Hydrogen production by supercritical water gasification of lignin over CuO–ZnO catalyst synthesized with different methods

In this study, lignin was gasified in supercritical water with catalysis of CuO–ZnO synthesized by deposition precipitation, co-precipitation and sol-gel methods. Sol-gel synthesized CuO–ZnO showed the highest catalytic performance, and the gasification efficiency was increased by 37.92% with it. The XRD, SEM-EDS and N₂ adsorption/desorption analysis showed that the priority of the sol-gel catalyst was the smallest crystallite size, largest specific surface area and high dispersion. For sol-gel synthesized CuO–ZnO, the increase of CuO/ZnO ratio improved the gasification efficiency but reduced H₂ selectivity. And the catalytic activity was reduced with the calcination temperature above 600 °C due to enlarged crystallites and reduced pores. During sol-gel preparation, both the addition of ethanol and PEG in the solvent reduced the agglomeration and improved the catalytic activity. With CuO–ZnO prepared with 1 g PEG + water as the solvent, the highest H₂ yield of 6.86 mol/kg was obtained, which was over 1.5 times of that without catalyst.     

Experimental investigation of Co and Fe-Doped CuO nanostructured electrode material for remarkable electrochemical performance

The current research work presents a facile and cost–effective co-precipitation method to prepare doped (Co & Fe) CuO and undoped CuO nanostructures without usage of any type of surfactant or capping agents. The structural analysis reveals monoclinic crystal structure of synthesized pure CuO and doped-CuO nanostructures. The effect of different morphologies on the performance of supercapacitors has been found in CV (cyclic voltammetry) and GCD (galvanic charge discharge) investigations. The specific capacitances have been obtained 156 (±5) Fg^?1, 168(±5) Fg^?1 and 186 (±5) Fg^?1 for CuO, Co-doped CuO and Fe-doped CuO electrodes, respectively at scan rate of 5 mVs^?1, while it is found to be 114 (±5) Fg^?1, 136 (±5) Fg^?1 and 170 (±5) Fg^?1 for CuO, Co–CuO and Fe–CuO, respectively at 0.5 Ag^-1 as calculated from the GCD. The super capacitive performance of the Fe–CuO nanorods is mainly attributed to the synergism that evolves between CuO and Fe metal ion. The Fe-doped CuO with its nanorods like morphology provides superior specific capacitance value and excellent cyclic stability among all studied nanostructured electrodes. Consequently, it motivates to the use of Fe-doped CuO nanostructures as electrode material in the next generation energy storage devices.     

Active sites of Cu-ZSM-5 for the decomposition of acrylonitrile

The catalytic decomposition of acrylonitrile (AN) over Cu-ZSM-5 prepared with various Cu loadings was investigated. AN conversion, during which the nitrogen atoms in AN were mainly converted to N₂, increased as Cu loading increased. N₂ selectivities as high as 90–95% were attained. X-ray diffraction measurements (XRD) and temperature-programmed reduction by H₂ (H₂-TPR) showed the existence of bulk CuO in Cu-ZSM-5 with a Cu loading of 6.4 wt% and the existence of highly dispersed CuO in Cu-ZSM-5 with a Cu loading of 3.3 wt%. Electron spin resonance measurements revealed that Cu-ZSM-5 contains three forms of isolated Cu²⁺ ions (square-planar, square-pyramidal, and distorted square-pyramidal). The H₂-TPR results suggested that in Cu-ZSM-5 with a Cu loading of 2.9 wt% and below, Cu⁺ existed even after oxidizing pretreatment. The activity of AN decomposition over Cu/SiO₂ suggested that CuO could form N₂, but, independent of the CuO dispersion, nitrogen oxides (NO_x) were formed above 350 °C. Cu⁺ and the square-pyramidal and distorted square-pyramidal forms of Cu²⁺ showed low activity for AN decomposition. Temperature-programmed desorption of NH₃ suggested that N₂ formation from NH₃ proceeded on Cu²⁺, resulting in the formation of Cu⁺. The Cu⁺ ions were oxidized to Cu²⁺ at around 300 °C. Thus, high N₂ selectivity over Cu-ZSM-5 with a wide range of temperature was probably attained by the reaction over the square-planar Cu²⁺, which can be reversibly reduced and oxidized.     

Air-Oxidation Behavior of a Cu60Hf25Ti15 Bulk Metallic Glass at 375–520 °C

The oxidation behavior of a Cu₆₀Hf₂₅Ti₁₅ bulk metallic glass was studied over the temperature range of 375–520 °C in dry air. The oxidation kinetics of the amorphous alloy generally followed the parabolic law at all temperatures, with an oxidation rate increasing with temperature. The oxidation rates of the amorphous alloy were much higher than those of polycrystalline pure-Cu, implying that the additions of Hf and Ti accelerated the oxidation reaction. The composition of the scales formed on the amorphous alloy was strongly temperature-dependent, since they consisted mostly of Cu₄O₃ and CuO with minor amounts of HfO₂ at T ≤ 450 °C, while mostly CuO with minor amounts of HfO₂ and Cu₂TiO₃ were detected at higher temperatures. In addition, nanocrystalline Cu₅₁Hf₁₄ and Cu₃Ti₂ phases were detected on the substrate after oxidation at T ≥ 450 °C, indicating the occurrence of phase transformation.     

