catalyst with low CN could generate more unoccupied Co 3d charges and tetrahedral cobalt(II) sites. The unoccupied Co 3d charge, in turn, promoted the electron donation from the Co active center to the antibonding π-orbital (π*) of N2 and expedites N2 hydrogenation. Furthermore, the Co-N2 catalyst with more tetrahedral cobalt(II) sites could effectively facilitate the desorption of N-containing intermediate species (such as *NH3 and *N2H4) to obtain a high NH3 synthesis rate. Download figure Download PowerPoint Introduction Ammonia (NH3) is not only an essential raw material for the synthesis of nitric acid, fertilizer, ammonium salt, and so on but also a promising renewable energy carrier.1,2 The state-of-the-art manufacture of NH3 comes from the Haber–Bosch (HB) process using iron-based catalysts that require harsh reaction conditions (400–500 °C, 10–30 MPa), thereby suffering from high energy consumption and environmental pollution problems.3–5 Therefore, it is urgent to develop effective routes that are both energy-saving and environment-friendly. Most recently, electric power generated from renewable energy sources is widely used for hydrogen (H2) production via water electrolysis. It becomes economically acceptable to NH3 synthesis from renewable H2 and N2 via an electrolysis-driven HB (eHB) process.6 The eHB route is attractive for realizing efficient utilization of renewable energy and a "carbon-free" society. However, the major challenge of NH3 synthesis lies in the activation of N2 (945 kJ mol−1) at mild conditions to realize desired NH3 synthesis rate,7 which would require a deep insight into the reaction mechanism; therefore, the development of advanced, efficient catalysts that can produce NH3 at mild conditions is beneficial. Currently, industrial applied Fe- or Ru-based catalysts that exist as nanoparticles usually obey the dissociative mechanism,8,9 requiring harsh conditions to dissociate the stable N≡N triple bond. In contrast to the N2 dissociative mechanism, most of the enzyme-catalyzed N2 fixation processes followed the associative mechanism, wherein the N≡N triple bond breaks stepwise after partial hydrogenation of the N2 molecule.10,11 Notably, the dissociation energy of the N–N bond (297 kJ/mol) from *N2H4 intermediates is less than a third of that from the N≡N triple bond. Consequently, the exploitation of advanced catalysts that obey the N2 hydrogenation process instead of direct N2 dissociation is promising for realizing the desired NH3 synthesis performance at mild conditions. Further, NH3 synthesis is a typical structure sensitivity reaction, where the pathway of N2 activation is closely related to the geometric and electronic structures of active sites.8,12 For instance, theoretical studies have demonstrated that N2 could preferentially undergo hydrogenation via an associative pathway other than direct dissociation on Ru(0001) surface,13 RhCo3 clusters,12 and Co3Mo3N catalysts.14 In addition, very recently, a limited number of researches have provided us with experimental evidence that the N2 hydrogenation to N2Hx species is preferred over atomically dispersed Ru and Co, as well as Li-promoted Ru catalysts.6,15,16 Among them, atomically dispersed catalysts present well, having the potential for NH3 synthesis at mild conditions, as the direct N2 dissociation is difficult while the N2 hydrogenation is feasible on single-atom sites.15 Meanwhile, atomically dispersed catalysts with definite structures offer the possibility to investigate the geometric and electronic effects on NH3 synthesis at the atomic level. Differing from nanoparticle catalysts, in which the particle size and crystal face usually play an important part in the reactivity, catalytic activity of atomically dispersed catalysts is mainly determined by the coordination environment of single-atom sites.17–19 However, up to now, the modulation of the coordination structure of single-atom active sites to optimize the catalytic activity of NH3 synthesis has not yet been researched. Moreover, the effects of geometric and electronic structures in these single-atom sites on the dynamic transformation of intermediates remain unclear. Herein, we synthesized a series of atomically dispersed Co-Nx (x = 2∼4) catalysts through the pyrolysis of nitrogen-anchored Co-based precursors. The coordination numbers (CNs) of Co-N over the as-prepared catalysts were modulated