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1.
Large‐area and uniform three‐dimensional (3D) β‐Ni(OH)2 and NiO nanowalls were synthesized on a variety of rigid and flexible substrates via a simple aqueous chemical deposition process. The β‐Ni(OH)2 nanowalls consist of single‐crystal Ni(OH)2 nanosheets that were vertically grown on different substrates. The height, crystallinity, and morphology of the Ni(OH)2 nanowalls can be readily modified by adjusting the reaction time and concentration of the NiCl2 solution. The synthesis mechanism of the Ni(OH)2 nanowalls was determined through heterogeneous nucleation and subsequent oriented crystal growth. 3D NiO nanowalls were obtained by thermal decomposition of the Ni(OH)2 nanowalls at 400 °C in Ar atmosphere. Highly sensitive, selective gas sensors and electrochemical sensors based on these NiO nanowalls were developed. The chemiresistive gas sensors based on the NiO nanowalls grown on ceramic substrates exhibited an excellent performance with low detection limit for formaldehyde (8 ppb) and NO2 (15 ppb). The electrochemical sensor based on the NiO nanowalls grown on an FTO glass substrate had a superior selectivity to non‐enzymatic glucose with a detection limit of 200 nm .  相似文献   

2.
Conversion of syngas (CO, H2) to hydrocarbons, commonly known as the Fischer–Tropsch (FT) synthesis, represents a fundamental pillar in today's chemical industry and is typically carried out under technically demanding conditions (1–3 MPa, 300–400 °C). Photocatalysis using sunlight offers an alternative and potentially more sustainable approach for the transformation of small molecules (H2O, CO, CO2, N2, etc.) to high‐valuable products, including hydrocarbons. Herein, a novel series of Fe‐based heterostructured photocatalysts (Fe‐x) is successfully fabricated via H2 reduction of ZnFeAl‐layered double hydroxide (LDH) nanosheets at temperatures (x) in the range 300–650 °C. At a reduction temperature of 500 °C, the heterostructured photocatalyst formed (Fe‐500) consists of Fe0 and FeOx nanoparticles supported by ZnO and amorphous Al2O3. Fe‐500 demonstrates remarkable CO hydrogenation performance with very high initial selectivities toward hydrocarbons (89%) and especially light olefins (42%), and a very low selectivity towards CO2 (11%). The intimate and abundant interfacial contacts between metallic Fe0 and FeOx in the Fe‐500 photocatalyst underpins its outstanding photocatalytic performance. The photocatalytic production of high‐value light olefins with suppressed CO2 selectivity from CO hydrogenation is demonstrated here.  相似文献   

3.
YBa2Cu3‐xZnxO7‐y compounds with x = 0, 0.05, 0.15, and 0.30 have been synthesized by standard solid state reaction method. The crystal structure, lattice parameters, and oxygen content are not changed by the substitution of Zn for Cu since both valence state and ionic radius are almost identical for Zn and Cu elements in YBa2Cu3‐xZnxO7‐y. However, the superconducting transition temperature Tc decreases with the increase of Zn content, reflecting the Tc‐suppression effect of Zn substitution. Heat treatment experiments indicate that the heat treatment at low temperature is beneficial to improve the superconductivity of the sample. But Tc decreases with the increase of annealing temperature when the treatment temperature is above 300°C, and finally the superconductivity disappears at approximately 920°C, 700°C and 550°C for the samples with x = 0.0, 0.05 and 0.15, respectively. Our experiments indicate that the superconductivity of the sample with higher Zn content is more sensitive to the oxygen content, and a small decrease in the oxygen content can lead to a considerable decrease of Tc.  相似文献   

