Evolution of the Cu/ZnO methanol synthesis catalyst during its reduction and re-oxidation

Summary Cu K EXAFS studies of the structure of Cu-Zn oxide catalyst were performed for the as prepared samples, those after its activation by hydrogen and after its subsequent re-oxidation. It was found that during the primary formation of the CuZnO solid solution, the copper ions are dissolved in the extended stacking faults of the ZnO lattice as ultra-small oxide clusters. Activation by hydrogen at 473 K leads to the reduction of most copper cations to Cu⁰with the formation of nanoparticles with the characteristic size of ca. 1.6 nm. The copper metal particles were re-oxidized to Cu²⁺at 523 K in<span lang=EN-US style='mso-ansi-language:EN-US'>ahelium flow containing 0.05 vol. % oxygen. The re-oxidized cations do not form a CuO phase. Instead, they return to the extended stacking faults of ZnO. However, this time they form stripe-like clusters of square-planar coordinated copper cations.     

Adsorptive property of Cu2+–ZnO/cetylpyridinium–montmorillonite complexes for pathogenic bacterium in vitro

Cu²⁺–ZnO/cetylpyridinium–montmorillonite (Cu²⁺–ZnO/CP–MMT) complexes were prepared using montmorillonite (MMT), Cu²⁺, Zn²⁺, and cetylpyridinium (CP). The goal was to assess comparatively the adsorption properties of Cu²⁺–ZnO/CP–MMT in vitro using pathogenic Escherichia coli. The results showed that Cu²⁺–ZnO/CP–MMT adsorbed significantly (P < 0.05) more E. coli compared with the parent clay. The adsorption process of bacterial cells occurring on the modified MMT surface reached equilibrium after 90 min. The percentages of E. coli adsorbed onto the surfaces of Cu²⁺–ZnO/CP–MMT and MMT in adsorption equilibrium were 84.66% and 47.01%, respectively. Adsorption data from the bacteria-clay systems followed the Langmuir and Freundlich isotherms, but not the BET isotherm. Adsorption of E. coli in acidic medium was higher than in alkaline medium. The extent of bacteria adsorption onto the modified MMT increased with decreasing ionic strength, and with increasing temperature. The processes of E. coli adsorption onto the tested adsorbents were endothermic and spontaneous at the experimental temperature. The mechanism of adsorption of bacteria on Cu²⁺–ZnO/CP–MMT may involve enhanced hydrophobicity and the reversal of surface charge from negative to positive.     

梨形核壳结构氧化锌/银亚微米球的制备、表征及光学性能

利用亚锡离子还原银离子生成的金属银沉积在合成的梨形氧化锌表面作为晶种,进一步生长银纳米粒子,制备了梨形的、核壳结构的、单分散的氧化锌/银亚微米球。利用X射线衍射、透射电镜、能量色散X射线谱、紫外可见吸收谱及光致发光谱对所制备样品的形貌、微观结构、组成和光学性能进行了表征。结果表明:(1)样品是由梨形亚微米氧化锌核和银纳米颗粒壳组成;(2)在氧化锌表面的银纳米粒子作为光激发产生的电子捕获剂提高了光产生的载流子的分离效率,在能量没有改变的情况下减少了紫外发射光的强度,淬灭了可见发射光。     

Synthesis of ZnO/Cu2S core/shell nanorods and their enhanced photoelectric performance

In this work, two kinds of ZnO/Cu₂S core/shell nanorods (NRs) have been successfully synthesized from ZnO NRs for photoelectrochemical (PEC) water splitting by a versatile hydrothermal chemical conversion method (H-ZnO/Cu₂S core/shell NRs) and successive ionic layer adsorption and reaction method (S-ZnO/Cu₂S core/shell NRs), respectively. The photoelectrode is composed of a core/shell structure where the core portion is ZnO NRs and the shell portion is Cu₂S nanoparticles sequentially located on the surface. The ZnO NRs array provides a fast electron transport pathway due to its high electron mobility properties. The optical property of both two kinds of core/shell NRs was characterized, and enhanced absorption spectrum was discovered. Our PEC system produced very high photocurrent density and photoconversion efficiency under 1.5 AM irradiation for hydrogen generation. On the basis of a versatile chemical conversion process based on the ion-by-ion growth mechanism, H-ZnO/Cu₂S core/shell NRs exhibit a much higher photocatalytic activity than S-ZnO/Cu₂S core/shell NRs. The photocurrent density and photoconversion efficiency of H-ZnO/Cu₂S core/shell NRs are up to 20.12 mA cm^?2 at 0.85 V versus SCE and 12.81 % at 0.40 V versus SCE, respectively.     