by varying the calcination temperature. The coordination-sensitive NH3 synthesis reaction in the case of Co-based catalyst is disclosed through a combination of a suite of elaborated experimental characterizations and theoretical calculations. The geometric and electronic structures of Co active sites could be simultaneously tuned via the modulation of Co-N CNs, which are closely related to the N2 activation and desorption of N-containing intermediate species (such as *N2H4 and *NH3), thus resulting in different catalytic behaviors in the NH3 synthesis. This finding is beneficial to rationally design advanced Co-based catalysts by regulating the geometric and electronic structures to realize efficient NH3 synthesis at mild conditions. Experimental Methods Catalyst preparation Synthesis of hollow N-doped porous carbon spheres support The synthetic method of hollow N-doped porous carbon spheres (HNPCSs) support was referenced in previous work.20 Briefly, NH3 solution (10 mL) and ethanol (240 mL) were dissolved in deionized water (80 mL) and stirred evenly at room temperature (RT). Then, tetraethyl orthosilicate (11.2 mL) was added to this solution and stirred further for 1 h. Subsequently, poloxamer, resorcinol, and formaldehyde (2.24 mL) were added to the above solution and continually stirred for 0.5 h. After the addition of melamine (1.26 g) and formaldehyde (1.68 mL), the mixture was treated at 100 °C for 24 h. After filtration and washing, the sample obtained was calcined under an Ar atmosphere at 700 °C for 2 h. Finally, the sample was etched by hydrofluoric acid (HF) solution to remove the SiO2 substrate. After filtration, washing, and drying, the resulting substance was herein referred to as HNPCSs support. Synthesis of Co-Nx and Co-NPs catalysts In detail, HNPCSs (120 mg) and cobalt phthalocyanine (CoPc; 80 mg) was dispersed in dimethylformamide (DMF; 120 mL), respectively, and the mixtures were stirred for 2 h. Then the CoPc and DMF mixed solution was added slowly to the HNPCSs suspension. After stirring for 24 h, the sample was dried in a vacuum dryer at 60 °C for 12 h. Finally, the samples were pyrolyzed under Ar atmosphere at different temperatures of 450, 550, and 650 °C for 2 h, denoted as Co-N4, Co-N3, and Co-N2, respectively. The synthetic procedure used for the Co-NPs catalyst was similar to that of Co-N2, except that the calcination was performed at 700 °C for 10 h. Synthesis of catalysts as reference The Cs-Co/MgO catalyst was synthesized by an impregnation method. In detail, a certain amount of cobalt nitrate hexahydrate and cesium nitrate was dissolved in deionized water. MgO support was added to this solution, and the mixture was stirred evenly. After impregnation at RT for 24 h, the mixture was dried at 80 °C for 24 h. The acquired catalyst was denoted as Cs-Co/MgO, in which the content of Co was the same as that over Co-N2, and the molar ratio of Cs to Co was ∼1.0. A Fe-based catalyst was purchased commercially from Fujian SJ. FD. Co. Ltd. (Fuzhou, Fujian, China) for comparative studies. NH3 synthesis performance test The NH3 synthesis activities over the as-synthesized catalysts were tested in a pressurized fixed bed reactor. In detail, the catalyst (0.2 g, 20–30 mesh) was loaded into the stainless steel reactor (inner diameter 10 mm). Before measurement, the catalysts were treated in a 25%N2–75%H2 feed gas at 300 °C for 2 h. Subsequently, the catalyst performance was evaluated in 300 °C at a weight hourly space velocity (WHSV) of 60,000 mL g−1 h−1 and 1 MPa. The outlet NH3 was trapped by diluted H2SO4 solution and then detected by ion chromatography (DIONEX, ICS-600; Thermo Scientific, Waltham, MA, USA). The turnover frequency (TOFCo) was calculated based on the total molar of Co metal using the following equation: TOF Co = r n M (1)where, r represents the NH3 synthesis rate (mol g−1 s−1), nM is the molar amounts of Co obtained from inductively coupled plasma (ICP) analysis. Catalyst characterization X-ray diffraction (XRD) measurement was recorded on a PANalytical X'Pert Pro diffractometer (PANalytical, Almelo, The Netherlands) using a Cu Kα radiation source. N2 adsorption/desorption isotherms were collected on an ASAP 2020 apparatus (MicroMetric, Lincolnshire, United Kingdom). Elemental analysis (EA) was conducted with a Vario EL-Cube instrument (Elementar, Jiangsu, China) to measure the N contents of the