4.
A series of novel CoFe‐based catalysts are successfully fabricated by hydrogen reduction of CoFeAl layered‐double‐hydroxide (LDH) nanosheets at 300–700 °C. The chemical composition and morphology of the reaction products (denoted herein as CoFe‐x) are highly dependent on the reduction temperature (x). CO2 hydrogenation experiments are conducted on the CoFe‐x catalysts under UV–vis excitation. With increasing LDH‐nanosheet reduction temperature, the CoFe‐x catalysts show a progressive selectivity shift from CO to CH4, and eventually to high‐value hydrocarbons (C2+). CoFe‐650 shows remarkable selectivity toward hydrocarbons (60% CH4, 35% C2+). X‐ray absorption fine structure, high‐resolution transmission electron microscopy, Mössbauer spectroscopy, and density functional theory calculations demonstrate that alumina‐supported CoFe‐alloy nanoparticles are responsible for the high selectivity of CoFe‐650 for C2+ hydrocarbons, also allowing exploitation of photothermal effects. This study demonstrates a vibrant new catalyst platform for harnessing clean, abundant solar‐energy to produce valuable chemicals and fuels from CO2.  相似文献   

5.
Cu‐exchanged LTA‐type aluminosilicate catalyst has been considered as an efficient catalyst for the selective catalytic reduction of NOx with ammonia (NH3‐SCR). However, expensive organic structure‐directing agents (OSDAs) and the corrosive fluoride medium are inevitably used to synthesize LTA‐type molecular sieve (high‐silica LTA‐type aluminosilicate and its analogue LTA‐type silicoaluminophosphate SAPO‐42). Herein, a series of cheap and commercialized OSDAs, which are successfully applied for the targeted synthesis of SAPO‐42 in the fluoride‐free system, are identified by a novel RSS (refine, summarize, and search) approach. Furthermore, Cu‐SAPO‐42 catalysts are utilized for NH3‐SCR. Among these catalysts, Cu‐SAPO‐42 prepared with 2‐(butylamino)ethanol (BAEA) as OSDA demonstrates the excellent activity even after hydrothermal aging at 800 °C for 16 h, which shows much better hydrothermal stability than the commercialized Cu‐SAPO‐34 catalyst with comparable Si and Cu contents. Electron paramagnetic resonance (EPR) spectroscopy and Rietveld refinement are performed to identify the locations of active Cu2+ ions. It turns out that the active Cu2+ ions are distributed near the center of single 6‐rings of the lta cage.  相似文献   

6.
Active and stable catalysts are highly desired for converting harmful substances (e.g., CO, NOx) in exhaust gases of vehicles into safe gases at low exhaust temperatures. Here, a solvent evaporation–induced co‐assembly process is employed to design ordered mesoporous CexZr1?xO2 (0 ≤ x ≤ 1) solid solutions by using high‐molecular‐weight poly(ethylene oxide)‐block‐polystyrene as the template. The obtained mesoporous CexZr1?xO2 possesses high surface area (60–100 m2 g?1) and large pore size (12–15 nm), enabling its great capacity in stably immobilizing Pt nanoparticles (4.0 nm) without blocking pore channels. The obtained mesoporous Pt/Ce0.8Zr0.2O2 catalyst exhibits superior CO oxidation activity with a very low T100 value of 130 °C (temperature of 100% CO conversion) and excellent stability due to the rich lattice oxygen vacancies in the Ce0.8Zr0.2O2 framework. The simulated catalytic evaluations of CO oxidation combined with various characterizations reveal that the intrinsic high surface oxygen mobility and well‐interconnected pore structure of the mesoporous Pt/Ce0.8Zr0.2O2 catalyst are responsible for the remarkable catalytic efficiency. Additionally, compared with mesoporous Pt/CexZr1?xO2‐s with small pore size (3.8 nm), ordered mesoporous Pt/CexZr1?xO2 not only facilitates the mass diffusion of reactants and products, but also provides abundant anchoring sites for Pt nanoparticles and numerous exposed catalytically active interfaces for efficient heterogeneous catalysis.  相似文献   

