Optoelectronic bio-synaptic plasticity on neotype kesterite memristor with switching ratio >104.

Optoelectronic memristors hold the most potential for realizing next-generation neuromorphic computation; however, memristive devices that can integrate excellent resistive switching and both electrical-/light-induced bio-synaptic behaviors are still challenging to develop. In this study, an artificial optoelectronic synapse is proposed and realized using a kesterite-based memristor with Cu2ZnSn(S,Se)4 (CZTSSe) as the switching material and Mo/Ag as the back/top electrode. Benefiting from unique electrical features and a bi-layered structure of CZTSSe, the memristor exhibits highly stable nonvolatile resistive switching with excellent spatial uniformity, concentrated Set/Reset voltage distribution (variation <0.08/0.02 V), high On/Off ratio (>104), and long retention time (>104 s). A possible mechanism of the switching behavior in such a device is proposed. Furthermore, these memristors successfully achieve essential bio-synaptic functions under both electrical and various visible light (470-655 nm) stimulations, including electrical-induced excitatory postsynaptic current, paired pulse facilitation, long-term potentiation, long-term depression, spike-timing-dependent plasticity, as well as light-stimulated short-/long-term plasticity and learning-forgetting-relearning process. As such, the proposed neotype kesterite-based memristor demonstrates significant potential in facilitating artificial optoelectronic synapses and enabling neuromorphic computation.

Neotype kuramite optoelectronic memristor for bio-synaptic plasticity simulations.

Memristive devices with both electrically and optically induced synaptic dynamic behaviors will be crucial to the accomplishment of brain-inspired neuromorphic computing systems, in which the resistive materials and device architectures are two of the most important cornerstones, but still under challenge. Herein, kuramite Cu3SnS4 is newly introduced into poly-methacrylate as the switching medium to construct memristive devices, and the expected high-performance bio-mimicry of diverse optoelectronic synaptic plasticity is demonstrated. In addition to the excellent basic performances, such as stable bipolar resistive switching with On/Off ratio of ∼486, Set/Reset voltage of ∼-0.88/+0.96 V, and good retention feature of up to 104 s, the new designs of memristors possess not only the multi-level controllable resistive-switching memory property but also the capability of mimicking optoelectronic synaptic plasticity, including electrically and visible/near-infrared light-induced excitatory postsynaptic currents, short-/long-term memory, spike-timing-dependent plasticity, long-term plasticity/depression, short-term plasticity, paired-pulse facilitation, and "learning-forgetting-learning" behavior as well. Predictably, as a new class of switching medium material, such proposed kuramite-based artificial optoelectronic synaptic device has great potential to be applied to construct neuromorphic architectures in simulating human brain functions.

Low-temperature liquid phase reduced TiO2 nanotube arrays: synergy of morphology manipulation and oxygen vacancy doping for enhancement of field emission.

The partially reduced TiO(2) nanotube arrays (TNAs) are prepared via an uncomplicated and low-cost liquid phase reduction strategy using NaBH(4) as the reducing agent. By controlling and adjusting the reduction temperatures from 30 to 90 °C, the reduction treatment can not only change their surface morphology but also introduce oxygen vacancies into them, resulting in an optimized morphology, elevated Fermi-level, reduced effective work function and improved conductivity of the TNAs. Meanwhile, the thermal and long-term stability of oxygen vacancy are also investigated, indicating that the oxygen vacancies retain long-term stability from room temperature up to 150 °C. More interesting, partially reduced TNAs show drastically enhanced field emission (FE) performances including substantially decreased turn-on field from 18.86 to 1.53 V µm(-1), a high current density of 4.00 mA cm(-2) at 4.52 V µm(-1), and an excellent FE stability and repeatability. These very promising results are attributed to the combination of the optimized morphology and introduced oxygen vacancies, which can increase FE sites, reduce effective work function and increase conductivity.

MoOx Synaptic Memristor with Programmable Multilevel Conductance for Reliable Neuromorphic Hardware.