samples. The Co contents of the catalysts were measured by ICP atomic emission spectroscopy (ICP-AES) analysis equipped with an Ultima 2 spectrometer (Perkin-Elmer, Waltham, MA, USA). Catalyst morphologies were detected on scanning electron microscopy (SEM; a Hitachi Model S-4800; Hitachi, Tokyo, Japan). Transmission electron microscopy (TEM) images of the catalysts were obtained on a JEM-2010 instrument (JEOL Ltd., Tokyo, Japan). Aberration-corrected high-angle annular dark-field scanning TEM (AC-HAADF-STEM) analysis was performed on a JEOL JEM-ARM 200 F instrument (JEOL Ltd., Tokyo, Japan). Raman spectroscopy was measured on a multichannel modular triple Raman system (Renishaw Co., London, United Kingdom). Ultraviolet photoelectron spectroscopy (UPS) was measured using a helium resonance lamp offering He I (hν = 21.2 eV) photons. X-ray photoelectron spectroscopy (XPS) was performed on an ESCALAB 250Xi photoelectron spectrometer (Thermo Fisher Scientific, Shanghai, China) with a monochromatic Al Kα source (hν = 1486.6 eV) as the X-ray source. The XPS binding energy was referenced to the C 1s peak at 284.6 eV of adventitious carbon. Electron-paramagnetic resonance (EPR) test was performed on an E500 spectrometer (Bruker-BioSpin, Shanghai, China) with a 100 KHz magnetic field modulation at RT. UV–vis diffuse reflection spectrum (DRS) data were obtained from a Perkin Elmer Lambda 750s UV–vis spectrometer (Perkin-Elmer, Waltham, MA, USA). The productions of NH3 synthesis were trapped at the aqueous solution containing sulfuric acid and para-(dimethylamino) benzaldehyde for the UV–vis DRS measurement. X-ray absorption spectroscopy (XAS), containing X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses were performed at the 1W1B beamline of the Beijing Synchrotron Radiation Facility (BSRF), China. Spectra were collected at the Co K-edge in transmission mode with a Si (111) double crystal monochromator. The Co foil and CoPc samples were used as references. Density functional theory (DFT) calculations First-principle calculations were performed using the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof (PBE),21 as implemented in the Vienna ab initio Simulation Package (VASP 5.4.4).22 The valence electronic states of all atoms were expanded in a plane-wave basis set with a cutoff energy of 400 eV, and gamma points were used for Brillouin zone integration. All atoms were allowed to relax until the forces fell below 0.02 eV Å−1. The energy convergence criterion was set to 10−5 eV. Grimme D3 method with the zero-damping function was used to describe van der Waals interactions.23 The graphene supercell with a surface periodicity of 10 × 10, including 200 atoms as a basis, was employed to construct the Co-Nx (x = 4, 3, and 2) moieties. A vacuum space of 20 Å was used in the normal direction of the graphene plane to ensure negligible interaction between the mirror images. Results and Discussion Structure characterization The process for the synthesis of Co-Nx catalysts with different Co-N CNs is depicted in Figure 1a. The atomically dispersed Co-Nx catalysts were prepared by CoPc pyrolysis supported on HNPCSs precursor. The CN of Co-Nx catalysts was modulated by varying the pyrolysis temperature (as shown in the "Catalyst preparation" section). To highlight the coordination structure of atomically dispersed Co center, Co nanoparticle loaded on the same support (Co-NPs) was prepared for comparison. EXAFS analyses of the Co K-edge were conducted to demonstrate the coordination structure of Co-Nx catalysts. The Co K-edge EXAFS spectra of as-synthesized catalysts and reference Co foil and CoPc, are illustrated in Figure 1b. An apparent peak located at 1.5 Å for the as-synthesized Co-Nx samples was attributed to Co-N coordination, compared with CoPc reference.24 Meanwhile, no typical peaks for Co-Co coordination at 2.2 Å were visible, indicating the atomically dispersed Co atoms on these Co-Nx catalysts. Besides, the peak intensity of Co-N coordination decreased with increased pyrolysis temperature, suggesting a decrease in Co-N CN. Based on fitting results, the average CNs of Co-N of the three samples were 3.9, 3.0, and 2.1 (Table 1), and thus, the samples were denoted as Co-N4, Co-N3, and Co-N2, respectively. Additionally, the fitting result of Co K-edge EXAFS spectra of Co-N2 based on our hypothetical model was consistent with the experimental