7.
Ferrites are magnetic ceramic materials which have additional metallic ion in ferrous oxide compounds. Ferrites are usually classified as soft or hard ferrites. In this study, characteristics and magnetic properties of magnetic materials having NiO1–xZnOxFe2O4 structure were investigated. Mechanical mixing of high purity NiO, ZnO and Fe2O3 powders were done to obtain homogenous NiO1–xZnOxFe2O4 powder mixture for x = 0.15, x = 0.50 and x = 0.85. These powder mixtures were pressed using hydraulic press machine and then subjected to sintering at same temperatures of 1000 °C for 1 hour. Obtained specimens were analyzed with scanning electron microscopy (SEM) imaging and energy dispersive X‐ray fluorescence (EDXRF) technique for the investigation of structural analysis; magnetic properties were determined using vibrating sample magnetometer (VSM). However, effects of composition, specimens and Zn% element in magnetic materials after energy dispersive X‐ray fluorescence on maximum magnetic moment (Ms) were analyzed using Taguchi orthogonal array design of experiments technique. The study indicates that Zn% element is the main process parameter that has the highest statistical influence on maximum magnetic moment. However, another parameter, composition, also has a significant effect on maximum magnetic moment. Then, Zn‐content was found to have a significant influence on the magnetic properties of the system.  相似文献   

8.
In this work, ordered mesoporous structures of In2O3-decorated NiO were prepared by a two-step process, comprising of the synthesis of ordered mesoporous NiO followed by injection of In3+ into their pores. The pore size distribution of the as prepared samples was between 4.1 and 21.1 nm. Furthermore, their sensing performances toward NO2 were tested systematically. The results showed the highest response about 3 towards 15 ppm NO2 sensing at room temperature for 5.0 at.% In2O3-decorated NiO compared to other decorated and pure samples. Moreover, the sensor displayed excellent selectivity towards NO2 in the presence of other interfering gases, such as carbon monoxide, ammonia, ethanol, methanol, formaldehyde, toluene, acetone. The exceptional NO2 sensing performance of the In2O3-decorated mesoporous NiO may be attributed to their high specific surface area and the formation of p–n junction with modified carrier concentration caused by In3+ doping. This method can act as an effective strategy for enhancement of gas-sensing properties of pure metal oxides.  相似文献   

9.
Hydrogen peroxide (H2O2) is a green oxidizer widely involved in a vast number of chemical reactions. Electrochemical reduction of oxygen to H2O2 constitutes an environmentally friendly synthetic route. However, the oxygen reduction reaction (ORR) is kinetically sluggish and undesired water serves as the main product on most electrocatalysts. Therefore, electrocatalysts with high reactivity and selectivity are highly required for H2O2 electrosynthesis. In this work, a synergistic strategy is proposed for the preparation of H2O2 electrocatalysts with high ORR reactivity and high H2O2 selectivity. A Co?Nx?C site and oxygen functional group comodified carbon‐based electrocatalyst (named as Co–POC–O) is synthesized. The Co–POC–O electrocatalyst exhibits excellent catalytic performance for H2O2 electrosynthesis in O2‐saturated 0.10 m KOH with a high selectivity over 80% as well as very high reactivity with an ORR potential at 1 mA cm?2 of 0.79 V versus the reversible hydrogen electrode (RHE). Further mechanism study identifies that the Co?Nx?C sites and oxygen functional groups contribute to the reactivity and selectivity for H2O2 electrogeneration, respectively. This work affords not only an emerging strategy to design H2O2 electrosynthesis catalysts with remarkable performance, but also the principles of rational combination of multiple active sites for green and sustainable synthesis of chemicals through electrochemical processes.  相似文献   

10.
Nitrogen dioxide (NO2) emission has severe impact on human health and the ecological environment and effective monitoring of NO2 requires the detection limit (limit of detection) of several parts‐per‐billion (ppb). All organic semiconductor‐based NO2 sensors fail to reach such a level. In this work, using an ion‐in‐conjugation inspired‐polymer (poly(3,3′‐diaminobenzidine‐squarine, noted as PDBS) as the sensory material, NO2 can be detected as low as 1 ppb, which is the lowest among all reported organic NO2 sensors. In addition, the sensor has high sensitivity, good reversibility, and long‐time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H‐bonding and ion‐dipole interaction to NO2. The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion‐in‐conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H‐bonding and ion‐dipole attraction.  相似文献   

