二氧化硅脱除羟基的动力学研究

醇盐水解法制备的纳米二氧化硅粉体中含有大量羟基,结合差热分析,采用Doyle-Ozawa法和Kissinger法研究二氧化硅粉体脱除羟基的动力学,得到反应表观活化能为134.78kJ.mol-1;并采用Coats-Redfern法进行验证,结果为140.22 kJ.mol-1.采用SEM和XRD对样品进行检测,表明非晶态二氧化硅样品颗粒大小没有变化,晶态没有改变.     

富勒烯C72分子静电势以及Sc2@C72的理论研究

已制备出来的富勒烯都遵循分离五元环规则(IPR)。C72虽然满足五元环分离规则具有D6d对称结构,然而迄今为止还没有实现其宏观量的合成,人们称之为“遗失的碳笼”。但人们合成出了内掺金属M@C72(M=Ca,La等),证实了C72的存在[1-4]。最近用两步高性能液体色谱方法又成功地分离出La2     

循环冲击载荷作用下页岩动力学响应及能量耗散特征

采用$varnothing $50 mm分离式霍普金森杆(split Hopkinson pressure bar,SHPB)实验系统开展页岩循环冲击实验,研究不同循环冲击载荷作用下页岩动力学响应及损伤演化特征,同时揭示了控制入射总能量不变条件下,不同气压梯度循环冲击页岩能量演化规律。随着冲击气压升高,试样破裂所需的冲击次数呈线性减少,峰值应力随循环冲击次数的增加先升高后降低,极限应变先减小后增大,试样在循环冲击下表现出先压密后损伤的力学机制。基于Weibull分布的统计损伤模型表明,升高循环冲击气压,试样损伤破坏形式由缓慢劣化逐渐转变为骤然破坏。入射总能量恒定的情况下,通过控制循环入射能量梯度能够产生不同的损伤效果,降压冲击和升压冲击下的能量吸收比均大于恒压冲击下的,且气压梯度的绝对值与能量吸收比呈现正相关性。

     

氧气分子参与的乙烯基单体自由基聚合

尽管被公认在自由基聚合中往往起着缓聚、阻聚或链转移的作用,越来越多的结果表明,在某些情况下,如高温、高压,或当某些催化剂存在时,氧气分子(O2)可以参与甚至加速乙烯基单体的自由基聚合。本文综述了上世纪90年代以来,O2参与的乙烯基单体的热/光诱导自由基聚合、化学引发自由基聚合、氧载体催化自由基聚合以及可逆加成-断裂链转移自由基聚合。以上结果表明,在上述情况下,O2,作为一个普通不饱和单体,可以与苯乙烯、甲基丙烯酸甲酯等乙烯基单体形成交替共聚物(聚过氧化物),而此类聚过氧化物均可裂解为自由基。     

PANI/TiO2/SiW12复合光催化剂的制备、表征及其光催化性能

以(NH4)2S2O8为氧化剂,通过化学氧化法在TiO2颗粒表面包覆聚苯胺(PANI)薄膜制得PANI/TiO2。通过静电自组装方法将SiW412-键合在PANI/TiO2表面,制备了一种新型的复合光催化剂PANI/TiO2/SiW12(1),用UV-Vis,FT-IR,XRD和SEM等对1的结构和光吸收性能进行了表征。以刚果红为目标降解物,研究了1在太阳光下的光催化性能。结果表明,PANI的敏化作用拓宽了TiO2的光响应范围,提高了光能的利用率,增强了复合材料的光催化活性。1的光催化活性明显高于TiO2和PANI/TiO2,90 min降解率达83.94%。     

Multiwalled Carbon Nanotubes Modified with Silylated-salicylaldimine Co(II) and Pd(II) Complexes as Precatalysts in Ethylene Oligomerization