result (Figure 1c), demonstrating the validity of the depicted models. In the case of Co-NPs, the Co-Co coordination existed predominant beside the weak Co-N coordination, indicating that Co entities were distributed mainly in the form of nanoparticles. Figure 1 | (a) Schematic diagram of the preparation process of Co-Nx with different CNs. (b) Co K-edge EXAFS spectra of as-prepared samples. (c) EXAFS spectra and the corresponding curve-fitting results of Co-N2 catalyst. Download figure Download PowerPoint Table 1 | EXAFS Data Fitting Results of the As-Synthesized Catalysts Samples Shell CN R (Å)a σ2 × 102 (Å2)b ΔE0 (eV)c R-Factor (%) Co foil Co-Co 12.0 2.49 0.7 6.3 0.9 Co-N4 Co-N 3.9 1.92 0.4 8.1 0.07 Co-N3 Co-N 3.0 1.91 0.3 7.2 0.09 Co-N2 Co-N 2.1 1.89 0.3 −1.1 0.8 Co-NPs Co-N 2.0 2.03 0.7 −1.8 0.7 Co-Co 2.1 2.49 0.7 −1.8 0.7 Note: The accuracy of parameters: CN, ±20%; R, ±1%; σ2, ±20%; ΔE0, ±10%. The fitting range in k- and R-space is 3.0–12.3 Å−1 and 1.0–2.7 Å, respectively. aR, bonding distance. bσ2, the Debye–Waller factor. cΔE0, inner potential shift. SEM ( Supporting Information Figure S1) and TEM images (Figures 2a and 2b) simultaneously displayed uniform microspheres with the hollow structure of Co-Nx and Co-NPs catalysts. The average diameter of the microspheres was ∼150 nm of these samples. The high-resolution TEM (HR-TEM) images (Figure 2c and Supporting Information Figure S2) did not show any Co nanoparticles sights, implying a high dispersion of Co species as clusters or single atoms over Co-Nx catalysts. We further used the AC-HAADF-STEM characterization to inspect the Co species over Co-Nx catalysts. We found that plenty of highly dispersed Co single atoms were visible over Co-N2 (Figure 2d), Co-N3 (Figure 2e), and Co-N4 (Figure 2f) catalysts. In comparison with Co-Nx catalysts, distinct nanoparticles were observed over the Co-NPs catalyst ( Supporting Information Figure S3). Combined with the EXAFS results, we deduced that atomically dispersed Co-Nx catalysts with different Co-N CNs were synthesized successfully. Figure 2 | (a and b) TEM and (c) HR-TEM images of Co-N2 catalyst. AC-HAADF-STEM images of (d) Co-N2, (e) Co-N3, and (f) Co-N4 catalysts. Download figure Download PowerPoint The XRD patterns ( Supporting Information Figure S4) showed that all Co-Nx displayed a broad diffraction peak at ∼26.4°, to the crystal plane of carbon The highly was by Raman measurement. The Raman spectra ( Supporting Information Figure displayed that samples peaks at and corresponding to the and of or carbon and Furthermore, the intensity of the to of these samples were ( Supporting Information Table that the coordination structure has a on carbon Notably, the diffraction peaks on the Co-N4 sample are attributed to the CoPc suggesting an of CoPc species and the of Co-N4 which with the fitting results of XRD diffraction peaks were related to Co or CoPc species in the Co-N3 and Co-N2 samples. to the above EXAFS and our demonstrated that the pyrolysis of CoPc would form atomically dispersed Co sites over Co-Nx catalysts after the pyrolysis of the at 700 °C for 10 h, the of diffraction peaks at and in Co-NPs catalyst were to the (111) and crystal of Co respectively. The average size of Co nanoparticles over Co-NPs was to the of (111) crystal plane via which with the particle observed in the HR-TEM ( Supporting Information Figure S3). showed that the Co contents in these samples were distributed in the range of ( Supporting Information Table to the results, the N contents of the synthesized Co catalysts ( Supporting Information Table S1) decreased with increased pyrolysis temperature. N2 ( Supporting Information Table S1) results showed that the surface of Co-Nx catalysts increased from to g−1 with increased pyrolysis temperature. However, at a high pyrolysis temperature, the surface of Co-NPs catalyst decreased to of the geometric and electronic structure was performed to insight into the of different CNs on the geometric and electronic structure of Co sites. to the results (Figure the peak intensity in the range of eV was of the geometric of Co that tetrahedral or The from the tetrahedral of Co sites were to to this The intensity of this peak over Co-N2 was than that of Co-N3 or Co-N4, indicating that more Co were at the tetrahedral sites in the Co-N2 Besides, the of the absorption in the images (Figure could be used to the states of Co A of