Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

Economic competitiveness of compact steam methane reforming technology for on-site hydrogen supply: A Foshan case study

On-site hydrogen production through steam-methane reforming (SMR) from city gas or natural gas is believed to be a cost-effective way for hydrogen-based infrastructure due to high cost of hydrogen transportation. In recent years, there have been a lot of on-site hydrogen fueling stations under design or construction in China. This study introduces current developments and technology prospects of skid-mounted SMR hydrogen generator. Also, technical solutions and economic analysis are discussed based on China's first on-site hydrogen fueling station project in Foshan. The cost of hydrogen product from skid-mounted SMR hydrogen generator is about 23 CNY/kg with 3.24 CNY/Nm³ natural gas. If hydrogen price is 60 CNY/kg, IRR of on-site hydrogen fueling station project reaches to 10.8%. While natural gas price fall to 2.3 CNY/Nm³, the hydrogen cost can be reduced to 18 CNY/kg, and IRR can be raised to 13.1%. The conclusion is that skid-mounted SMR technology has matured and is developing towards more compact and intelligent design, and will be a promising way for hydrogen fueling infrastructures in near future.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

Mass transfer in polycrystalline ytterbium monosilicate under oxygen potential gradients at high temperatures

Mass transfer in polycrystalline Yb₂SiO₅ wafers with precise composition control was evaluated and analyzed by oxygen permeation experiments at high temperatures using an oxygen tracer. Oxygen permeation proceeded due to mutual grain boundary diffusion of oxide ions and Yb ions without synergistic effects such as acceleration or suppression. The oxygen shielding properties of Yb₂SiO₅ were compared with those of the other line compounds such as Yb₂Si₂O₇ and Al₂O₃ based on the determined mass transfer parameters. It was found that the more preferentially an oxide ion diffuses in the grain boundary compared to the interior of the grain, the greater the effect of suppressing the movement of the oxide ion by applying an oxygen potential gradient becomes.     

Revealing Electrical-Poling-Induced Polarization Potential in Hybrid Perovskite Photodetectors

Despite recent rapid advances in metal halide perovskites for use in optoelectronics, the fundamental understanding of the electrical-poling-induced ion migration, accounting for many unusual attributes and thus performance in perovskite-based devices, remain comparatively elusive. Herein, the electrical-poling-promoted polarization potential is reported for rendering hybrid organic–inorganic perovskite photodetectors with high photocurrent and fast response time, displaying a tenfold enhancement in the photocurrent and a twofold decrease in the response time after an external electric field poling. First, a robust meniscus-assisted solution-printing strategy is employed to facilitate the oriented perovskite crystals over a large area. Subsequently, the electrical poling invokes the ion migration within perovskite crystals, thus inducing a polarization potential, as substantiated by the surface potential change assessed by Kelvin probe force microscopy. Such electrical-poling-induced polarization potential is responsible for the markedly enhanced photocurrent and largely shortened response time. This work presents new insights into the electrical-poling-triggered ion migration and, in turn, polarization potential as well as into the implication of the latter for optoelectronic devices with greater performance. As such, the utilization of ion-migration-produced polarization potential may represent an important endeavor toward a wide range of high-performance perovskite-based photodetectors, solar cells, transistors, scintillators, etc.     

Electroactive polymers containing 3-arylcarbazolyl units as hole transporting materials for OLEDs

Monomers and their polymers containing 3-arylcarbazolyl electrophores have been synthesized by the multi-step synthetic route. The materials were characterized by thermo-gravimetric analysis, differential scanning calorimetry and electron photoemission technique. The polymers represent materials of high thermal stability having initial thermal degradation temperatures in the range of 331–411 °C. The glass transition temperatures of the amorphous polymeric materials were in the rage of 148–175 °C. The electron photoemission spectra of thin layers of monomers showed ionization potentials in the range of 5.6–5.65 eV. Hole-transporting properties of the polymers were tested in the structures of organic light emitting diodes with Alq₃ as the green emitter. The device containing hole-transporting layers of polyether with 3-naphthylcarbazolyl groups exhibited the best overall performance with a maximum current efficiency of 3.3 cd/A and maximum brightness of about 1000 cd/m².     

Prediction of methane adsorption content in continental coal-bearing shale reservoir using SLD model

Shale gas, as an important unconventional resource, has drawn global attention. It is mainly composed of adsorption gas and free gas. Adsorption gas content could play an important guiding role on both the selection of favorable perspective area and the exploration and exploitation of shale gas resources. In order to accurately measure adsorption gas content, a new approach was established to predict the adsorption isotherm of methane on shale. Based on the simplified local-density (SLD) method, both the adsorption isotherms of illite, illite/smectite mixed-layer, cholorite and type III kerogen and the total shale rock could be well fitted. The fitting results show good coincidences with the true experimental test data, which proves the method is reasonable and dependable and the prediction results are effective and credible. In addition, the good simulation results show that the SLD parameters can reflect the pore structure characteristics and corresponding adsorption characteristics of the shale samples, which can be used for the quantitative characterization of shale pore system.     

Forging furnace with thermochemical waste-heat recuperation by natural gas reforming: Fuel saving and heat balance

This paper considers thermochemical recuperation (TCR) of waste-heat using natural gas reforming by steam and combustion products. Combustion products contain steam (H₂O), carbon dioxide (CO₂), and ballast nitrogen (N₂). Because endothermic chemical reactions take place, methane steam-dry reforming creates new synthetic fuel that contains valuable combustion components: hydrogen (H₂), carbon monoxide (CO), and unreformed methane (CH₄). There are several advantages to performing TCR in the industrial furnaces: high energy efficiency, high regeneration rate (rate of waste-heat recovery), and low emission of greenhouse gases (CO₂, NO_x). As will be shown, the use of TCR is significantly increasing the efficiency of industrial furnaces – it has been observed that TCR is capable of reducing fuel consumption by nearly 25%. Additionally, increased energy efficiency has a beneficial effect on the environment as it leads to a reduction in greenhouse gas emissions.     

含煤盆地深层“超饱和”煤层气形成条件

中国深层煤层气资源丰富，但总体勘探和认识程度较低，尚未形成较为系统的深层煤层气地质理论。通过解剖分析准噶尔盆地白家海凸起和鄂尔多斯盆地临兴区块深层"超饱和"煤层气井的试气/生产动态，估算原地游离气的含气量，分析了深层"超饱和"煤层气的形成条件。研究表明：①深层"超饱和"煤层气储层中除吸附气外，还含有原地游离气，用常规试气方法可直接获得气流，煤层气的产出不明显依赖于排水降压；②埋藏超过一定深度，在煤阶和温度的综合作用下，煤的吸附能力将随埋深的继续增加而降低，煤层中吸附气的饱和度有增加的趋势，在达到吸附饱和后，出现原地游离气并形成"超饱和"煤层气，盆地深层具有"超饱和"煤层气形成的优势条件；③由于地温梯度和压力梯度的不同，不同盆地"超饱和"煤层气出现的临界深度不同，异常高压和异常高热流可以降低深层"超饱和"煤层气形成的临界深度；④深层"超饱和"煤层气开发具有大大缩短见气时间、充分利用地层能量和累积产水量低等优势，有望成为未来煤层气勘探开发的一个重要领域。