食用级大豆油极度氢化工艺探索

研究了大豆油极度氢化的速率和氢化工艺参数之间的关素,讨论了氢气压力、反应温度、催化剂浓度对大豆油极度氢化速度和选择性的影响。并得出结论:大豆油在较高的氢气压力、适中的反应温度和适量的催化剂浓度的条件下极度氢化可以得到较满意的加氢速度及较理想的产品质量;并通过研究证实,用快速熔点测定法判断极度氢化反应终点,简便易行且比较可靠,对油脂极度氢化工业生产具有指导意义。

超临界CO_2条件下大豆油极度氢化的研究

以机榨大豆油为原料,在超临界CO_2体系中,选取Pd/C作为催化剂催化极度氢化反应,通过单因素试验,确定催化剂添加量、氢气压力、反应时间、反应温度及搅拌速度的最适量。在最优条件下制备出极度氢化大豆油的碘值为2.6 gI_2/100 g,反式脂肪酸含量为0.23%(可看作零反式脂肪酸含量),VE含量186.7 mg/kg。与常规极度氢化反应相比,反应温度降低了70℃,反应时间缩短了60 min,提高了极度氢化油的质量。Pd/C催化剂可回收重复使用6次,降低了生产成本。

酶催化酯交换制备零反式脂肪酸食品专用油脂基料的性质研究

研究了以大豆油和极度氢化棕榈油为原料,采用脂肪酶Lipozyme TLIM催化酯交换反应制备的零反式脂肪酸食品专用油脂基料的性质。酶法酯交换反应条件为反应温度60℃、反应时间3 h、酶添加量4%(占油脂总质量)、大豆油与极度氢化棕榈油质量比4∶3。对比了酯交换反应前后混合油脂的热性质、固体脂肪含量、晶体形态和微观形态。结果表明:酶法酯交换反应后,产物熔融、结晶温度均降低;酯交换产物以β'晶型为主,晶体颗粒均匀、较小;当温度高于25℃后固体脂肪含量减小,产物在高于45℃时可全部融化。因此,酯交换油脂适用于制备烘焙型食品专用油脂基料。

Improvement of hydrogen embrittlement and stress corrosion cracking by annealing for Al-4.4Mg-0.6Mn alloy

With no annealing treatment, cathodic polarization trends in 5083F A1 alloy revealed concentration polarization and activation polarization. However, the annealed specimens have lower current densities at corrosion protection potential compared to the non-annealed specimen. The results of SSRTs conducted in seawater at the applied potential range of-l.8 V to -0.5 V indicated that the maximum tensile strength, elongation, and time-to-fracture had high values at applied potentials of -0.7 to -1.4 V. The maximum tensile strength, elongation, and time-to-f？acture decreased when the potential values were beyond this range in either anodic or cathodic direction. In general, the increased shear lip caused by annealing treatment indicates elongation. Time-to-fracture would likely increase with elongation. Potentials between -0.5 V to -0.6 V were found to be in the region of stress corrosion cracking. The corrosion protection zone was determined to be -0.7 V to -J,4 V because these potential ranges produced good mechanical properties. Potential less than -1.4 V produced a fractured surface with a mixture of dimples （ductile fractures） and a quasi-cleavage pattern resulting from the effects of hydrogen gas.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

Discrepant roles of adsorbed OH^* species on IrWOx for boosting alkaline hydrogen electrocatalysis

Improving the slow kinetics of alkaline hydrogen electrode reactions, involving hydrogen oxidation and evolution reactions(HOR/HER) is highly desirable for accelerating the commercialization of alkaline exchange membrane-based fuel cells(AEMFCs) and water electrolyzers(AEMWEs). However, fundamental understanding of the mechanism for HOR/HER catalysis under alkaline media is still debatable. Here we develop an amorphous tungsten oxide clusters modified iridium-tungsten nanocrystallines(Ir WOx)which exhibited by far the highest exchange current density and mass activity, about three times higher than the commercial Pt/C toward alkaline HOR/HER. Density functional theory(DFT) calculations reveal the WOxclusters act as a pivotal role to boost reversible hydrogen electrode reactions in alkaline condition but via different mechanisms, which are, hydrogen binding energy(HBE) mechanism for HOR and bifunctional mechanism for HER. This work is expected to promote our fundamental understanding about the alkaline HOR/HER catalysis and provide a new avenue for rational design of highly efficient electrocatalysts toward HOR/HER under alkaline electrolytes.

Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells

Noble metal-free and highly efficient electrocatalytic materials with hierarchically porous structures continue to be studied for the oxygen reduction reaction(ORR) in microbial fuel cells(MFCs). We report bimetal-organic framework(bi-MOF)-derived nanocubic Swiss cheese-like carbons with a novel three-dimensional hierarchically porous structure(3D Co-N-C) prepared by utilizing cetyltrimethylammonium bromide(CTAB) as a structure-directing agent to control the formation of a nanocubic skeleton, and silica spheres as a template to form a mesoporous structure. The elemental composition and chemical morphology of this material can be tuned through the Zn/Co ratio to optimize its ORR catalytic activity. The optimized 3D Co-N-C displays excellent ORR catalytic performance(half-wave potential as high as 0.754 V vs. reversible hydrogen electrode and diffusion-limiting current density of 5.576 mA cm^(-2)) in 0.01 mol L^(-1) phosphate-buffered saline(PBS electrolyte),showing it can compete with the commercial 20 wt% Pt/C catalysts. The catalytic capability and long-term durability of 3D Co-N-C as an air-filled cathode electrocatalyst in an MFC device are tested, showing that the 3D CoNC-MFC can reach a high power density of 1257 mW m^(-2) and provide a competitive voltage during a periodic feeding operation for 192 h;these values are much higher than those of the Pt/C-MFC.

Facile electrodeposition of 3D concentration-gradient Ni-Co hydroxide nanostructures on nickel foam as high performance electrodes for asymmetric supercapacitors

Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three- electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g^-1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g^-1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg^-1 at a power density of 3.0 kW·kg^-1, and excellent rate capability-energy densities of about 70.4 and 26.0 Wh·kg^-1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg^-1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g^-1 was achieved, which compares very well with the traditional doublelayer supercapacitors.

Ternary PtRuTe alloy nanofibers as an efficient and durable electrocatalyst for hydrogen oxidation reaction in alkaline media

Sluggish kinetics of anodic hydrogen oxidation reaction(HOR)in alkaline media,which arises from the two orders of magnitude lower HOR activity in alkali than that in acid media for platinum group metals,hinders the commercial implementation of anion exchange membrane fuel cells(AEMFCs).Consequently,the development of platinum-based catalysts combined with high efficiency and durability is urgently required.Herein,we report a facile route for the synthesis of ternary PtRuTe alloy nanofibers with Pt atomic ratio of only 11%via a simple galvanic replacement reaction.We optimize the adsorption strength of platinum and ruthenium towards hydrogen and hydroxyl species by regulating the electron donation from tellurium to platinum and ruthenium.Hence,the obtained trimetallic alloy catalyst exhibits an impressive kinetic current density of 30.6 mA cm^(−2)_(geo) at 50 mV and an exchange current density of 0.426 mA cm^(−2)_(metal),which shows 3.0-and 2.5-fold enhancement compared with the commercial Pt/C in alkaline electrolyte,respectively.Moreover,the catalyst also demonstrates excellent stability with merely 5%activity attenuation after 2000 potential cycles.This work offers new pathways to boost alkaline HOR by rationally designing multicomponent alloys.