Polymerization Reactions in an Al(OBus)3-(COOH)2 System

Reactions in an Al(OBu^s)₃-(COOH)₂ (OA)-tetrahydrofuran (THF)/(CD₃)₂SO (DMSO-d₆) system (Al(OBu^s)₃: THF : DMSO-d₆: OA = 1 : 5 : 5 : x, x = 0.01 –3) were studied, without the addition of water and the process was monitored by NMR. When x 0.3, homogeneous solutions were obtained, whereas white precipitates formed with x 0.7. The formation of sec-butyl alcohol was evident with x 0.6, indicating that oxalate groups coordinate to aluminum to release sec-butyl alcohol. ¹³C NMR spectra of the solutions after 1 day suggest the presence of polymeric species if 0.03 x 0.6. The addition of a small amount of water resulted in the formation of a white precipitate (Al(OBu^s)₃: THF : DMSO-d₆ : OA : H₂O = 1 : 5 : 5 : 0.3 : y,y = 0.03–0.3), indicating that water, possibly formed by esterification in the Al(OBu^s)₃-OA-THF/DMSO-d₆ system, does not take a major role in the present system.     

石墨负载Pt催化剂的制备、表征及活性研究

Pt/graphite catalyst was prepared by incipient wetness impregnation using H₂PtCl₆·6H₂O as precursor. The catalyst was characterized by SEM, XRD, XPS and its degradation ability for oxalic acid was evaluated. The preparation parameters, including the reduction temperature, Pt loading and pyrolysis were studied. The optimal preparation conditions were 350 ℃ with Pt loading of 1.0%. Results show that the loading of Pt can significantly enhance catalytic activity of graphite and that Pt/graphite catalytic ozonation can effectively remove oxalic acid in aqueous solution. The BET surface area of graphite is much smaller than that of activated carbon, however, the catalytic activity of Pt/graphite towards oxalic acid degradation is higher than that of Pt/AC. The XPS results indicate that the active phase at catalyst surface is in the form of Pt⁰. Compared with that of reduction process in hydrogen, the activity of Pt/graphite catalyst decreases when it is prepared by pyrolysis in air due to the lower Pt dispersion on graphite surface.     

Zirconia Aerogels: Effect of the Use of Mono- and Dicarboxylic Acids in the Sol-Gel Process on Structural Properties

Zirconia aerogels were prepared from tetra-n-butoxy zirconium(IV) using acid catalysis with different types of mono- and dicarboxylic acids and ensuing supercritical drying of the gels either at high temperature (578 K, HT-aerogels) or by semicontinuous extraction with supercritical CO₂ at low temperature (318 K, LT-aerogels). The resulting HT- and LT-aerogels were calcined in air at 573 and 773 K, respectively, and characterized by nitrogen physisorption, X-ray diffraction, Raman spectroscopy, thermal analysis, and thermal desorption of ammonia. All HT-aerogels were mesoporous and possessed a high specific surface area between ca. 90 and 170 m²·g^-1 after calcination at 773 K. With oxalic acid the pore size distributions were either bimodal (R = 1) or unimodal R = 2), depending on the acid-to-alkoxide ratio, R. In contrast, the use of acetic and adipic acid, respectively, afforded bimodal pore size distributions. Generally, the crystalline part of the raw HT-aerogels prepared with acetic and adipic acid was made up of tetragonal ZrO₂ with traces of monoclinic zirconia, whereas with oxalic acid at higher acid-to-alkoxide ratio (R = 2) the monoclinic phase became dominant. Calcination in air at 773 K had no influence on the phase distribution and crystallite size. With LT-aerogels, the sample prepared with the largest acetic acid-to-alkoxide ratio (R = 2) afforded the highest BET surface area (ca. 90 m²·g^-1). All LT-aerogels were X-ray amorphous after extraction and calcination in air at 573 K. Crystallization resulted in the formation of tetragonal zirconia. The crystallization temperature increased with higher acetic acid-to-alkoxide ratio, whereas the crystallite size decreased.     

Thermochemical conversion of polysaccharides in concentrated alkali to glycolic acid

Degradation of starch and cellulose in alkaline solutions above 8N NaOH favored the production of glycolic acid. In 16N NaOH, starch and cellulose degraded at 240°C to produce, respectively, 46 and 43% yields of glycolic acid. At these same conditions, 24 and 12% yields of oxalic acid were also produced from starch and cellulose. Raising the amount of starch or cellulose above 10 g in 250 mL 16 N NaOH lowered the percent yields of glycolic and oxalic acids, but increased absolute yields sufficiently to consider larger polysaccharide: 16 N NaOH ratios for commercial use. Substituting KOH for NaOH lowered glycolic and oxalic acid yields, and demonstrated the effect of the alkali cation on the conversion reactions.     

Fast determination of reaction kinetic parameters with the use of microwave heating. Kinetics of decomposition of organic substances with nitric acid

A mathematical model for the kinetics of a chemical reaction under microwave irradiation in a close volume in the simplest approximation of the uniform temperature and pressure distribution in a system was proposed. The previously proposed dynamic method for determination of the activation energy of oxidation of organic substances with nitric acid was substantiated. According to this method, the activation energy is determined from the experimental exponential plot for the pressure in the nonisothermic system vs. inverse temperature of the reaction mixture. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1371–1375, June, 2005.     