Memristor holds great potential for enabling next-generation neuromorphic computing hardware. Controlling the interfacial characteristics of the device is critical for seamlessly integrating and replicating the synaptic dynamic behaviors; however, it is commonly overlooked. Herein, we report the straightforward oxidation of a Mo electrode in air to design MoOx memristors that exhibit nonvolatile ultrafast switching (0.6-0.8 mV/decade, <1 mV/decade) with a high on/off ratio (>104), a long durability (>104 s), a low power consumption (17.9 µW), excellent device-to-device uniformity, ingeniously synaptic behavior, and finely programmable multilevel analog switching. The analyzed physical mechanism of the observed resistive switching behavior might be the conductive filaments formed by the oxygen vacancies. Intriguingly, upon organization into memristor-based crossbar arrays, in addition to simulated multipattern memorization, edge detection on random images can be implemented well by parallel processing of pixels using a 3 × 3 × 2 array of Prewitt filter groups. These are vital functions for neural system hardware in efficient in-memory computing neural systems with massive parallelism beyond a von Neumann architecture.

Multifunctional black phosphorus pressure sensors with bending angle monitoring and direction recognition characteristics.

Flexible pressure sensors, an important class of intelligent sensing devices, are widely explored in body-motion and medical health monitoring, artificial intelligence and human-machine interaction. As a unique layered nanomaterial, black phosphorus (BP) has excellent electrical, mechanical, and flexible characteristics, which make it a promising candidate for fabricating high-performance pressure sensors. Herein, hierarchically structured BP-based pressure sensors were constructed. The sensors exhibit high sensitivity, stability and a wide sensing range and respond to various human motions including finger pressure, swallowing, and wrist bending. The sensors can identify different handwriting processes with featured signals. In particular, benefiting from the unique structure of loose-dense layers, the sensors show a distinctive response to bending angles and directions, revealing a characteristic of direction recognition. This feature facilitates the sensors to monitor human motions. The sensors have been successfully powered by a home-made Cu2ZnSn(S,Se)4 thin-film solar cell, which demonstrates the sustainability, flexibility and low power consumption of integrated devices. This work offers a strategy to construct hierarchically structured pressure/strain sensors with direction recognition and provides further insights into manufacturing portable sensing devices for realistic and innovative applications.

Artificial Neural Synapses Based on Microfluidic Memristors Prepared by Capillary Tubes and Ionic Liquid.

Neuromorphic simulation, i.e., the use of electronic devices to simulate the neural networks of the human brain, has attracted a lot of interest in the fields of data processing and memory. This work provides a new method for preparing a 1,3-dimethylimidazolium nitrate ([MMIm][NO3]:H2O) microfluidic memristor that is ultralow cost and technically uncomplicated. Such a fluidic device uses capillaries as memory tubes, which are structurally similar to interconnected neurons by simple solution treatment. When voltage is applied, the transmission of anions and cations in the tube corresponds to the release of neurotransmitters from the presynaptic membrane to the postsynaptic membrane. The change of synaptic weights (plasticity) also can be simulated by the gradual change of conductance of the fluid memristor. The learning process of microfluidic memristors is very obvious, and the habituation and recovery behaviors they exhibit are extremely similar to biological activities, representing its good use for simulating neural synapses.

Optoelectronic Memristive Synapse Behavior for the Architecture of Cu2ZnSnS4@BiOBr Embedded in Poly(methyl methacrylate).

The great potential of artificial optoelectronic devices that are capable of mimicking biosynapse functions in brain-like neuromorphic computing applications has aroused extensive interest, and the architecture design is decisive yet challenging. Herein, a new architecture of p-type Cu2ZnSnS4@BiOBr nanosheets embedded in poly(methyl methacrylate) (PMMA) films (CZTS@BOB-PMMA) is presented acting as a switching layer, which not only shows the bipolar resistive switching features (SET/RESET voltages, ∼ -0.93/+1.35 V; retention, >104 s) and electrical- and near-infrared light-induced synapse plasticity but also demonstrates electrical-driven excitatory postsynaptic current, spiking-time-dependent plasticity, paired pulse facilitation, long-term plasticity, long- and short-term memory, and "learning-forgetting-learning" behaviors. The approach is a rewarding attempt to broaden the research of optoelectric controllable memristive devices for building neuromorphic architectures mimicking human brain functionalities.

