探究Cu/ZnO相互作用对CO2加氢制甲醇反应性能的影响

Using renewable green hydrogen and carbon dioxide (CO₂) to produce methanol is one of the fundamental ways to reduce CO₂ emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO₂ catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO₂ (Nor-CZS), co-precipitation Cu/ZnO-SiO₂ (Co-CZS), and reverse precipitation Cu/ZnO-SiO₂ (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO₂ to methanol. The results of temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO₂ interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO₂ conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO₂ conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO₂ conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts.     

基于多齿席夫碱的双核Dy(Ⅲ)配合物的合成、晶体结构和磁性

以2-肟基丙烷酰肼缩2-羟基萘甲醛席夫碱(H2L)为主配体,乙酰丙酮(Hacac)为辅配体,构筑了一例双核稀土镝配合物[Dy2(L)2(acac)2(CH3CH2OH)2](1).通过单晶X射线衍射、元素分析以及磁性测试对其结构和磁行为进行了表征.结构分析表明,配合物1是一个结构呈中心对称的双核镝(Ⅲ)配合物,其结构的...     

Effects of mussel-inspired co-deposition of 2-hydroxymethyl methacrylate and poly (2-methoxyethyl acrylate) on the hydrophilicity and binding tendency of common hemodialysis membranes: Molecular dynamics simulations and molecular docking studies

Despite advances in the field, hemoincompatibility remains a critical issue for hemodialysis (HD) as interactions between various human blood constituents and the polymeric structure of HD membranes results in complications such as activation of immune system cascades. Adding hydrophilic polymer structures to the membranes is one modification approach that can decrease the extent of protein adsorption. This study conducted molecular dynamics (MD) simulations to understand the interactions between three human serum proteins (fibrinogen [FB], human serum albumin, and transferrin) and common HD membranes in untreated and modified forms. Poly(aryl ether sulfone) (PAES) and cellulose triacetate were used as the common dialyzer polymers, and membrane modifications were performed with 2-hydroxymethyl methacrylate (HEMA) and poly (2-methoxyethyl acrylate) (PMEA), using polydopamine-assisted co-deposition. The MD simulations were used as the framework for binding energy simulations, and molecular docking simulations were also performed to conduct molecular-level investigations between the two modifying polymers (HEMA and PMEA) and FB. Each of the three proteins acted differently with the membranes due to their unique nature and surface chemistry. The simulations show PMEA binds less intensively to FB with a higher number of hydrogen bonds, which reflects PMEA's superior performance compared to HEMA. The simulations suggest PAES membranes could be used in modified forms for blood-contact applications as they reflect the lowest binding energy to blood proteins.     

Solid-state reactions of organometallic aldehydes with optically active primary β-hydroxyamines

The solid-state reactions of crystalline ferrocenyl- and ruthenocenylaldehydes with optically active primary β-hydroxyamines were studied at ∼20 °C. The yield of the products increases substantially in the presence of K₂CO₃. The tautomeric equilibrium between imines and diastereomeric oxazolidines with the predominant formation of one of them is established in solutions of the products in CDCl₃. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2240–2243, December, 1997.     

Synthesis and structure of azomethines based onN-vinyl derivatives of 2-amino- and 2-formylimidazoles

New Schiff's bases of theN-vinylimidazole andN-vinylbenzimidazole series were synthesized.¹H NMR data suggest that the azomethines exist in theE-form with respect to the CH=N bond and that the vinyl groups havetrans-orientation relative to each other. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 1857–1859, October, 1997.     

Investigation of the interactions in emulsions stabilized by a polymeric surfactant and its mixtures with an anionic surfactant

 The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation. Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed concerned the extent of the linear viscoelasticity region. Received: 22 November 1996 Accepted: 24 March 1997     

Coordination behavior of N-benzoylamino acids: Synthesis and structure of mixed-ligand complexes of palladium (II) with N-benzoylamino acid dianion and diamine

Four new mixed-ligand complexes of palladium (II) with L₁ (N-benwyl-α-amino acid dianion) and L₂ [ethyldiamine (en), 2. 2′-bipyridine (Bpy) and 1.10-phenanthroline (Phen)] were synthesized. All the complexes have been characterized by elemental analyses, molar conductance, infrared and¹H NMR spectra and thermo-gravimetric analyses. Crystal structures of [Pd(Bpy)(Bzval-N, O)] and [Pd(en)(Bzphe-N, O) ·H₂O have been determined by X-ray diffraction analysis. The results indicate that in all the complexes’ ligand L₁ coordinates to palladium (II) through deprotonated amide nitrogen and carboxylic oxygen, and there are some intramolecular noncovalent interactions in the complexes. Project supported by the Natural Science Foundation of Zhejiang Province, China.     

Characterisation of Sol-Gel TiO2 Films by Etching

This article describes the SmartKom Companion, one of three demonstrators developed within the SmartKom project whose goal has been to provide an intuitive and intelligent interface for non-expert users to everyday computer-based applications in different scenarios of use. Conceived for the SmartKom Mobile scenario, the Companion allows intuitive multimodal interaction for drivers and pedestrians. The development of the SmartKom prototypes was constantly accompanied by Wizard-of-Oz experiments as well as system evaluations at different stages of the project. Some usability evaluation results relative to the SmartKom Companion will also be presented.     

Effect of 1,1,2,2-tetrachloroethane on IR spectra of HCl complexes withN,N-dimethylformamide and 1-methyl-2-pyrrolidone formed by a strong quasi-symmetric hydrogen bond

The effect of 1,1,2,2-tetrachloroethane (TCE) on the IR spectra of HCl complexes withN,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (N-MP) with strong quasisymmetric hydrogen bonds was studied using Multiple Attenuated Total Reflection (MATR) IR spectroscopy. The addition of TCE does not change the background absorption spectra, but results in a change in the extinction coefficients of some bands of these complexes. The analysis of the spectra shows that the HCl−DMF complexes interact only with one molecule of TCE, and the HCl−N-MP complexes interact with two molecules of TCE. It is shown that the neutral component of the system (TCE) has no effect on the parameters of the strong quasi-symmetric H-bond in the complexes studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 956–960, May, 1997.