The impact of surface Cu2+ of ZnO/(Cu1−xZnx)O heterostructured nanowires on the adsorption and chemical transformation of carbonyl compounds

The surface cation composition of nanoscale metal oxides critically determines the properties of various functional chemical processes including inhomogeneous catalysts and molecular sensors. Here we employ a gradual modulation of cation composition on a ZnO/(Cu_1−xZn_x)O heterostructured nanowire surface to study the effect of surface cation composition (Cu/Zn) on the adsorption and chemical transformation behaviors of volatile carbonyl compounds (nonanal: biomarker). Controlling cation diffusion at the ZnO(core)/CuO(shell) nanowire interface allows us to continuously manipulate the surface Cu/Zn ratio of ZnO/(Cu_1−xZn_x)O heterostructured nanowires, while keeping the nanowire morphology. We found that surface exposed copper significantly suppresses the adsorption of nonanal, which is not consistent with our initial expectation since the Lewis acidity of Cu²⁺ is strong enough and comparable to that of Zn²⁺. In addition, an increase of the Cu/Zn ratio on the nanowire surface suppresses the aldol condensation reaction of nonanal. Surface spectroscopic analysis and theoretical simulations reveal that the nonanal molecules adsorbed at surface Cu²⁺ sites are not activated, and a coordination-saturated in-plane square geometry of surface Cu²⁺ is responsible for the observed weak molecular adsorption behaviors. This inactive surface Cu²⁺ well explains the mechanism of suppressed surface aldol condensation reactions by preventing the neighboring of activated nonanal molecules. We apply this tailored cation composition surface for electrical molecular sensing of nonanal and successfully demonstrate the improvements of durability and recovery time as a consequence of controlled surface molecular behaviors.

Unexpected features of surface Cu²⁺ on ZnO/(Cu1−xZnx)O nanowires for molecular transformation and electrical sensing of carbonyl compounds were found.     

Oxidation‐induced nanostructures on Cu{100}, Cu(Ag) and Ag/Cu{100} studied by photoelectron spectroscopy

Initial surface oxidation and nanoscale morphology on Cu{100}, Cu(Ag) and Ag/Cu{100} have been investigated in situ by X‐ray photoelectron spectroscopy (XPS), X‐ray induced Auger electron spectroscopy (XAES) and the inelastic electron background analysis as a function of oxygen exposure at 3.7 × 10^?2 and 213 mbar pressures at a surface temperature of 373 K. Relative Cu₂O concentrations have been quantified by analysis of the peak shape of the XAES Cu LMM transition. The surface morphology of Cu₂O islands and the Ag layer has been characterized by inelastic electron background analysis of XAES O KLL and Ag 3d transitions. Oxygen‐induced segregation of Cu, as well as the subsequent Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces, has been investigated quantitatively. Our results indicate that Ag has a clear inhibitive effect on the initial oxidation and Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces. The Cu₂O islands are also observed to remain highly strained on Ag/Cu{100} even at higher O₂ exposures. The results suggest that strained Cu₂O islands eventually penetrate through the buried Ag layer, and in conjunction with segregating Cu atoms enable the oxidation to proceed at a similar rate to or even faster than on the unalloyed Cu surface. Copyright © 2007 John Wiley & Sons, Ltd.     

M2+(M=Cu、Cd、Ag、Fe)掺杂氧化锌纳米粉晶的抗菌性能

采用柠檬酸溶胶-凝胶法制备了ZnO及M²⁺掺杂ZnO纳米粉晶(M=Cu、Cd、Ag、Fe),用现代测试技术表征了样品的组成、结构和形貌,以大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)和白色念珠菌(Candida albicans)为测试菌株,用抑菌圈、最小抑菌浓度和最小杀菌浓度等方法研究了样品在日光照射下的抗菌活性。结果表明,与母体ZnO相比,Cu、Ag、Cd掺杂样品的抗菌性能明显地增强,这可能是由于掺杂金属离子置换Zn²⁺生成了晶格缺陷和电荷缺陷,阻止了光生电子和光生空穴对的复合从而增强了光催化活性和抗菌活性。     