Preparation of solar selective absorbing CuO coating for medium temperature application

A new method of preparing CuO solar selective absorbing coating for medium temperature is presented. After pretreatment, brass was overlaid with CuO by chemical plating. The effects of reactant concentration, reaction temperature and reaction time on the absorptivity of CuO coating were investigated. The optimized condition of preparing CuO coating was obtained. The CuO coating was analyzed with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). In order to prolong the period of use, the CuO coating was protected by TiO₂. The experiment shows that the TiO₂/CuO coating is more heat-resistant, acid-resistant, and wear resistant than CuO coating, without losing absorptivity markedly. The TiO₂ coating can reduce emissivity and protect the CuO coating. Translated from Journal of Tianjin University, 2006, 39(12): 1485–1489 [译自: 天津大学学报]     

Effect of Pretreatment Atmosphere on CuO/TiO2 Activities in NO + CO Reaction

Using TiO₂ as carrier, CuO/TiO₂ catalysts with different CuO loading were prepared by the impregnation method. The catalytic activities in NO+CO reaction were examined with a micro-reactor gas chromatography reaction system and the methods of TPR, XPS and NO-TPD. It was found that the catalytic activities were affected by pretreatment atmosphere, i.e. H₂ atmosphere > reduction–reoxidation > 10%CO/He > reaction gas (fresh sample). NO decomposition was better by low-valence Cu species than by high-valence Cu species, i.e. Cu⁰>Cu⁺>Cu²⁺. The XPS results indicated that Cu species on CuO/TiO₂ were Cu⁰, Cu⁺, normal Cu²⁺(Cu²⁺(I)) and chain-structured Cu²⁺(Cu²⁺(II)) as –Cu–O–Ti–O–. The activities of Cu²⁺(II) were much higher than that of Cu²⁺(I), but both species were very unstable in the reaction atmosphere and easily reduced by CO, which accounted for the variable activities of fresh catalysts with increasing reaction temperature. In NO+CO reaction, the redox process was a cycle of Cu⁺–Cu²⁺(I) at low reaction temperature but was a cycle of Cu⁰–Cu⁺ at high reaction temperature. As shown by NO-TPD, high catalytic activities could be attributed to the following factors, e.g. oxygen caves on the catalyst’s surface after pretreatment with H₂ and reduction–reoxidation, formation of Cu⁰ after pretreatment with H₂, and increment of Cu species dispersion and formation of Cu²⁺(II) after pretreatment with reduction–reoxidation.     

超声和微波作用下制备纳米氧化铜

以氢氧化铜为前驱体，在超声和微波作用下制备纳米氧化铜。借助透射电镜（TEM）、X射线衍射（XRD）、粒度分析等手段，研究了超声、分散剂、微波等制备条件的影响。结果表明：采用该法可以制备粒径小（15nm）、分散良好的纳米氧化铜粉体；超声可使前驱体Cu（OH）2转变为CuO，并粉碎颗粒间形成的团聚；分散剂通过表面修饰抑制颗粒的团聚；微波加热促进了前驱体的转化，并抑制颗粒的长大。     

水热碱性条件下(糖)醇对Cu2+的还原

研究了不同水热(180℃)碱性条件下(糖)醇对Cu2 的还原,通过控制不同水热条件及添加不同种类和质量的(糖)醇,借助XRD和SEM分析,得到了不同的产物及产物形貌.当不加任何(糖)醇时,产物为CuO,其形貌随c(OH-)/c(Cu2 )增大而由薄带和球形颗粒向薄片转变;当在不同c(OH-)/c(Cu2 )中添加同量的D-Sorbitol,c(OH-)/c(Cu2 )=2时产物主要为Cu2O,具有多种形貌,c(OH-)/c(Cu2 )=4和6时产物都为金属Cu,但c(OH)/c(Cu2 )=4时产物形貌有线状、棒状及立方六角状,c(OH-)/c(Cu2 )=6时产物主要为颗粒状;当保持c(OH-)/c(Cu2 )=4而添加不同质量的D-Sorbitol时,产物也都为金属Cu,形貌上有较大差异;当保持c(OH-)/c(Cu2 )=4而添加等摩尔数的不同(糖)醇D-Sorbitol,Mannitol,Xylitol时,产物还都是金属Cu,形貌随(糖)醇不同而发生显著变化.研究结果表明,水热(180℃)条件下,c(OH-)/c(Cu2 )值可以决定产物形貌,(糖)醇的加入不仅可以与Cu2 或其配合物发生氧化还原反应,而且其加入的质量和种类可以决定产物的形貌.     

The effect of steam treatment on MeO/Al2O3 model catalysts (Me = Ni,Co, Cu,Fe)

To study the influence of steam on the solid state reaction between MeO (Me = Ni, Co, Cu or Fe) and Al₂O3, MeO/-Al₂O₃ and MeO/-Al₂O₃ model catalysts were kept in either N₂/20% O₂ or N₂/O₂/30% H₂O at 500–1000°C. The samples were subsequently analyzed with RBS and FTIR. Surprisingly, nickel, cobalt and copper volatilized when MeO/-Al₂O₃ or MeAl₂U₄/-Al₂O₃ samples were annealed in the presence of 0.3 atm steam at 1000°C. Especially copper was found to volatilize very rapidly in the presence of steam, even at a temperature as low as 800°C. FTIR spectra of steam-treated NiO/-Al₂O₃ samples showed the incorporation of hydroxyl groups in the nickel oxide layer. This observation and an excellent agreement with thermochemical calculations support our conclusion that the volatile species are metal hydroxides. The solid state reaction of MeO with-Al₂O₃ was found to proceed at a much higher rate in the presence of 0.3 atm steam at 500–800°C, presumably as a result of an enhanced surface mobility of Me and Al ions along the grain boundaries and the surfaces of the internal pores of the-Al₂O₃ support, when steam is present.