Hydrophobic modification of nanocellulose and all-cellulose composite films using deep eutectic solvent as a reaction medium

Cellulose - In this work, deep eutectic solvent (DES) based on imidazole and triethylmethylammonium chloride was used as a reaction medium for the esterification of cellulose nanofiber (CNF) and...     

Ru/CeO2催化剂催化苯乙烯氢甲氧基羰基化反应高选择性制备直链酯类化合物

酯类化合物在工业上具有广泛应用,例如可用于合成香水、调味剂(味精)、洗涤剂和表面活性剂等.其中,烯烃的氢烷氧基羰基化反应是一种合成酯类化合物的重要方法,其低消耗、100%的原子经济性和原料的易获得等优势使其在制备酯类化合物中成为一个有效且实际可行的方法.对于该反应,文献多采用Pd或Rh的络合均相催化剂,其中控制反应过程中直链酯类化合物(L)和支链酯类化合物(B)的选择性是一项颇具挑战性的课题.虽然目前可通过配体的设计和修饰来调节,但多集中在均相催化体系,因此在选择性调变方面的研究仍很欠缺.相对于均相催化,多相催化由于产物易分离和提纯、催化剂可循环使用等优势而逐渐引起了研究者的广泛关注.在多相催化体系中, Pd负载在强酸性树脂作为催化剂已被应用于苯乙烯氢甲氧基羰基化反应,但在该反应中支链酯类化合物为主要产物.因此,寻找一个可有效改善多相反应体系中选择性问题的方法是非常有意义的.在本研究工作中,我们分别以CeO2纳米颗粒(NP)、CeO2纳米棒(Rod)和CeO2纳米立方体为载体,利用浸渍法制备了Ru/CeO2、Ru/CeO2-rod和Ru/CeO2-cube三种催化剂,并进一步用于苯乙烯氢甲氧基羰基化反应.探究了CO压力、反应温度和反应时间对三种催化剂催化苯乙烯氢甲氧基羰基化反应的影响.结果表明, Ru/CeO2作为多相催化剂催化苯乙烯氢甲氧基羰基化反应时,苯乙烯选择性高于99%,直链酯选择性为83%,支链酯选择性为12%.机理研究表明,该反应为自由基机理.动力学分析表明,该反应的反应活化能为48.50 k Jmol^–1.结合三种催化剂的反应活性以及HRTEM结构表征结果可知,该反应中L/B比值与Ru的尺寸有较大关系.进一步的拉曼表征和NH3-TPD表征结果证明, Ru的尺寸与金属-载体之间的相互作用以及催化剂表面的氧空位浓度有直接关系.     

The Effect of Surface Site Ensembles on the Activity and Selectivity of Ethanol Electrooxidation by Octahedral PtNiRh Nanoparticles

Direct ethanol fuel cells are attractive power sources based on a biorenewable, high energy-density fuel. Their efficiency is limited by the lack of active anode materials which catalyze the breaking of the C−C bond coupled to the 12-electron oxidation to CO₂. We report shape-controlled PtNiRh octahedral ethanol oxidation electrocatalysts with excellent activity and previously unachieved low onset potentials as low as 0.1 V vs. RHE, while being highly selective to complete oxidation to CO₂. Our comprehensive characterization and in situ electrochemical ATR studies suggest that the formation of a ternary surface site ensemble around the octahedral Pt₃Ni₁Rh_x nanoparticles plays a crucial mechanistic role for this behavior.     

Halogen,hydrogen and electrostatic interactions in 2‐amino‐5‐chloro‐1,3‐benzoxazol‐3‐ium nitrate and 2‐amino‐5‐chloro‐1,3‐benzoxazol‐3‐ium perchlorate

In the title compounds, C₇H₆ClN₂O⁺·NO₃⁻ and C₇H₆ClN₂O⁺·ClO₄⁻, the ions are connected by N—H...O hydrogen bonds and halogen interactions. Additionally, in the first compound, co‐operative π–π stacking and halogen...π interactions are observed. The energies of the observed interactions range from a value typical for very weak interactions (1.80 kJ mol⁻¹) to one typical for mildly strong interactions (53.01 kJ mol⁻¹). The iminium cations exist in an equilibrium form intermediate between exo‐ and endocyclic. This study provides structural insights relevant to the biochemical activity of 2‐amino‐5‐chloro‐1,3‐benzoxazole compounds.     

Spherical silica particles decorated with graphene oxide nanosheets as a new sorbent in inorganic trace analysis

Graphene oxide (GO) is a novel material with excellent adsorptive properties. However, the very small particles of GO can cause serious problems is solid-phase extraction (SPE) such as the high pressure in SPE system and the adsorbent loss through pores of frit. These problems can be overcome by covalently binding GO nanosheets to a support. In this paper, GO was covalently bonded to spherical silica by coupling the amino groups of spherical aminosilica and the carboxyl groups of GO (GO@SiO₂). The successful immobilization of GO nanosheets on the aminosilica was confirmed by scanning electron microscopy and X-ray photoelectron spectroscopy. The spherical particle covered by GO with crumpled silk wave-like carbon sheets are an ideal sorbent for SPE of metal ions. The wrinkled structure of the coating results in large surface area and a high extractive capacity. The adsorption bath experiment shows that Cu(II) and Pb(II) can be quantitatively adsorbed at pH 5.5 with maximum adsorption capacity of 6.0 and 13.6 mg g⁻¹, respectively. Such features of GO nanosheets as softness and flexibility allow achieving excellent contact with analyzed solution in flow-rate conditions. In consequence, the metal ions can be quantitatively preconcentrated from high volume of aqueous samples with excellent flow-rate. SPE column is very stable and several adsorption–elution cycles can be performed without any loss of adsorptive properties. The GO@SiO₂ was used for analysis of various water samples by flame atomic absorption spectrometry with excellent enrichment factors (200–250) and detection limits (0.084 and 0.27 ng mL⁻¹ for Cu(II) and Pb(II), respectively).     

Garlic Powder as a Safe Environment Green Corrosion Inhibitor for Mild Steel in Acidic Media; Adsorption and Quantum Chemical Studies

The corrosion inhibition of mild steel in H3PO4 solution by garlic powder was investigated using weight loss and polarization techniques. The adsorption of garlic powder was found to obey Langmuir adsorption isotherm. Maximum inhibition efficiency was 75% at 50 °C and 250 ppm inhibitor concentration. The values of heat of adsorption were negative indicating the spontaneous adsorption process. Quantum chemical calculations were used successfully to evaluate the theoretical inhibitor efficiency. Mathematical and statistical analyses were also used to represent the corrosion rate data with high correlation coefficients. Polarization measurements showed that garlic powder was a mixed — type inhibitor.     

In situ detection of a single carotenoid crystal in a plant cell using Raman microspectroscopy

It is the first report of direct, in situ detection of carotenoids at the subcellular level by using Raman microspectroscopy. Single crystals sequestered in a carrot cell were measured using FT-Raman spectrometer equipped with a microscope and 40× objective. The observed characteristic bands centered at 1518 cm⁻¹ and 1156 cm⁻¹ proved the crystals were composed of carotenoids with β-carotene being predominant. The obtained results show the potential of Raman microspectroscopy for identification and analysis of compounds localized in cytoplasm by taking measurements directly from a single plant cell.