Decomposition of Al13 promoted by salicylic acid under acidic condition: Mechanism study by differential mass spectrometry method and DFT calculation

Decomposition of the polycation Al₁₃O₄(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) promoted by ligand is a vital subject to advance our understanding of natural and artificial occurrence and evolution of aluminum ions, especially in the case of acidic condition that dissolved Al³⁺ species can be released from the Al-bearing substances. However, the microscopic pathway of synchronous proton-promoted and ligand-promoted decomposition process for Al₁₃ is still in the status of ambiguity. Herein, we applied differential mass spectrometry method and DFT calculation to study the initial detailed process of Al₁₃ decomposition under the presence of proton and salicylic acid (H₂Sal). Mass results showed that the mononuclear Al³⁺-H₂Sal complexes dominated the resulting Al species, whereas the monodentate complex Al₁₃HSal⁶⁺ was not observed in the spectra. The difference of decomposition levels between the ligand/Al ratio 0.2 and 0.5 cases revealed that proton and ligand performed synergistic effect in initial Al₁₃ decomposition process, and the proton transfer determined the ring closure efficiency. The ring closure reaction is the prerequisite for the collapse of Al₁₃ structure and detachment of the mononuclear complex. DFT calculations reveal that hydrogen bond plays an important role in inducing the formation of chelated complex accompanying proton transfer. Attachment of protons at the bridging OH⁻ can elongate and weaken the critical bond between targeted Al³⁺ and µ₄-O^2- resulting from delocalization of electron pairs in the oxygen atom. These results demonstrate the detailed mechanism of Al₁₃ composition promoted by ligand and proton, and provide significant understanding for further application and control of Al₁₃.     

涡轮叶片NiCoCrAlYTa涂层抗高温氧化和腐蚀性能测试研究

目的保障涡轮叶片的安全可靠应用,研究NiCoCrAlYTa涂层的高温氧化和燃气热腐蚀行为。方法针对有无涂层的涡轮叶片试样,分别进行1050℃/100 h的抗氧化试验和950℃/100 h的燃气热腐蚀试验,同时分析试验后合金基体和涂层的微观形貌。结果抗氧化试验后,无涂层试样的平均氧化皮脱落量和平均氧化速率分别是带涂层试样的10倍和3倍左右,无涂层试样叶身表面可见大量氧化皮脱落形成的凹坑,带涂层试样的涂层完好,基体未见氧化特征。燃气热腐蚀试验后,无涂层试样的腐蚀速率是带涂层试样的3倍,无涂层试样叶身表面可见较多腐蚀坑,有涂层试样的涂层未被明显腐蚀。结论 NiCoCrAlYTa涂层在经过长时间高温氧化和腐蚀后仍能形成完整的Al_2O_3膜,从而起到较好的保护作用。Ta、Y等元素对Al_2O_3氧化膜的形成及质量具有促进作用。     

毛细柱气相色谱法测定天然水中痕量铍、铝、铬

介绍一个用毛细柱气相色谱法同时测定铍、铝、铬酌新方法。在pH为5.6的醋酸-醋酸钠缓冲溶液中,铍、铝、铬与三氟乙酰丙酮生成挥发性和热稳定性的金属整合物。可萃取至苯中,注射至熔融石英WCOT OV—101柱上,在140℃分离测定,用电子捕获检测器检测。铍、铝、铬的回收率分别为83—103％,88—105％,90—103％。变异系数分别为6.5％,6.5％,2.0％。可用于天然水中亚ppb级铍、铝、铬的分析。测定了海水、河口水、矿泉水、雪水等样品。     

天津市“十三五”期间PM2.5减排效果评估

为了解“十三五”期间天津市PM_2.5减排效果,基于2015～2020年不同大气污染治理措施的减排量核算结果,利用空气质量模型和高时空分辨率PM_2.5监测数据,对“十三五”期间天津市PM_2.减排效果进行分析.结果表明,2015～2020年,天津市SO₂、 NO_x、 VOCs和PM_2.5的排放量分别减少4.77×10⁴、 6.20×10⁴、 5.37×10⁴和3.53×10⁴t,其中工艺过程、散煤和电力治理对SO₂的减排贡献大,工艺过程、电力和钢铁治理对NO_x的减排贡献大,工艺过程对VOCs的减排贡献最大,工艺过程、散煤和钢铁治理对PM_2.5的减排贡献大.“十三五”期间天津市PM_2.5浓度平均值、污染天数和重污染天数明显下降,分别较2015年下降31.4%、 51.2%和60.0%;与前...     