Optimizing performance of iron-rich sludge ash as cost-effective oxygen carrier by calcium-based additive for syngas production from biomass chemical-looping gasification.

Chemical-looping gasification tests were conducted on pine sawdust using thermogravimetric analyzer and horizontal sliding resistance furnace to investigate the regulation effects of calcium-based additive on iron-rich sludge ash oxygen carrier. The impacts of temperature, CaO/C in mole, multiple redox cycles, CaO addition modes on gasification performances were analyzed. The TGA results indicated that the CaO addition could effectively capture CO2 from syngas to from CaCO3, which subsequently decomposed at high temperatures. From in-situ CaO addition experiments, the temperature rise resulted in higher syngas yields, while a decrease in syngas LHV. With the CaO/C growing, the H2 yield grew from 0.103 to 0.256Nm3/kg at 800.0℃, and the CO yield boosted from 0.158 to 0.317Nm3/kg. Multiple redox manifested that the SA oxygen carrier and calcium-based additive kept higher reaction stability. The possible reaction mechanisms showed that the syngas variations from BCLG were influenced by the calcium roles and valence change of iron.

Enhanced field emission from hydrogenated TiO2 nanotube arrays.

The field emission (FE) properties of TiO(2) nanotube arrays (TNAs) synthesized by anodization are dramatically improved after hydrogenation at various temperatures in a range of 400-550 °C. Compared with pristine TNAs, the turn-on fields of hydrogenated TNAs (H:TNAs) are significantly decreased from 18.23 to 1.75 V µm(-1), and closely related to hydrogenation temperature. Importantly, the optimized sample of H:TNAs prepared at 550 °C shows excellent FE performances involving both a low turn-on field of 1.75 V µm(-1), a high current density of 4.0 mA cm(-2) at 4.50V µm(-1), and a remarkable FE stability over 480 min. The substantially enhanced FE properties can be attributed to the combination of a typical tubular morphology, a reduced work function and the improved conductivity of H:TNAs.

Influence of iron-containing petrochemical sludge ash on the pyrolysis of pine wood: Thermal behaviors, thermodynamic analysis, and kinetic parameters.

The pyrolysis characteristics and kinetics of pine wood (PW) with the presence of iron-containing petrochemical sludge ash (PSA) were studied using thermogravimetric analysis at non-isothermal conditions. The thermal conversion of PW with the presence of PSA could be characterized via a three-stage reaction, including the moisture release, pyrolysis reactions and gas-solid reaction, and solid-solid reaction between char and iron oxides. The pyrolysis characteristic parameters analysis showed that the presence of PSA indeed promoted the conversion of PW. Thermodynamic analysis revealed that the Fe2O3 in PSA was characterized by a gradual loss of oxygen during co-pyrolysis. The kinetic parameters were calculated by the Starink method combined with master-plots method. The presence of PSA would decrease the activation energy, and the minimum average value was 167.00 kJ/mol at 15% PSA addition. The most suitable kinetic models for the pyrolysis of PW and its mixtures with PSA were D3 and D4, respectively.

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol-1 and 94.86-169.18 kJ mol-1, respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data.

Investigation into THF hydrate slurry flow behaviour and inhibition by an anti-agglomerant.

Hydrate plugs are one of the highest risks for gas and oil transportation in pipelines, especially in deep sea environments. In a newly built-up loop, pilot-scale experiments were carried out to study typical hydrate plug phenomena and to explore the specific reasons behind these. A tetrahydrofuran (THF) hydrate slurry was formed and investigated in this loop fluid at two liquid loadings (50 vol% and 100 vol%) with/without a typical anti-agglomerant, KL-1. Morphology and temperature variations revealed that THF hydrate slurry evolution had four stages: (a) flowable fluid; (b) particle formation; (c) agglomeration; and (d) plug. The effect of liquid loading (LL) and an anti-agglomerant (AA) on morphology and temperature in three cases were studied. The morphologies in each stage were compared for the three cases. Hydrate conversion was calculated according to the liquid and solid volume proportion in these morphologies. From these morphologies, heterogeneous hydrate deposition was found to be more likely to happen in 50 vol% than in the 100 vol% LL system. The hydrate plug was also found to be induced by hydrate deposition rather than the bed at the bottom of the pipeline. By dispersing hydrate particle agglomeration, AA compressed hydrate deposition and the plug.