溶剂极性对微波辐射老化制备前驱体及CuO/ZnO/Al2O3催化剂结构的影响

在制备CuO/ZnO/Al2O3催化剂的老化过程中,采用微波辐射老化技术,着重研究了溶剂极性对前躯体物相组成,烧后CuO/ZnO/Al2O3催化剂结构及其在浆态床合成甲醇工艺中催化性能的影响。通过XRD、DTG、H2-TPR,FTIR、HR-TEM和XPS对前驱体及催化剂表征表明,沉淀母液在微波辐射条件下进行老化,溶剂的极性对前躯体物相组成及催化剂结构影响显著。随着溶剂极性的增大,Zn2+/Cu2+取代Cu2(CO3)(OH)2/Zn5(CO3)2(OH)6中Cu2+/Zn2+的取代反应增强,使得前躯体中(Cu,Zn)5(CO3)2(OH)6和(Cu,Zn)2(CO3)(OH)2物相的含量增多,结晶度提高,导致烧后CuO/ZnO/Al2O3催化剂中CuO-ZnO协同作用增强,且CuO晶粒减小,表面Cu含量增加,催化剂活性和稳定性提高。水溶剂的极性最大,制备的催化剂活性和稳定性最好,甲醇的时空收率(STY)和平均失活率分别为320 mg.g-1.h-1和0.11%.d-1。     

Enhanced activity of CuO/ZnO catalyst on the decomposition of dimethylhexane-1,6-dicarbamate into dimethylhexane-1,6-diisocyanate

To decompose dimethylhexane-1,6-dicarbamate (HDC) to hexamethylene diisocyanate (HDI), mixed CuO and ZnO catalysts with Cu/(Cu?+?Zn) ratio of 4 and 8% were prepared by coprecipitation (CP), sequential precipitation (SP) and incipient wetness impregnation (IW). The SP-derived CuO/ZnO catalysts showed higher HDC yields than those derived by CP and IW. The IW method produced CuO/ZnO catalysts consisting of larger CuO and ZnO particles compared to the two precipitation methods. The CP method led to substitution of Zn²⁺ by Cu²⁺ in the hydrozincite precursor phase, resulting in higher BET and Cu surface areas of CuO–ZnO catalysts due to intimate intergrowth of nano-sized particles. However, the inherent character of ZnO in the CP-derived catalysts was modified by interfacial contact between CuO and ZnO identified by UV–visible and Raman spectra. In contrast, the properties of CuO and ZnO, as well as the relatively large surface areas, were kept in the SP-derived catalysts owing to deposition of Cu precipitates to fully aged Zn precipitates. This is believed to be a benefit of the SP method for the reaction. Therefore, our preparation approach has great potential to be extended to various mixed oxide catalysts.     

X-ray absorption near edge structures (xanes) of Cu/ZnO/Al2O3 Co shift catalysts

X-ray absorption near edge structures (XANES) of some Cu/ZnO/Al₂O₃CO shift catalysts have been measured at high resolution using synchrotron radiation, and compared to reference compounds Prior to reduction. CuO and ZnO are present, after reduction ZnO and highly dispersed Cu, no indication was found for Cu₂O or the presence of spinels. The results are qualitatively confirmed by preliminary analysis of EXAFS spectra.     

微波辐射对浆态床合成甲醇CuO/ZnO/Al2O3催化剂前驱体晶相转变的影响

在微波辐射条件下,对CuO/ZnO/Al2O3催化剂的沉淀母液进行老化,通过XRD、TG、H2-TPR,FTIR、HR-TEM和XPS对前驱体及催化剂微观结构的进行表征,探讨了CuO/ZnO/Al2O3催化剂前驱体晶相转变过程中微波辐射的作用。结果表明,微波辐射有利于Cu2+取代Zn5(CO3)2(OH)6中Zn2+的同晶取代反应。微波辐射的老化过程中,首先发生Cu2+取代Zn5(CO3)2(OH)6中Zn2+生成(Cu,Zn)5(CO3)2(OH)6的同晶取代反应,并于1.0 h内基本完成;随着老化时间继续延长,主要进行Zn2+取代Cu2(CO3)(OH)2中Cu2+生成(Cu,Zn)2(CO3)(OH)2的同晶取代反应,同时(Cu,Zn)5(CO3)2(OH)6进一步结晶。与常规老化1 h制备的前驱体相比,微波辐射老化1.0 h制备的前驱体含有较多的(Cu,Zn)5(CO3)2(OH)6物相,有助于增强焙烧后CuO/ZnO/Al2O3催化剂中CuO-ZnO协同作用,提高表面铜含量,进而提高CuO/ZnO/Al2O3催化剂在浆态床合成甲醇的催化活性和稳定性,在400 h浆态床合成甲醇评价期间,甲醇时空收率最大达318.9 g.kg-1.h-1,失活率仅为0.11%.d-1。     