MWCNTs-Co(II) and Pd(II) were prepared through grafting silylated-salicylaldimine Pd(II) and Co(II) on multiwalled carbon nanotubes(MWCNTs) for ethylene oligomerization. The structures of the two MWCNTs-supported catalysts were characterized by means of scanning electron microscopy(SEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, thermogravimetric analyses(TGA) and nitrogen adsorption and desorption. And the influence of the supported pattern on the catalytic properties for ethylene oligomerization was investigated. The results revealed that the silylated-salicylaldimine complexes were grafted on the inner and outer surfaces of the carbon nanotubes and the pore size and BET surface area of MWCNTs decreased. Compared with the homogeneous catalysts, the two MWCNTs-supported catalysts had higher selectivity for hexene and 1-hexene in the presence of diethylaluminum chloride(DEAC) with a small molecule size due to confinement effect. MWCNTs-Pd exhi-bited higher activity and higher selectivity for C₈⁺ olefin compared to MWCNTs-Co due to electronic factors. The catalytic activities of MWCNTs-Pd and MWCNTs-Co decreased from 24.18×10⁵g·(mol Pd·h)^–1 and 20.57×10⁵g·(mol Co·h)^–1 to 19.79×10⁵g·(mol Pd·h)^–1 and 13.14×10⁵g·(mol Co·h)^–1 after the third recycle reaction, respectively.     

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Zeolite imidazole frameworks 8(ZIF-8) and modified ones after pyrolysis are highly promising toward oxygen reduction reaction(ORR). Especially, the compositional modification of ZIF-8 is crucial to the enhancement of ORR performance, yet limited to the substitution of skeletal Zn(II) with other cations or simple physical adsorption of cations. Herein, we report the decoration of ZIF-8 with ORR active hemin(FeP) and Co(III) protoporphyrin(CoP) via the coordination between the peripheral carboxylic group of FeP and CoP with skeletal Zn(II). This allows well control over the quantity of loaded FeP and CoP, critical to the synthesis of advanced electrocatalysts. Subsequent pyrolysis of FeP and CoP co-decorated ZIF-8 leads to highly active ORR electrocatalysts with a half-wave potential(E_1/2) of 0. 913 V(vs. RHE) in 0.1 mol/L KOH aq. and an E_1/2 of 0.803 V(vs. RHE) in 0.1 mol/L HClO₄ aq. Moreover, our electrocatalyst shows much more improved and comparable durability in alkaline and acidic media, respectively, during 3000 cycles of cyclic voltammetry(CV) scanning relative to commercial Pt/C.     

Regulating Phase Junction and Oxygen Vacancies of TiO2 Nanoarrays for Boosted Photoelectrochemical Water Oxidation

In this study, we have provided a facile solution to synthesize well-aligned titanium dioxide nanorods by using hydrothermal reaction. By calcining the materials under different atmospheres and temperatures, a batch of titanium dioxides with excellent oxygen evolution reaction(OER) catalytic efficiency were obtained. This new structured TiO₂ photoanode material yields a high photocurrent density of 5.69 mA/cm² at 1.23 V vs. reversible hydrogen electrode(RHE) under simulated solar light(100 mW/cm²). Surface photovoltage techniques and other measurements were carried out to confirm that the enhanced photoelectrochemical performances were attributed to the synergistic effect of the phase junction and a certain content of surface states, which accelerate the separation and transmission of the photogenerated charges. This material with phase junction and surface states promises a potential application in the field of photoelectric catalysis under solar light.     

一步法高通量可控制备生物相容水/水微囊及其响应释放

生物相容水/水微囊在药物递送、 医学治疗等领域具有重要应用. 本文通过设计同轴微流控器件, 结合数值模拟优化和流动阻力分析, 实现一步法高通量可控制备大小均匀、 尺寸可控、 壁厚可调、 生物相容的水/水微囊. 采用实验研究和数值模拟相结合的方式, 研究了微流控器件结构、 内相流速、 外相流速、 外相/空气界面张力、 内相/外相界面张力、 内相黏度和外相黏度等参数对水/水微囊直径和壁厚的调控规律. 通过微通道流动阻力分析, 设计多通道平行放大微流控器件, 实现尺寸均匀可控水/水微囊的高通量制备. 验证了生物相容水/水微囊作为活性物质的理想载体, 可以通过改变pH或溶解囊壁释放载体, 进而实现活性物质的pH响应释放, 为其实际应用奠定了基础.     

基础理论纵贯化学学科:吉林大学“统计力学与分子模拟”课程建设*

化学的基础理论的演进不断重塑着化学学科。传统的教学体系所依据的理论范式落后于现代化学理论的发展。吉林大学化学学院面向本科学生开设了“统计力学与分子模拟”课程。针对吉林大学本科学生的特点,精心安排了教学内容,通盘考虑知识体系的衔接,优化了教学方法。同时,淬炼了课程中的思政元素,从而在思想、道德、知识等3个方面进一步提升学生的综合素质。