Evaluation of agricultural residues pyrolysis under non-isothermal conditions: Thermal behaviors, kinetics, and thermodynamics.

The thermal conversion characteristics, kinetics, and thermodynamics of agricultural residues, rape straw (RS) and wheat bran (WB), were investigated under non-isothermal conditions. TGA experiments showed that the pyrolysis characteristics of RS were quite different from those of WB. As reflected by the comprehensive devolatilization index, when the heating rate increased from 10 to 30Kmin-1, the pyrolysis performance of RS and WB were improved 5.27 and 5.96 times, respectively. The kinetic triplets of the main pyrolysis process of agricultural residues were calculated by the Starink method and the integral master-plots method. Kinetic analysis results indicated that the most potential kinetic models for the pyrolysis of RS and WB were D2 and F2.7, respectively. The thermodynamic parameters (ΔH, ΔG, and ΔS) were determined by the activated complex theory. The positive ΔH, positive ΔG, and negative ΔS at characteristic temperatures validated that the pyrolysis of agricultural residues was endothermic and non-spontaneous.

Comparative evaluation of thermal oxidative decomposition for oil-plant residues via thermogravimetric analysis: Thermal conversion characteristics, kinetics, and thermodynamics.

Thermal oxidative decomposition characteristics, kinetics, and thermodynamics of rape straw (RS), rapeseed meal (RM), camellia seed shell (CS), and camellia seed meal (CM) were evaluated via thermogravimetric analysis (TGA). TG-DTG-DSC curves demonstrated that the combustion of oil-plant residues proceeded in three stages, including dehydration, release and combustion of organic volatiles, and chars oxidation. As revealed by combustion characteristic parameters, the ignition, burnout, and comprehensive combustion performance of residues were quite distinct from each other, and were improved by increasing heating rate. The kinetic parameters were determined by Coats-Redfern approach. The results showed that the most possible combustion mechanisms were order reaction models. The existence of kinetic compensation effect was clearly observed. The thermodynamic parameters (ΔH, ΔG, ΔS) at peak temperatures were calculated through the activated complex theory. With the combustion proceeding, the variation trends of ΔH, ΔG, and ΔS for RS (RM) similar to those for CS (CM).

Evaluation of co-pyrolysis petrochemical wastewater sludge with lignite in a thermogravimetric analyzer and a packed-bed reactor: Pyrolysis characteristics, kinetics, and products analysis.

Co-pyrolysis characteristics of petrochemical wastewater sludge and Huolinhe lignite were investigated using thermogravimetric analyzer and packed-bed reactor coupled with Fourier transform infrared spectrometer and gas chromatography. The pyrolysis characteristics of the blends at various sludge blending ratios were compared with those of the individual materials. Thermogravimetric experiments showed that the interactions between the blends were beneficial to generate more residues. In packed-bed reactor, synergetic effects promoted the release of gas products and left less liquid and solid products than those calculated by additive manner. Fourier transform infrared spectrometer analysis showed that main functional groups in chars gradually disappeared with pyrolysis temperatures increasing, and H2O, CH4, CO, and CO2 appeared in volatiles during pyrolysis. Gas compositions analysis indicated that, the yields of H2 and CO clearly increased as the pyrolysis temperature and sludge blending ratio increasing, while the changes of CH4 and CO2 yields were relatively complex.

Pyrolysis and oxy-fuel combustion characteristics and kinetics of petrochemical wastewater sludge using thermogravimetric analysis.

The pyrolysis and oxy-fuel combustion characteristics of petrochemical wastewater sludge (PS) were studied in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres using non-isothermal thermogravimetric analysis (TGA). Pyrolysis experiments showed that the weight loss profiles were almost similar up to 1050K in both N2 and CO2 atmospheres, while further weight loss took place in CO2 atmosphere at higher temperatures due to char-CO2 gasification. Compared with 20%O2/80%N2, the drying and devolatilization stage of PS were delayed in 20%O2/80%CO2 due to the differences in properties of the diluting gases. In oxy-fuel combustion experiments, with O2 concentration increasing, characteristic temperatures decreased, while characteristic combustion rates and combustion performance indexes increased. Kinetic analysis of PS decomposition under various atmospheres was performed using Coats-Redfern approach. The results indicated that, with O2 concentration increasing, the activation energies of Step 1 almost kept constant, while the values of subsequent three steps increased.