Decomposition products of halonitroacetic acid derivatives

The halonitro group O₂NCHX of chloro- and bromonitroacetic acid derivatives underwent reduction to H₂NCO upon boiling. The same derivatives decomposed to oxalic acid upon long storage. Likely chemical transformation pathways are discussed.Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 151–153, January, 1992.     

The Utilization of Douglas-Fir Bark for the Production of Oxalic Acid and High Density Carbon Pellets

The production of oxalic acid by the catalytic oxidation of Douglas-fir (Psedotsuga menfiesii (Mirb) Franco) bark and subsequent pyrolysis of the residue to produce high density carbon pellets is discussed. Kinetic rate data are presented for oxalic acid production from Douglasfir bark. A maximum yield of 38 wt% oxalic acid has been obtained in 8 h at 80°C with 62.5 vol% HNO₃ and 0.5 mg V₂O₅/g of bark. Additional oxalic acid can be produced by the conversion of pyrolytic oils and tars (obtained during carbonization of the residue) to increase the total yield to 45 wt%. An economic analysis based on the current cost of oxalic acid indicates the viability of the proposed process.     

Synthesis and Properties of N,N′‐Bis(difuroxano [3,4‐b:3′,4′‐d]phenyl)oxalic Amide

N,N′‐Bis(difuroxano[3,4‐b:3′,4′‐d]phenyl)oxalic amide was synthesized via acylation, nitration, azidation, and pyrolysis‐denitrogenation from the starting materials of oxalyl chloride and 3,5‐dichloroaniline, under mild reaction conditions, with the yields of 81.0%, 82.0%, 86.0% and 81.7% respectively. The title compound and its precursors were characterized by ¹H NMR, IR, MS, and elemental analysis. The title compound has a density of 1.92 g·cm^?3 by a suspension method, a standard formation enthalpy of 979 kJ·mol^?1 calculated by Gaussian programs, a detonation velocity of 8.17 km·s^?1, and a detonation pressure of 31 GPa obtained by Kamlet Equation. The thermal decomposition reactions of the title compound at different heating rates were tested by differential scanning calorimetry (DSC). The kinetics parameters of the pyrolysis of the compound were calculated by Kissinger's method. The values of apparent activation energy (E_a) and pre‐exponential constant (A) were 226.7 kJ·mol^?1 and 10^23.17 s^?1 respectively. It was presupposed that N,N′‐bis(difuroxano[3,4‐b:3′,4′‐d]phenyl)oxalic amide would be a promising high energetic explosive with low sensitivity.     

草酸改性空气凤梨生物炭吸附甲醛的机理研究

探究草酸改性园林废弃物类生物炭对溶液中甲醛的吸附效率和固定的机理,为园林废弃物类生物炭在甲醛污染控制方面的应用提供科学依据。利用马弗炉在低氧条件下将空气凤梨原材料和草酸改性后的原材料制备成生物炭。然后利用实验室模拟法,研究不同反应时间、甲醛浓度、pH对生物炭吸附效果的影响,并分析草酸改性如何提高园林废弃物类生物炭对甲醛的吸附性能。(1)生物炭对乙酰丙酮和酚试剂两种甲醛检测方法的精度有影响,对乙酰丙酮检测法的影响较小;(2)相比于未改性生物炭,草酸改性通过酸化分解杂质能够使改性生物炭比表面积提高约17倍,孔隙体积增加195.9%;(3)草酸改性后生物炭对甲醛的吸附量为11.6 mg g^-1,比未改性生物炭提高了12.95%,并且在60 min时趋于吸附平衡的状态;(4)Boehm滴定法表明草酸改性能够显著提高制备后生物炭上的官能团(羧基51.8%,羰基13.7%和内酯基35.9%),但酚羟基(4.5%)含量增加不明显,而相关性分析证实比表面积、羧基和内酯基官能团的增加是提高生物炭吸附甲醛的主要因素。实验证明,空气凤梨制备成生物炭用于溶液中甲醛的吸附是可行的,并且草酸改性能够进一步通过官能团提高其吸附能力,这为园林废物资源化利用提供了新的思路。     

草酸配体修饰的锆取代型硅钨-氧簇合物的合成、结构和电化学性质研究

通过水热反应,成功合成了一个草酸配体修饰的四核锆取代的夹心型硅钨-氧簇合物H₁₂Na₂[Zr₄(μ₃-O)₂(μ₂-OH)₂(Ox)₂(α-SiW₁₀O₃₇)₂]·22H₂O (Ox=oxalic acid)。该夹心型硅钨-氧簇是由两个{α-SiW₁₀O₃₇}簇块通过一个{Zr₄(μ₃-O)₂(μ₂-OH)₂(Ox)₂}簇连接构成的。通过X-射线单晶衍射、IR、TG以及元素分析对该簇合物进行表征。晶体结构分析表明: 该簇合物结晶于单斜晶系,P2₁/c空间群,a=2.132 2 (6) nm, b=1.271 6 (4) nm, c=2.223 1 (7) nm, β=110.933(4)°,V=5.629 9(3) nm³,Z=2,R₁=0.061 5,wR₂=0.164 4。电化学和电催化性质研究表明标题簇合物对NO^-₂的还原有很好的电催化效果。