Preparation of Shell-Core Cu(2)O-Cu Nanocomposite Particles and Cu Nanoparticles in a New Microemulsion System

Shell–core Cu₂O–Cu nanocomposite particles and metal Cu nanoparticles are synthesized in a new microemulsion system which consists of saturated Cu²⁺ salt aqueous solution dispersed in isopropanol and stabilized by polyvinylalcohol (PVA). The size of the composite particles and the thickness of the Cu₂O shell layer can be controlled by the volume ratio of isopropanol to H₂O (the ratio is defined as R). When R ≥ 1000, it is available to obtain metal Cu nanoparticles.     

油溶性Cu纳米颗粒的两相法制备

在四氢呋喃-饱和氯化钠水溶液的两相体系中利用两相法化学合成了双正十六烷氧基二硫代磷酸(DDP)表面修饰的Cu纳米颗粒. 系统探讨了不同因素对制备Cu纳米颗粒的影响, 并采用透射电子显微镜(TEM)比较分析不同还原剂的用量、Cu^2＋浓度、修饰剂双正十六烷氧基二硫代磷酸铵盐(ADDP)和Cu^2＋的物质的量之比对Cu纳米颗粒粒径及分布的影响; 通过红外光谱仪(IR)、X射线粉末衍射仪(XRD)、X射线光电子能谱仪(XPS)等测试技术对优化条件下所合成的铜纳米颗粒进行了结构表征. 结果表明, 合成粒径细小、分布均匀的铜纳米颗粒的工艺条件为pH值在12左右, 反应温度高于30 ℃, 铜离子浓度小于0.05 mol•L^－1, NaBH₄与Cu^2＋的物质的量之比在8∶1到12∶1之间, ADDP和Cu^2＋的物质的量之比为2∶1和2.5∶1; 所制备的铜纳米颗粒是由无定形的金属Cu无机纳米核及通过化学键键合在其表面的DDP分子所组成, 并且修饰剂在反应前后结构没发生变化.     

Preparation, microstructure characterization and catalytic performance of Cu/ZnO and ZnO/Cu composite nanoparticles for liquid phase methanol synthesis

Stearate@Cu/ZnO nanocomposite particles with molar ratios of ZnO?∶?Cu = 2 and 5 are synthesized by reduction of the metal-organic Cu precursor [Cu{(OCH(CH(3))CH(2)N(CH(3))(2))}(2)] in the presence of stearate@ZnO nanoparticles. In the case of ZnO?∶?Cu = 5, high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) combined with electron-energy-loss-spectroscopy (EELS) as well as attenuated total reflection Fourier transform infrared (ATR-IR) spectroscopy are used to localize the small amount of Cu deposited on the surface of 3-5 nm sized stearate@ZnO particles. For ZnO?∶?Cu = 2, the microstructure of the nanocomposites after catalytic activity testing is characterized by HAADF-STEM techniques. This reveals the construction of large Cu nanoparticles (20-50 nm) decorated by small ZnO nanoparticles (3-5 nm). The catalytic activity of both composites for the synthesis of methanol from syn gas is evaluated.     

表面助剂改性对Cu/ZnO/Al2O3甲醇合成催化剂性能的影响

采用共沉淀-后浸渍方法制备了表面助剂改性的Cu/ZnO/Al₂O₃ (CZA)甲醇合成催化剂, 在固定床反应器上以合成气为原料分别考察了三种助剂(Zr、Ba和Mn)对CZA催化剂性能的影响; 以Zr为助剂时反应温度的影响; 并进行了催化稳定性试验. 利用粉末X射线衍射(XRD)、低温氮气吸脱附(N₂-sorption)、氧化亚氮(N₂O)反应吸附技术、X射线光电子能谱(XPS)、氢气程序升温吸脱附(H₂-TPD)、扫描电子显微镜(SEM)和高分辨透射电子显微镜(HR-TEM)技术对催化剂进行了表征.结果显示: 以Zr或Ba作为助剂能够明显提高CZA催化剂耐热前后的甲醇时空收率(STY); Mn的引入降低了CZA催化剂的耐热前活性; Zr的引入降低了CZA催化剂最高活性温度点, 增强了CZA催化剂的催化稳定性; 还原态CZA催化剂表面Cu⁰和ZnO都能吸附活化氢气, Cu⁰与ZnO的强相互作用有利于提高催化剂的性能, 耐热后催化剂性能的降低归因于Cu晶粒的长大. 在实验和表征结果基础上,提出了CZA催化剂上合成气制甲醇的“双向同步催化反应历程”.     