absorption from Co-N4 to Co-N2 was indicating that the valence of Co species decreased with decreased CN of the Co-Nx catalysts. Figure | Co K-edge spectra and the images in the range of (a) eV and (b) eV. Download figure Download PowerPoint Further, XPS were performed to obtain the valence of Co and N species over the as-synthesized catalysts. shown in Figure the Co spectra were fitting into the peaks with binding of and eV, to and peaks of surface Co were observed on these catalysts, except for Co-NPs, which with the results of XRD and The atomic ratio of over the Co-N4, Co-N3, and Co-N2 catalysts determined from XPS results were and (Table This finding was supported by the of Co entities over Co-N2 as shown in the (Figure results, that the decreased CN have been promoted to generate more unoccupied Co 3d over the Co-N2 results were further by The spectra ( Supporting Information Figure showed that the of and over these catalysts were attributed to an electron in the of and carbon We found that the intensity of increased with the of CN, indicating that more on the Co-N2 catalyst. The N 1s spectra (Figure three of N and N over Co-Nx the comparison of the content of different N species from the peak (Table we observed that the N content increased from to while the N content decreased from to with of CN over Co-Nx catalysts. This result that the atomically dispersed Co mainly with the these demonstrated that the geometric and electronic structures of the atomically dispersed Co catalyst were modulated through different CNs of the in turn, the catalytic activity the NH3 synthesis. Figure | (a) Co and (b) N 1s XPS spectra of the as-synthesized catalysts. Download figure Download PowerPoint Table 2 | The XPS Spectra Results of the As-Synthesized Catalysts Samples N (%) N (%) N (%) (%) (%) (%) Co-N4 24 60 Co-N3 12 Co-N2 20 Co Catalyst activity and Figure the NH3 synthesis rate over the as-synthesized catalysts with a 25%N2–75%H2 gas and a of mL The NH3 synthesis rate in the case of Co-N2 was 85.3 gCo−1 h−1 at mild conditions of 300 °C and 1 MPa, than over Co-N3 gCo−1 and Co-N4 gCo−1 An NH3 synthesis rate of gCo−1 h−1 was acquired over Co-NPs, which is more to over the atomically dispersed Co-Nx catalysts. Meanwhile, the NH3 synthesis rate over the carbon as support was mmol h−1 at 300 °C and 1 MPa, as shown in Supporting Information Table suggesting that the of support to the catalytic activity of Co-Nx could be results that NH3 synthesis is a coordination-sensitive reaction, and the Co-N2 catalyst with the CN the highest NH3 synthesis rate at mild conditions. It has been reported that the addition of a electronic to Co-based catalysts could NH3 synthesis performance, referred to as an electronic Herein, we the of to the highly active Co-N2 catalyst on NH3 synthesis It showed that the NH3 synthesis rate over was that of the (Figure The typical Cs-Co/MgO and the Fe-based catalysts were also performed and evaluated for comparison ( Supporting Information Table 300 °C and 1 MPa, the NH3 synthesis rate over Co-N2 mmol gCo−1 was than of Cs-Co/MgO mmol and Fe-based mmol catalysts, indicating the performance of NH3 synthesis activity over Co-N2 catalyst. For based on the total number of Co active sites on these catalysts, were calculated and depicted in Figure Notably, the of Co-N2 and were and respectively, which outperformed most of the previously reported Co-based catalysts in Supporting Information Table Figure | (a) NH3 synthesis rate based on Co content over as-synthesized catalysts at 1 and 300 (b) TOF was calculated on the total number of Co atoms basis over the catalysts. (c) N2 and (d) H2 reaction over Co-N2 and Co-NPs catalysts. Download figure Download PowerPoint A test of the Co-N2 catalyst was conducted at 300 °C and 1 MPa. shown in Supporting Information Figure the NH3 synthesis rate a stable of mmol gCo−1 h−1 a The used catalyst was further tested using HR-TEM and EXAFS shown in the Supporting Information Figure no or at different were observed over the used Co-N2 catalyst. Moreover, the Co K-edge EXAFS spectrum of the used Co-N2 catalyst ( Supporting Information Figure showed that existed the Co-N coordination, while no Co-Co coordination was indicating the of a highly stable Co-N2 active in the process of NH3 synthesis. the of these demonstrated the of Co-N2 catalyst in NH3 synthesis at mild conditions. studies studies were conducted to demonstrate the of N2 and H2 activation over the Co-Nx catalysts. The reaction of N2 and H2 usually as related to the and the of hydrogen For most catalysts, the reaction of N2 is to suggesting that the could be the direct dissociation of the N≡N triple bond. shown in Figure the reaction of N2 over Co-N2 was than that of over low reaction of N2 has been reported over Ru-based catalysts supported by or where the of bond than direct N≡N triple bond dissociation was Additionally, the reaction of H2 on Co-NPs was (Figure The demonstrated that the of H2 on Co to hydrogen