Al改性柠条生物炭对P的吸附特性及其机制

为高效利用生物质能源,以常见农林废弃物柠条为原料,在650℃、3h条件下,采用限氧热裂解法制备生物炭,通过直接修饰法用Al改性柠条生物炭,进行批量吸附P实验.利用4种等温吸附模型（Langmuir、Freundlich模型、Temkim、D-R模型）和4种吸附动力学模型（准一级动力学、准二级动力学、Elovich模型、颗粒内扩散模型）以及pH值、添加量影响试验,探讨Al改性生物炭对P的吸附特性.同时,使用FTIR红外、元素分析、SEM和比表面积及孔径分析等技术表征了生物炭的理化性质,揭示了Al改性生物炭对P的吸附机理,并对比了多种改性生物炭对P的吸附效果.结果表明：柠条生物炭（NB）对P的吸附量很低,Al改性柠条生物炭（Al-NB）最佳改性比例为0.2：1,对P的吸附量是NB的8.35倍.Langmuir模型能够很好的描述Al-NB对P的等温吸附过程;Al-NB对P的吸附动力学符合准一级动力学模型,说明其吸附通过边界扩散完成的单层吸附.Al-NB对P的理论最大吸附量为19.97mg/g,平衡时间为24h.随着添加量的增大,Al-NB对P的吸附量不断减小,去除率逐渐增加,2.5g/L为最佳添加量;最适pH为4～10,当pH=7时,达到最大;吸附P后,溶液的pH值向中性范围倾靠,有一定缓冲作用.吸附机理包括：静电吸附作用,配体交换（羟基）,P与阴离子（NO₃^-）交换,颗粒内表面络合作用等.以期为水体富营养化治理提供科学依据.     

Ferron逐时络合比色法研究TEOS－PAC中AI的形态

以TEOS为原料,将其与AlCl_3溶液混合后再缓慢滴加Na0H溶液,合成出具有不同Si/Al比和B值的复合絮凝剂样品TEOS-PAC。用Ferron逐时络合比色法对其Al形态分布及转化特征进行了研究,并与以硅酸钠(Na_2SiO_3·9H_2O)为原料相同条件下制备的样品作了比较,初步得出了Si/Al比和β值对TEOS-PAC复合絮凝剂中Al形态的影响规律。     

高铝粉煤灰脱硅反应工艺优化及机理探讨

为探究高铝粉煤灰脱硅最佳工艺条件及了解其脱硅过程物相转化机理,通过正交试验研究了w(NaOH)(10%~30%)、灰碱比(质量比,取1∶0.3~1∶2.0)、时间(1.0~4.0 h)和温度(90~150 ℃)对脱硅效率及铝硅比(质量比)的影响. 结果表明:w(NaOH)为20%、灰碱比为1∶0.5、反应时间为2.0 h、反应温度为120 ℃是粉煤灰脱硅反应的最佳条件;在最佳条件下铝硅比由原灰的1.23升至2.02以上,脱硅效率达38.6%.反应温度、灰碱比、碱液浓度、时间对脱硅率的影响依次减弱. 通过定量X射线衍射(XRD)分析了脱硅前后物相的变化,当温度高于120 ℃时,有大量方钠石形成,并且方钠石生成量(X)与铝硅比(Y)呈显著负相关,有Y=-0.012 8X+2.03 (R2=0.930,P<0.01). 由扫描电镜(SEM)对粉煤灰脱硅前后的表观形貌变化观察可知,粉煤灰在脱硅过程中非晶态SiO₂部分溶解,从而进一步证实了方钠石的生成是影响脱硅效率的关键因素.      

超声辐射浸渍法制备Fe-Ni-Mn/Al2O3催化剂及性能研究

以Al2O3为载体,分别采用超声辐射浸渍法和普通浸渍方法制备Fe-Ni-Mn/Al2O3催化剂。采用BET、XRD和SEM对催化剂的理化性质和孔结构进行了分析,以模拟酸性绿B废水为研究对象考察催化剂的催化性能。实验结果表明,浸渍溶液pH值和焙烧温度显著影响催化剂的性能。与普通浸渍法相比,超声浸渍法制备的Fe-Ni-Mn/Al2O3催化剂对酸性绿B脱色反应表现出较高的催化活性。     

Role of dissolved humic acids in the biodegradation of a single isomer of nonylphenol by Sphingomonas sp

This study shows the important role of humic acids in the degradation of ¹⁴C and ¹³C labeled isomer of NP by Sphingomonas sp. strain TTNP3 and the detoxification of the resulting metabolites. Due to the association of NP with humic acids, its solubility in the medium was enhanced and the extent of mineralization of nonylphenol increased from 20% to above 35%. This was accompanied by the formation of significant amounts of NP residues bound to the humic acids, which also occurred via abiotic reactions of the major NP metabolite hydroquinone with the humic acids. Gel permeation chromatography showed a non-homogenous distribution of NP residues with humic acids molecules, with preference towards molecules with high-molecular-weight. Solid state ¹³C nuclear magnetic resonance spectroscopy indicated that the nonextractable residues resulted exclusively from the metabolites. The chemical shifts of the labeled carbon indicated the possible covalent binding of hydroquinone to the humic acids via ester and possibly ether bonds, and the incorporation of degradation products of hydroquinone into the humic acids. This study provided evidences for the mediatory role of humic acids in the fate of NP as a sink for bacterial degradation intermediates of this compound.