11.
In situ monitoring of hydrogen peroxide (H2O2) during its production process is needed. Here, an electrochemical H2O2 sensor with a wide linear current response range (concentration: 5 × 10?8 to 5 × 10?2 m ), a low detection limit (32.4 × 10?9 m ), and a high sensitivity (568.47 µA mm ?1 cm?2) is developed. The electrocatalyst of the sensor consists of cobalt nanoparticles and atomic Co‐Nx moieties anchored on nitrogen doped carbon nanotube arrays (Co‐N/CNT), which is obtained through the pyrolysis of the sandwich‐like urea@ZIF‐67 complex. More cobalt nanoparticles and atomic Co‐Nx as active sites are exposed during pyrolysis, contributing to higher electrocatalytic activity. Moreover, a portable screen‐printed electrode sensor is constructed and demonstrated for rapidly detecting (cost ≈40 s) H2O2 produced in microbial fuel cells with only 50 µL solution. Both the synthesis strategy and sensor design can be applied to other energy and environmental fields.  相似文献   

12.
Solar‐driven Fischer–Tropsch synthesis represents an alternative and potentially low‐cost route for the direct production of light olefins from syngas (CO and H2). Herein, a series of novel Co‐based photothermal catalysts with different chemical compositions are successfully fabricated by H2 reduction of ZnCoAl‐layered double‐hydroxide nanosheets at 300–700 °C. Under UV–vis irradiation, the photothermal catalyst prepared at 450 °C demonstrates remarkable CO hydrogenation performance, affording an olefin (C2–4=) selectivity of 36.0% and an olefin/paraffin ratio of 6.1 at a CO conversion of 15.4%. Characterization studies using X‐ray absorption fine structure and high‐resolution transmission electron microscopy reveal that the active catalyst comprises Co and Co3O4 nanoparticles on a ZnO–Al2O3 mixed metal oxide support. Density functional theory calculations further demonstrate that the oxide‐decorated metallic Co nanoparticle heterostructure weakens the further hydrogenation ability of the corresponding Co, leading to the high selectivity to light olefins. This study demonstrates a novel solar‐driven catalyst platform for the production of light olefins via CO hydrogenation.  相似文献   

13.
The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self‐refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In2O3 hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO2 nanoclusters is uniformly loaded onto In2O3 hollow spheres via layer‐by‐layer (LBL) assembly. Moreover, In2O3 sensors LBL‐coated with CeO2 nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In2O3 sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO2 and the chemical interaction among CeO2, In2O3, and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring.  相似文献   

14.
Osteocytes are bone cells encapsulated in a mineralized matrix. Since they are connected to nutrient blood vessels via narrow canaliculii which provide narrow, tortuous and often long diffusion pathways, the question arises as to how osteocytes are sufficiently supplied with O2 and metabolites. Furthermore, different oxygen partial pressures (PO2) ‐ resulting from O2 supply and local oxygen consumption ‐ may influence cellular proliferation and differentiation. In this context, O2 consumption rates of bone cells were measured and results were related to published blood flow values. This should allow to estimate mean venous PO2 and PO2 distribution in bone. O2 consumption of bone cells inside spongious calvarial fragments of neonatal rats and adult guinea pigs were measured polarographically in a thermostabilized recording chamber containing Hepes‐buffered saline. PO2 declined linearly as long as the PO2 ranged above 20 mmHg. At 27°C and 37°C, the O2 consumption rate of calvarial fragments from adult animals amounted to 0.06 and 0.1 ml/100 g?min, respectively. Calvaria from newborn rats showed 5‐fold higher values. At 45 °C, oxygen consumption was irreversibly abolished. The blood flow to bones amounts to 5–6 ml/100 g?min being equivalent to an oxygen delivery of about 1 ml/100 g?min. Based on the hemoglobin‐oxygen binding curve and on an O2 consumption of 0.1 ml/100 g ? min, venous PO2 calculates to ca. 60 mmHg. This appears to be a luxurious oxygen supply in bone. With respect to the long diffusion pathways, however, high PO2 values appear necessary to ensure sufficiently steep PO2 gradients for the the supply of cells remote from nutrient vessels. The resulting local oxygen gradients may orchestrate proliferation and differentiation of bone cells via oxygen‐dependent gene expression. Based on these considerations a model is proposed which comprises known factors influencing blood flow and oxygen tension in bone.  相似文献   