Role of iodate ions in chemical mechanical and electrochemical mechanical planarization of Ta investigated using time-resolved impedance spectroscopy

Ion-gel-based memory devices can effectively change their resistance states even at low voltages, owing to the rapid mobility of ions and the formation of an electric double layer. However, their volatile characteristics limit their use in nonvolatile memory and neuromorphic applications. In this paper, we report an ion-gel-based memristive device capable of both digital data storage and analog data processing through the incorporation of silver nanoparticles (AgNPs). The memristive device exhibited reliable resistive switching behavior, characterized by forming-free and a butterfly shaped bipolar resistive switching (BRS) profile. Notably, the ion-gel-based memristive device with AgNPs demonstrated excellent data retention for over 105 s even at 85 °C, attributed to the charge storage stability provided by Ag+-based ion pairing. In addition to memory functionality, the device successfully emulated various synaptic behaviors, including long-term potentiation (LTP), long-term depression (LTD), and the transition from short-term memory (STM) to long-term memory (LTM). Furthermore, it achieved clear digit classification results in learning and inference tasks, with a recognition accuracy of up to 96.4%.

Due to the low carrier scattering and scale‐down capability, two‐dimensional (2D) materials are promising for building high‐temperature neuromorphic electronics that are highly needed for performing complex tasks above 125°C. However, current 2D high‐temperature neuromorphic devices based on conventional resistive switching mechanisms still have key problems, e.g., severe gate leakage in three‐terminal devices and a limited number of resistance states in two‐terminal devices at high operating temperatures. Here, we report a gate‐free, high‐temperature MoS 2 neuromorphic device with up to 256 tunable resistance states, representing the state‐of‐the‐art resistance state number in a two‐terminal device operating at high temperatures. In addition to the multi‐state function, the device also has an enhanced resistive switching ratio of ∼10 3 at 200°C and simulates diverse synaptic plasticities at 350°C. Such superior performance is enabled by Schottky barrier modulation through thermal‐activated directional migration of sulfur vacancies. The device further demonstrates remarkable potential for high‐temperature neuromorphic computing in handwritten digit recognition and reservoir‐computing‐based temporal data processing. This work provides a new strategy for developing high‐temperature neuromorphic devices based on 2D materials.

This investigation deals with the effect of growth temperature on the microstructure, nitrogen content, and crystallinity of C–N nanotubes. The X-ray photoelectron spectroscopic (XPS) study reveals that the atomic percentage of nitrogen content in nanotubes decreases with an increase in growth temperature. Transmission electron microscopic investigations indicate that the bamboo compartment distance increases with an increase in growth temperature. The diameter of the nanotubes also increases with increasing growth temperature. Raman modes sharpen while the normalized intensity of the defect mode decreases almost linearly with increasing growth temperature. These changes are attributed to the reduction of defect concentration due to an increase in crystal planar domain sizes in graphite sheets with increasing temperature. Both XPS and Raman spectral observations indicate that the C–N nanotubes grown at lower temperatures possess higher degree of disorder and higher N incorporation.

Alloying process at the interface of silver nanoparticles deposited on Au(1 1 1) substrate due to the high-temperature treatments