Pyrolysis of oil-plant wastes in a TGA and a fixed-bed reactor: Thermochemical behaviors, kinetics, and products characterization.

Pyrolysis characteristics of four distinct oil-plant wastes were investigated using TGA and fixed-bed reactor coupled with GC. TGA experiments showed that the pyrolysis behaviors were related to biomass species and heating rates. As the heating rate increased, TG and DTG curves shifted to the higher temperatures, and the comprehensive devolatilization index obviously increased. The remaining chars from TGA experiments were higher than those obtained from the fixed-bed experiments. The crack of tars at high temperatures enhanced the formation of non-condensable gases. During the pyrolysis, C-O and CO2 were the major gases. Chars FTIR showed that the functional groups of O-H, C-H(n), C=O, C-O, and C-C gradually disappeared from 400 °C on. The kinetic parameters were calculated by Coats-Redfern approach. The results manifested that the most appropriate pyrolysis mechanisms were the order reaction models. The existence of kinetic compensation effect was evident.

TG/DSC-FTIR and Py-GC investigation on pyrolysis characteristics of petrochemical wastewater sludge.

The pyrolysis characteristics of petrochemical wastewater sludge (PS) were evaluated using TG/DSC-FTIR and fixed-bed reactor with GC. TGA experiments indicated that the pyrolysis of PS proceeded in three phases, and the thermographs shifted to higher temperatures with increasing heating rate. Chars FTIR showed that the absorption of O-H, C-H, C=O and C-C decreased with pyrolysis temperatures increasing. Gases FTIR correspondingly showed that H2O, CO, and CH4 generated at higher temperatures. For the fixed-bed reactor tests, H2 and CO were relatively higher in the pyrolysis gases, and CH4 was negligible at 436K. The kinetic triplets of PS pyrolysis were estimated by Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, and integral master-plots method. The results suggested that the most potential kinetic models for the first and second phase were the order reaction model, while the random nucleation and nuclei growth model for the third phase.

Pyrolysis behaviors and kinetics of refining and chemicals wastewater, lignite and their blends through TGA.

Co-pyrolysis behaviors of refining and chemicals wastewater solid (RS) and Huolinhe lignite (HL) were investigated via thermogravimetric analysis (TGA). The thermal degradation process of RS and the blends proceeded in three stages, while two stages for HL. The increased percentage of RS in the blends reduced the characteristic temperature (Ti, Tp, Tf) and residual mass (Mr), while raised the characteristic reaction rate (Rp, Rv) and comprehensive devolatilization parameter (D). The results indicated that there existed some inhibitive interactions between RS and HL. The activation energies were calculated by using the Friedman and Starink method. The activation energy of RS increased first and then decreased with conversion degree, and the variation wasn't as great as that of the blends and lignite. No matter which conversion degree is, the activation energy decreased with the percentage of RS in the blends increasing. The minimum value was obtained by blending 75wt.% RS.

Enhancement of the field emission from the TiO2 nanotube arrays by reducing in a NaBH4 solution.

A mass of oxygen vacancies are successfully introduced into TiO2 nanotube arrays using low-cost NaBH4 as a reductant in a liquid-phase environment. By controlling and adjusting the reduction time over the range of 0-24 h, the doping concentration of the oxygen vacancy is controllable and eventually reaches saturation. Meanwhile, the thermal stability of oxygen vacancies is also investigated, indicating that part of the oxygen vacancies remain stable up to 250 °C. In addition, this liquid-phase reduction strategy significantly lowers the requirements of instruments and cost. More interesting, reduced TiO2 nanotube arrays show drastically enhanced field emission performances including substantially decreased turn-on field from 25.01 to 2.65 V/µm, a high current density of 3.5 mA/cm(2) at 7.2 V/µm, and an excellent field emission stability and repeatability. These results are attributed to the oxygen vacancies obtained by reducing in NaBH4 solution, resulting in a reduced effective work function and an increased conductivity.