15.
Herein, an approach is reported for fabrication of Co‐Nx‐embedded 1D porous carbon nanofibers (CNFs) with graphitic carbon‐encased Co nanoparticles originated from metal–organic frameworks (MOFs), which is further explored as a bifunctional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Electrochemical results reveal that the electrocatalyst prepared by pyrolysis at 1000 °C (CoNC‐CNF‐1000) exhibits excellent catalytic activity toward ORR that favors the four‐electron ORR process and outstanding long‐term stability with 86% current retention after 40 000 s. Meanwhile, it also shows superior electrocatalytic activity toward OER, reaching a lower potential of 1.68 V at 10 mA cm?2 and a potential gap of 0.88 V between the OER potential (at 10 mA cm?2) and the ORR half‐wave potential. The ORR and OER performance of CoNC‐CNF‐1000 have outperformed commercial Pt/C and most nonprecious‐metal catalysts reported to date. The remarkable ORR and OER catalytic performance can be mainly attributable to the unique 1D structure, such as higher graphitization degree beneficial for electronic mobility, hierarchical porosity facilitating the mass transport, and highly dispersed CoNxC active sites functionalized carbon framework. This strategy will shed light on the development of other MOF‐based carbon nanofibers for energy storage and electrochemical devices.  相似文献   

16.
Two different ceramic tool concepts for the semi‐solid processing (Thixoforming) of steel alloys are presented. Materials selection is adapted to forming technology (Thixoforging, Thixoextrusion), preset die temperature, and resulting process conditions. Gas‐pressure sintered silicon nitride (Si3N4) is chosen as die material in low tool temperature (300...400 °C) thixoforging experiments due to its high strength and outstanding thermal shock resistance. High purity dense alumina (Al2O3) is applied as die material for high temperature (1200 °C) thixoextrusion tests. Thixoforging results using Si3N4 dies pre‐heated to 300 °C show sufficient thermal shock and corrosion resistance of Si3N4 and confirm the applicability of this tool concept. The high temperature tool concept developed at the Institute of Mineral Engineering (GHI) effectively reduced thermal shock impacts on extrusion dies. As expected, corrosion resistance of Al2O3 proved to be excellent. Further research will be carried out concerning long‐term behaviour of Si3N4 thixoforging dies as well as on the influence of extrusion speed and tool temperature on the quality of products extruded through Al2O3 dies at high temperature.  相似文献   

17.
Pd@CeO2/Al2O3 catalysts are of great importance for real applications, such as three‐way catalysis, CO oxidation, and methane combustion. In this article, the Pd@CeO2 core@shell nanospheres are prepared via the autoredox reaction in aqueous phase. Three kinds of methods are then employed, that is, electrostatic interaction, supramolecular self‐assembly, and physical mixing, to support the as‐prepared Pd@CeO2 nanospheres on γ‐Al2O3. A model reaction of catalytic methane‐combustion is employed here to evaluate the three Pd@CeO2/γ‐Al2O3 samples. As a result, the sample Pd@CeO2‐S‐850 prepared via supramolecular self‐assembly and calcined at 850 °C exhibits superior catalytic performance to the others, which has a far lower light‐off temperature (T50 of about 364 °C). Moreover, almost no deterioration of Pd@CeO2‐S‐850 is observed after five sequent catalytic cycles. The analysis of H2‐TPR curves concludes that there exists hydrogen spillover related to the strong metal–support interaction between Pd species and oxides. The strong metal–support interaction and the specific surface areas might be responsible for the catalytic performance of the Pd@CeO2 samples toward catalytic methane combustion.  相似文献   