Synthesis and thermo-physical properties of water-based novel Ag/ZnO hybrid nanofluids

The comparative study on the thermo-physical properties of water-based ZnO nanofluids and Ag/ZnO hybrid nanofluids is reported in the present study. The outer surface of ZnO nanoparticles was modified with a thin coating of Ag nanoparticles by a wet chemical method for improved stability and heat transfer properties. The ZnO and Ag/ZnO nanofluids were prepared with varying volume concentration (??=?0.02–0.1%). The synthesized nanoparticles and nanofluids were characterized with different characterization methods viz., scanning electron microscopy, X-ray diffraction, dynamic light scattering, thermal conductivity measurement, and viscosity measurement. Results show that thermal conductivity of Ag/ZnO hybrid nanofluids is found to be significantly higher compared to ZnO nanofluids. The maximum thermal conductivity an enhancement for Ag/ZnO nanofluid (??=?0.1%) is found to 20% and 28% when it compared with ZnO nanofluid (??=?0.1%) and water, respectively.     

Das Gleichgewicht des Cu2+−Cu+−Cu-systems in konzentrierten Perchloratlösungen

The equilibrium of the reaction Cu²⁺+Cu?2 Cu⁺ has been investigated in cone. solutions of Ca(ClO₄)₂. The apparent equilibrium constants of this reaction and the formal potentials of the Cu²⁺/Cu⁺, Cu²⁺/Cu and Cu⁺/Cu redox systems were determined. From these data the hydration numbers of the Cu²⁺ and Cu⁺ ions were estimated and the scheme of the reaction studied was proposed and discussed. In addition the equilibrium constants of the reaction Cu²⁺+Cu(Hg)?2 Cu⁺ were calculated and discussed.     

Ag/ZnO Catalysts with Different ZnO Nanostructures for Non‐enzymatic Detection of Urea

Silver coated ZnO nanorods and nanoflakes with different crystallographic orientations were synthesized by a combination of sputter deposition and solution growth process. Catalytic properties of morphology‐dependent Ag/ZnO nanostructures were then investigated for urea sensors without enzyme. Ag/ZnO nanorods on carbon electrodes exhibit a higher catalytic activity and an improved efficiency than Ag/ZnO nanoflakes on carbon electrodes. Ag/ZnO nanorod catalysts with more electrochemically surface area (169 cm² mg^?1) on carbon electrode facilitate urea electrooxidation due to easier electron transfer, which further promotes the urea electrolysis. The Ag/ZnO nanorod catalysts also show a significant reduction in the onset voltage (0.410 V vs. Ag/AgCl) and an increase in the current density (12.0 mA cm^?2 mg^?1) at 0.55 V vs Ag/AgCl. The results on urea electrooxidation show that Ag/ZnO nanostructures can be a potential catalyst for non‐enzymatic biosensors and fuel cells.     

Microstructure of metallic copper nanoparticles/metallic disc interface in metal–metal bonding using them

This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu²⁺ (0.01 M (CH₃COO)₂Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10^?4 M citric acid and 5 × 10^?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd.     

One pot synthesis of Ag nanoparticle modified ZnO microspheres in ethylene glycol medium and their enhanced photocatalytic performance

Ag nanoparticles (NPs) modified ZnO microspheres (Ag/ZnO microspheres) were prepared by a facile one pot strategy in ethylene glycol (EG) medium. The EG played two important roles in the synthesis: it could act as a reaction media for the formation of ZnO and reduce Ag⁺ to Ag⁰. A series of the characterizations indicated the successful combination of Ag NPs with ZnO microspheres. It was shown that Ag modification could greatly enhance the photocatalytic efficiency of ZnO microspheres by taking the photodegradation of Rhodamine B as a model reaction. With appropriate ratio of Ag and ZnO, Ag/ZnO microspheres showed the better photocatalytic performance than commercial Degussa P-25 TiO₂. Photoluminescence and surface photovoltage spectra demonstrated that Ag modification could effectively inhibit the recombination of the photoinduced electron and holes of ZnO. This is responsible for the higher photocatalytic activity of Ag/ZnO composites.