18.
High‐performance and inexpensive platinum‐group‐metal (PGM)‐free catalysts for the oxygen reduction reaction (ORR) in challenging acidic media are crucial for proton‐exchange‐membrane fuel cells (PEMFCs). Catalysts based on Fe and N codoped carbon (Fe–N–C) have demonstrated promising activity and stability. However, a serious concern is the Fenton reactions between Fe2+ and H2O2 generating active free radicals, which likely cause degradation of the catalysts, organic ionomers within electrodes, and polymer membranes used in PEMFCs. Alternatively, Co–N–C catalysts with mitigated Fenton reactions have been explored as a promising replacement for Fe and PGM catalysts. Therefore, herein, the focus is on Co–N–C catalysts for the ORR relevant to PEMFC applications. Catalyst synthesis, structure/morphology, activity and stability improvement, and reaction mechanisms are discussed in detail. Combining experimental and theoretical understanding, the aim is to elucidate the structure–property correlations and provide guidance for rational design of advanced Co catalysts with a special emphasis on atomically dispersed single‐metal‐site catalysts. In the meantime, to reduce H2O2 generation during the ORR on the Co catalysts, potential strategies are outlined to minimize the detrimental effect on fuel cell durability.  相似文献   

19.
Nanoscale surface‐engineering plays an important role in improving the performance of battery electrodes. Nb2O5 is one typical model anode material with promising high‐rate lithium storage. However, its modest reaction kinetics and low electrical conductivity obstruct the efficient storage of larger ions of sodium or potassium. In this work, partially surface‐amorphized and defect‐rich black niobium oxide@graphene (black Nb2O5?x@rGO) nanosheets are designed to overcome the above Na/K storage problems. The black Nb2O5?x@rGO nanosheets electrodes deliver a high‐rate Na and K storage capacity (123 and 73 mAh g?1, respectively at 3 A g?1) with long‐term cycling stability. Besides, both Na‐ion and K‐ion full batteries based on black Nb2O5?x@rGO nanosheets anodes and vanadate‐based cathodes (Na0.33V2O5 and K0.5V2O5 for Na‐ion and K‐ion full batteries, respectively) demonstrate promising rate and cycling performance. Notably, the K‐ion full battery delivers higher energy and power densities (172 Wh Kg?1 and 430 W Kg?1), comparable to those reported in state‐of‐the‐art K‐ion full batteries, accompanying with a capacity retention of ≈81.3% over 270 cycles. This result on Na‐/K‐ion batteries may pave the way to next‐generation post‐lithium batteries.  相似文献   

20.
The large‐scale commercial application of lithium–oxygen batteries (LOBs) is overwhelmed by the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) associated with insoluble and insulated Li2O2. Herein, an elaborate design on a highly catalytic LOBs cathode constructed by N‐doped carbon nanotubes (CNT) with in situ encapsulated Co2P and Ru nanoparticles is reported. The homogeneously dispersed Co2P and Ru catalysts can effectively modulate the formation and decomposition behavior of Li2O2 during discharge/charge processes, ameliorating the electronically insulating property of Li2O2 and constructing a homogenous low‐impedance Li2O2/catalyst interface. Compared with Co/CNT and Ru/CNT electrodes, the Co2P/Ru/CNT electrode delivers much higher oxygen reduction triggering onset potential and higher ORR and OER peak current and integral areas, showing greatly improved ORR/OER kinetics due to the synergistic effects of Co2P and Ru. Li–O2 cells based on the Ru/Co2P/CNT electrode demonstrate improved ORR/OER overpotential of 0.75 V, excellent rate capability of 12 800 mAh g?1 at 1 A g?1, and superior cycle stability for more than 185 cycles under a restricted capacity of 1000 mAh g?1 at 100 mA g?1. This work paves an exciting avenue for the design and construction of bifunctional catalytic cathodes by coupling metal phosphides with other active components in LOBs.  相似文献   

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